Multi-functional material having photo-catalytic function and production method therefor

Multifunctional material which has a specification photocatalyst function, and a manufacturing method for the same Technical field

It is To demonstrate about functions, such as this invention, a deodorization function, an antibacterial function, a sterilization function, and an antifouling function. It is related with Multifunctional material and its manufacturing method. Background art

receiving organic compounds, such as a bad smell ingredient, by irradiating with the former to ultraviolet rays -- acid base -- adsorption or desorption of a molecule is made to cause -- decomposition (oxidization) the function to promote -- To demonstrate considering it as Substance -- Ti 0₂V₂0₅Z_nO, W0₃etc is known -- especially -- crystal T i0 of a Anatase type [ type ]₂Since the effect as a photocatalyst is high, particles are from the former. It is Light touch to the surfaces, such as wall material, a tile, glass (mirror), a circular filtration apparatus, or sanitary chinaware. The proposal which forms Medium layer is made.

as how to form the above-mentioned photocatalyst layer -- a plastic, ceramics, and resin etc. -- the substrate surface -- the C V D method, the sputtering method, electron beam evaporation method, etc. The direct T i 0₂The method of forming the photocatalyst layer which consists of particles etc. is known.

However, the C V D method, the sputtering method, electron beam evaporation method, etc. are used. In a To case, in equipment, since the yield is also bad again, a manufacturing cost is highly to large-scale. It becomes.

It is Mixed to a binder about photocatalyst particles as other methods of forming a photocatalyst layer. Kneading is carried out and it applies to the substrate surface with Splay , a coating method, etc., Dice How to heat-treat after carrying out an immersion application with A and a coating method (Provisional Publication No. 5 -- 2 0 1 7 4 No. 7 gazette) It is known.

However, T iO₂Photocatalyst particles, such as particles, are To demonstrates about the effect as a photocatalyst. Photocatalyst particles are [ that To is irradiated with ultraviolet rays at photocatalyst particles, and ] bad smell gases etc. Although it is required to contact the quality of a decomposition subject, Provisional Publication No. 5 -- 2 0 1 7 4 If photocatalyst particles were kneaded to the binder like No. 7 gazette and being applied to the substrate, many photocatalyst particles are buried into a binder layer -- ultraviolet rays will not arrive or bad smell gas etc. will be contacted -- exhibit sufficient catalyst function it is -- .

It is real extraction of a square root 5 as other methods of forming a photocatalyst layer. -- 7 3 9 In No. 4 gazette The alkoxide process indicated is known. a this method and glass board material top -- Chi tongue Alkoxide is applied -- after [ one ] dryness 0 it is calcinating by 0 °C -- photocatalyst layer it forms -- irradiating this photocatalyst layer with ultraviolet rays -- part of an underwater organic matter A solution is carried out.

It excels in the above-mentioned alkoxide process and the point which can form a thin film at low temperature comparatively. Bookmark, it was called pyrex glass and silica glass as a substrate -- 5 [ like ] 0 Power in which it is effective when the substrate which is hard to soften to a 0 °C grade is used as materials for example, -- the case where the low material of the melting points, such as soda glass, is used as a substrate -- thin film it is the temperature to form, *-ization of a substrate already starts, and the formed photocatalyst thin film is buried into a substrate -- therefore -- light does not reach a photocatalyst layer -- it is exertion about a photocatalyst function It will come and will produce the fault that there is nothing.

Provisional Publication No. 1--2 8 8 3 2 With No. 1 gazette, it is T i O.₂It is nature material of textiles about sol. Cerami It Splay to Cucka and is 4. 0 0*7 0 S n0 after heat-treating by 0 °C₂Sol is sprayed and it is 4. 0 0*7 0 It is oxidization of aldehyde by heat-treating by 0 °C. He is trying to form the photocatalyst tunic which can raise decomposition.

Provisional-Publication-No. 11 -- 2 8 8 3 2 if it is in the method indicated by No. 1 gazette -- T i 0₂More Active low S n0₂It will be alike and all the surfaces of a tunic will be covered. When it is going to raise film strength, it is easy to generate a crack. That is, it is tile 1 as shown in Drawing 1 (a). 0 It is Ti O to the surface of 0.₂particles 1 0 applying the sol containing 1 -- it is heat treatment about and this (sintering) if it carries out -- The 1 figure -- it is shown in (b) -- as -- crack 1 0 2 occurs. It is T i0 as it is shown in The 2 figure (a), if the phase transition to this cause and a rutile type causes volume contraction (density becomes high) and also it is before sintering.₂Particles 1 0 The interval between one is L. what came out and existed -- a rutile type -- after sintering -- The 2 figure -- (b) -- To indicate -- like -- the volume diffusion to the other party -- the interval between particles -- 1^ (L!) < L₀It is short. It is considered crack Chikao To disturb as the result. on the other hand -- Japanese Patent Publication No. 41 -- 4 6 6 0 No. 9 gazette It is contained in the bad smell in vehicle indoor air. They are decomposition or the method of carrying out property modification and purifying a vehicle indoor bad smell about a bad smell substance, Half-Guiding If the solid photocatalyst of the semiconductor which supported metal or a metal oxide on the body is irradiated The vehicle indoor air which should be purified to the both photocatalysts is contacted, Inside of the air It is [ decomposition or ] Special about carrying out property modification by a photochemical reaction in the bad smell substance contained in a bad smell. It is indicated about the purification method of the vehicle indoor bad smell considered as the mark.

It is however, like for example, the inside of sewage, or an outer wall for the substrate which applied the photocatalyst to the substrate surface. If it uses in an environment, The polymers contained in the inside of the atmosphere, or underwater, dust, fungi, etc. It is light because of adhesion of the dirt by the kind of dirt that Ri and dirt adhere easily. A catalyst function may fall.

As a measure against a fall of the photocatalyst function by the dirt adhesion in the former, it is Japanese Patent Publication No. 6. -- 7 9 0 There is a No. 5 gazette. Japanese Patent Publication No. 6 -- 7 9 0 In No. 5 gazette, light which consists of semiconductors From a catalyst bed, the ultraviolet-rays light and heating element which were countered and provided in it, and a fan the whole photocatalyst layer is heated one by one -- as It is indicated about the deodorization apparatus by the photocatalyst which a photocatalyst layer, a heating element or a photocatalyst layer, and a heating element move. Dirt according to polymers, dust, etc. by heating to Am and near 4 O CTC It removes and is aiming at reproduction of the photocatalyst layer.

carrying out -- power and power [ carry out ] , -- Establishment indoors attached in the method according to reproduction of this photocatalyst It is actually difficult to perform this about the member used in detail. therefore, it becomes dirty in a photocatalyst layer, and after carrying out power adhesion, it does not remove -- becoming dirty in a photocatalyst layer rather it is hard to adhere -- or adhesion of dirt -- photocatalyst function power -- < -- it does not fall -- as -- To do -- rather than -- fundamental solution is desired.

Japanese Patent Publication No. 6 - 7 9 0 If it sets in No. 6 gazette, it is light with strong ultraviolet-rays intensity to a photocatalyst. The method of removing the bad smell in Home office is indicated by glaring. It is. However, at the thing which has strong ultraviolet-rays intensity and which carries out light irradiation, it is the structure of a photocatalyst. The decomposition rates of a bad smell differ. moreover -- since the substrate is porous in the above-mentioned example of precedence although mechanical strength sufficient by methods, such as being impregnated, is obtained -- a substrate -- a glazing tile -- comparatively -- Mechanical strength sufficient in the case of the material which is not porous as for the ceramics of the quality of precise, etc. obtains. , -- Re -- there is nothing. moreover -- T i O 2 -- a you 1Ze type and Burukai Crystal from which a A type and a rutile type differ there is type -- about optical activity, the Anatase type is excellent -- case where they are other crystallized types To -- optical activity is not so large. carrying out -- power -- it carries out -- rutile type T i 0₂It is a magazine that optical activity improves by coming out, and making metal, such as , p t, and Ag, support even if it is. "surface" 1 9 8 7 and V 0 1 2 The power reported to 5, a bad smell extraction ratio, precise nature, and adhesion It is not enough in respect of a sex. They are these if Ag and AgO are used especially as an addition metal. Since it is black, it is unsuitable for a tile or building materials.

the titanium oxide sol produced by hydrothermal method or a sulfuric acid method -- ultrafine particle , -- it is easy to condense to a sake. When a condensation thing is applied to the substrate surface, they are gloss nonuniformity and Kula. It becomes a cause which produces A. in order [ therefore, ] to prevent condensation conventionally -- Tri the method of making organic dispersing agents, such as evening Nord amine, adhering to the titanium oxide sol surface -- , -- It has been .

However, it is With to the titanium oxide sol surface about organic dispersing agents, such as Triethanolamine. They are heat-resistant low of a resin base material etc., and a basis about the titanium oxide sol single-distributed by the method of making it worn. If it applies to material and calcination fixation is carried out by less than 3 O CTC, active point of titanium oxide sol in order to fix an organic dispersing agent firmly and not to fully carry out evaporation decomposition at a calcination process, the member obtained by making such does not have sufficient photocatalyst operation -- deodorization nature and antibacterial properties -- Sufficient a part -- it is not .

Provisional Publication No. 5 -- 2 5 3 5 4 No. 4 gazette -- you -- 1 Ze type titanium oxide -- Ba it kneads to Inge 1 -- the method of applying this to the substrate surface and heat-treating it is indicated It is. Tabular member from which this method constitutes the wall surface, floor, or ceiling surface of habitation space One layer of binders are formed in the surface, the surface of this binder layer -- announcer evening 1 Ze type acid 0 (more than TC 9 0 O) That part exposes the photocatalyst fine powder which makes-izing titanium a subject from one layer of binders. it sprays like and makes it adhere -- ranking next -- 3^eIt heats in the range of less than C. It cools and makes a binder layer solidify, after carrying out and making a binder layer fuse. It is made like.

However, with this method, it is 3. 0 More than 0 °C is 9. 0 It will be Depart if it heat-treats by less than 0 °C. It is 3 although Odor is good. 0 The good deodorization characteristic is not acquired at the low temperature of less than 0 °C. it carried out To -- light with the good deodorization characteristic excellent in substrates, such as a plastic without heat resistance, etc. It was difficult to add catalyst activity. as the reason -- a substrate -- photocatalyst particles in order to apply uniformly -- a previous process -- Photocatalytic fine particles -- the inside of suspension -- single distribution it is necessary to carry out -- therefore, the dispersing agent of an organic system is added -- that much -- powder medicine 3 0 it does not fully decompose and evaporate by less than 0 °C -- active Sai on photocatalyst particles A It thinks because it remains so that it may cover. Therefore, the present invention is [ exposing a photocatalyst layer from a substrate, and ] 10 about a photocatalyst effect. While being able to demonstrate to a part, the multifunctional material excellent in maintenance of the photocatalyst layer by a substrate is provided. It aims at carrying out.

it was called the present invention, glass, a tile, metal, and a plastic -- comparatively precise are . It aims at forming ToL and a photocatalyst layer for exfoliating on a substrate.

(The substrate of the present invention and a low melting point, for example, soda which it is comparatively cheap and is easy to process it, It aims at forming a photocatalyst layer on glass etc.)

functional fall which moreover makes dirt a cause that the present invention and dirt do not adhere easily it has the antibacterial properties or deodorization nature which can be prevented -- the multifunctional material excellent in mechanical strength -- Offer It aims at offering.

the present invention and you -- 1 Ze type T i 0₂It aims at providing the multifunctional material excellent in peel strength, even if it is the photocatalyst layer made into the subject.

The present invention and rutile type T i0₂The photocatalyst activity of the photocatalyst layer made into the subject is improved. It aims at carrying out.

The present invention and rutile type T i0₂The photocatalyst layer made into the subject is made to support A g. They are eyes about decolorizing a photocatalyst layer and improving appearance, raising photocatalyst activity. -like is used.

The present invention is 3. 0 O^eIt has a photocatalyst function also with good heat treatment of the low temperature of less than C. It aims at providing Multifunctional material. The indication of an invention

Ceramics, such as multifunctional material concerning the present invention, a tile, sanitary chinaware, and glass, Direct or a binder layer is passed to the surface of substrates, such as resin, metal, and wood, and it is a photocatalyst layer. It forms, The crevice formed between the kind of photocatalyst particles which constitute especially a photocatalyst layer, diameter of a particle, and photocatalyst particles, the particles with which relation between the rate of a stoma, a binder layer, and a photocatalyst layer and the gap between photocatalyst particles are filled up -- further -- a photocatalyst particle surface -- fixation -- it devises about To be metal particles etc. -- these, Light of photocatalyst layers, such as deodorization The effect as a catalyst was made into the multifunctional material excellent also in antibacterial Wear resistance from the first. It is a thing. Brief explanation of the drawings

(a) of Drawing 1 is conventional T iO.₂The figure showing the state before sintering of sol and (b) are Les. Figure showing the state after the Chill type sintering.

(a) of Drawing 2 is conventional T iO.₂The figure showing the state before sintering of particles and (b) are glow. Figure showing the state after Connection.

photocatalyst layer among the multifunctional material which has Drawing 3 and a photocatalyst function concerning this invention the photocatalyst particles to constitute -- Mutually -- joining together with potential energy Figure showing typically the state where Configuration is carried out.

The photocatalyst particles which constitute a photocatalyst layer among Drawing 4 and the multifunctional material are Solid mutually. Figure showing typically the state where it has joined together by phase sintering.

between the photocatalyst particles which constitute a photocatalyst layer among Drawing 5 and the multifunctional material -- formation -- Figure showing typically the state where the To be gap is filled up with small particles.

Metal particles fix Drawing 6 to the surface of the photocatalyst particles of the multifunctional material shown in Drawing 3. Figure showing typically the state where it has turned.

Metal particles fix Drawing 7 to the surface of the photocatalyst particles of the multifunctional material shown in Drawing 4. Figure showing typically the state where it has turned.

Metal particles fix Drawing 8 to the surface of the photocatalyst particles of the multifunctional material shown in Drawing 5. Figure showing typically the state where it has turned.

a photocatalyst layer passes a binder layer among Drawing 9 and the multifunctional material -- it is junction to a substrate it is carried out -- the photocatalyst particles which constitute a photocatalyst layer -- mutual -- potential energy -- Connection Figure showing typically the state where it has united.

The 1st A photocatalyst layer passes a binder layer among 0 figures and the multifunctional material, and it is Contact to a substrate. It was united and the photocatalyst particles which constitute a photocatalyst layer have combined with each other by solid phase sintering. Figure showing a state typically.

The 1st A photocatalyst layer passes a binder layer among 1 figure and the multifunctional material, and it is Contact to a substrate. State where the gap which is put together and formed among photocatalyst particles is filled up with small particles Figure shown typically.

The 1st In 2 figures, metal particles are Solid to the surface of the photocatalyst particles of the multifunctional material shown in Drawing 9. Figure showing typically the state where it is law-ized.

The 1st 3 figures are the 1st. Metal particles on the surface of the photocatalyst particles of the multifunctional material shown in 0 figure Figure showing typically the state where it is fixed.

The 1st 4 figures are the 1st. Metal particles on the surface of the photocatalyst particles of the multifunctional material shown in 1 figure Figure showing typically the state where it is fixed.

The 1st The manufacturing method of the multifunctional material which has a photocatalyst function concerning 5 figures and the present invention is explained. Figure carried out.

The 1st (a) of 6 figure and (b) are T i0.₂The enlarged drawing between particles.

The 1st (a) of 7 figure * (c) is T i 0.₂The figure explaining the mechanism of sintering of particles. The 1st Graph 8 figures indicate the test result about antigenecity study to be.

The 1st Graph which compared the test result about the amount of C u support when 9 figures cannot enter with the case where a drying process is put in before B L B lamp radiation.

The 2nd Graph 0 figures indicate the relation between the amount of C u support, and the amount of C u applications to be.

The 2nd 1 figure is a figure showing the manufacturing process of another example.

The 2nd Graph 2 figures indicate the test result about antigenecity study to be.

The 2nd Graph which compared the test result about the amount of C u support when 3 figures cannot enter with the case where a drying process is put in before B L B lamp radiation.

The 2nd Graph 4 figures indicate the relation between the amount of C u support, and the amount of C u applications to be.

The 2nd Graph 5 figures indicate the relation between the amount of A g support, and the bacillus probability of survival to be.

The 2nd 6 figures are E P M A (electron beam micro analyzer 1) about the direction of a section of multifunctional material. Key map of a basic profile when it observes.

The 2nd 7 figures are E P MA (electron beam micro analyzer) about the direction of a section of multifunctional material. Key map of a basic profile when it observes. Drawing 28 is Ti0.₂Graph which shows the relation between combination and film strength of SnO 2, and optical activity Graph Drawing 29 indicates heat treatment temperature and the relation of optical activity to be.

Drawing 30 is a figure explaining the activity measurement method of the photocatalyst thin film.

Drawing 31 is a figure explaining the activity measurement method of the photocatalyst thin film.

Drawing 32 is a figure explaining the activity measurement method of the photocatalyst thin film.

The graph Drawing 33 indicates the relation between ultraviolet exposure time and the amount of change of p H to be.

Drawing 34 R₃. When The graph which shows a relation with the amount of change of pH.

The graph Drawing 35 indicates the relation between the rate of a stoma, deodorization nature (Rao), and abrasion resistance to be. The 36 figures are film thickness and deodorization nature. (R)₃.) -- graph which shows a relation with .

Drawings 37 are film thickness and deodorization nature. (R)₃₀And the graph which shows a relation with fissility-proof. Drawing 38 is SnO.₂The amount of addition, and deodorization nature (R)₃.) -- A which shows the relation between and abrasion resistance Rough.

Drawing 39 is SnO.₂The graph which shows the relation between the amount of addition, and the difficulty of attaching of dirt. Drawing 40 S etatheta₂The amount of addition, and T i 0₂Graph which shows a relation with the rate of an open pore on the surface of a layer Drawing 41 S etatheta₂The amount of addition, and T i 0₂Graph o which shows a relation with the open pore width on the surface of a layer

Drawing 42 is SnO.₂The amount of addition, and deodorization nature R₃. (L) And a relation with fissility-proof is shown. Graph. t

Drawings 43 are a rate of a stoma, and deodorization nature (R).₃₀(L) And Grad who shows a relation with fissility-proof Off.

The graph Drawing 44 indicates the relation between the number of times of Co 1 Tyng, and the difficulty of attaching of dirt to be. The graph which shows the relation of the number of times of coating and abrasion resistance. [ figure / The 45 ]

Drawings 46 are the number of times of coating, and Ti0.₂A which shows a relation with the rate of an open pore on the surface of a layer Rough.

Drawing 47 irradiates with ultraviolet rays and is a part preferentially about the thermosetting resin on photocatalyst particles. Figure showing a solution and the state of making it evaporating and exposing intermediation particles in the open air.

Drawing 48 is The 47 figure and the same figure showing another example.

Drawing 49 is The 47 figure and the same figure showing another example. The 5th 0 figures are figures showing the state where the crevice between photocatalyst particles was filled up with small particles. The 5th 1 figure is rutile type T i 0.₂Plock which shows the manufacturing process of the used multifunctional material Figure.

The 5th C u solution concentration and photoactive, when 2 figures dry C u solution and carry out optical reduction Graph which shows a relation.

The 5th C u solution concentration and light when 3 figures carry out optical reduction without drying C u solution Graph which shows a relation with activity.

The 5th 4 figures are rutile type T i O.₂The C u solution concentration and bad smell extraction ratio R at the time of setting to C u metal supported to a thin film₃. Graph which shows a relation (reduction of metal Iron was performed after making metal salt solution dry)

the 5th 5 figures use a substrate as a wall tile -- rutile type T i 0₂Graph which shows the relation between the C u solution concentration at the time of setting to C u metal supported to a thin film, and bad smell extraction ratio R 30 (reduction of metal Iron was performed after making metal salt solution dry)

The 5th 6 figures are rutile type T i 0.₂Calcination temperature and C u fixation for forming a thin film Next bad smell extraction ratio R₃. The graph which Show(ed).

The 5th Graph 7 figures indicate the relation between the solution concentration of A g and C u, and color difference to be.

The 5th 8 figures are a rate of a stoma, and R.₃. And the graph which shows a relation with abrasion resistance.

The 5th Graph 9 figures indicate the relation between the copper amount of support, and the bacillus probability of survival to be.

The 6th Graph 0 figures indicate the relation between the copper amount of applications, and the copper amount of support to be.

The 6th Graph 1 figure indicates the relation between the silver amount of support, and the bacillus probability of survival to be.

The 6th Graph 2 figures indicate the relation between the silver amount of support, and color difference to be.

The 6th Graph which shows the effect of decolorization processing according [ 3 figures ] to K I solution.

the 6th p H of K I solution before and after decolorization processing according [ 4 figures ] to K I solution -- strange -izing and bad smell extraction ratio R₃. The graph which shows a relation with Change.

The 6th Graph with which 5 figures compared the antibacterial action

The 6th Graph which shows abrasion resistance [ as opposed to the oxidization Tin weight ratio in a thin film in 6 figures ]. The 6 Graph 7 figures indicate the optical activity to turning Weight ratio in a thin film to be.

The 6th 8 figures are Show about the abrasion resistance to the oxidization Tin weight ratio in the thin film as a comparative example. To graph The 6th 9 figures show the optical activity to the oxidization Tin weight ratio in the thin film as a comparative example. Graph.

The 7th Graph 0 figures indicate the relation between the silver amount of support, and the bacillus probability of survival to be. The best form for inventing

o which explains this according to an attached drawing in order to describe the present invention in detail

Drawing 3 thru/or The 1 Structure of the multifunctional material which has a photocatalyst function which requires 4 figures for the present invention it divides for every type -- multifunctional material which has a photocatalyst function concerning the present invention It belongs to one of structures.

photocatalyst layer 2 which has a photocatalyst function is directly provided in the surface of the multifunctional material shown in Drawing 3, and substrate 1 -- photocatalyst particles 3 with this detailed photocatalyst layer 2 -- mutual -- surface Enel it joins together with potential energy, such as the Gyi curved surface energy, -- thing composition is carried out To.

photocatalyst layer 2 which has a photocatalyst function is directly provided in the surface of the multifunctional material shown in Drawing 4, and substrate 1 -- This with which photocatalyst particles 3 combine this photocatalyst layer 2 by solid phase sintering It is constituted.

Photocatalyst layer 2 which has a photocatalyst function is directly provided in the surface of the multifunctional material shown in Drawing 5, and substrate 1, while being formed among photocatalyst particles 3 which constitute this photocatalyst layer 2 spare time is filled up with particles 4 smaller than the gap concerned -- passing this small particle 4 It comprises that both photocatalyst particle 3 are combined.

it sets to a figure -- the structure which filled up even the internal gap with particles 4 is shown particles 4 -- if the gap of surface photocatalyst particles 3 is filled up at least -- right -- it is -- . That is, since it is thought that combination of the outermost surface is important in order that the mechanical strength of a photocatalyst layer and transfer of external force may decline inside, they are particulates only to the gap of surface photocatalyst particles. It may be filled up. However, internal photocatalyst particles are potential energy at this time. In order to obtain sufficient intensity of a photocatalyst layer to join together, the average particle diameter of photocatalyst particles is desirable 0.0 power.

photocatalyst layer 2 directly formed in the surface of the multifunctional material shown in Drawing 6, and substrate 1 -- style photocatalyst particles 3 which carry out Formation are mutually combined with potential energy -- further -- light the surface of catalyst particles 3 -- Ag, Cu, and C u₂Electronic capture particles 5 of the 0th grade are fixed. It is.

photocatalyst layer 2 directly formed in the surface of the multifunctional material shown in Drawing 7, and substrate 1 -- style photocatalyst particles 3 which carry out Formation are mutually combined by solid phase sintering -- metal particles 5, such as A g and P t, are further fixed by the surface of photocatalyst particles 3.

Photocatalyst layer 2 which has a photocatalyst function is directly provided in the surface of the multifunctional material shown in Drawing 8, and substrate 1, While being formed among photocatalyst particles 3 which constitute this photocatalyst layer 2 At spare time, it fills up with particles 4 smaller than the gap concerned -- passing this small particle 4 both photocatalyst particle 3 are combined -- further -- the surface of photocatalyst particles 3 -- gold, such as Ag and P t Genus particle 5 is fixed.

passing binder layer 6 to the surface of the multifunctional material shown in Drawing 9, and substrate 1 -- photocatalyst machine photocatalyst layer 2 which has ability is provided -- this photocatalyst layer 2 -- a layer part -- the exterior -- Expose, a lower layer part is laid under the binder layer 6 -- photocatalyst whose layer part is detailed again comprising that particles 3 combine with MutuallyL with potential energy -- L and To. the 1st the multifunctional material shown in 0 figure -- passing binder layer 6 similarly -- photocatalyst layer 2 -- Establishment it is kicked -- as for the layer part of this photocatalyst layer 2, photocatalyst particles 3 are combination by solid phase sintering mutually It comprises carrying out.

The 1st Photocatalyst layer 2 is provided on substrate 1 via the multifunctional material shown in 1 figure, and binder layer 6, smaller in the gap formed among photocatalyst particles 3 which constitute this photocatalyst layer 2 than and the gap concerned -- particle 4 power restoration is carried out -- passing this small particle 4 -- Light touch Both intermediation particle 3 are combined.

the 1st passing binder layer 6 to the surface of the multifunctional material shown in 2 figure, and substrate 1 -- photocatalyst layer 2 is formed -- photocatalyst particles 3 which constitute this photocatalyst layer 2 -- mutual -- Poten it is combined with the Shal energy -- further -- the surface of photocatalyst particles 3 -- AgC u and C u₂Electronic capture particles 5 of the 0th grade are fixed.

the 1st passing binder layer 6 to the surface of the multifunctional material shown in 3 figure, and substrate 1 -- photocatalyst layer 2 is formed -- photocatalyst particles 3 which constitute this photocatalyst layer 2 -- mutual -- solid phase glow it is combined in Connection -- further -- the surface of photocatalyst particles 3 -- Ag, Cu, and C u₂Electron capture of the 0th grade Trapped particles 5 is fixed.

The 1st Photocatalyst layer 2 is provided on substrate 1 via the multifunctional material shown in 4 figure, and binder layer 6, the gap formed among photocatalyst particles 3 which constitute photocatalyst layer 2 is filled up with particles 4 smaller than the gap concerned -- passing this small particle 4 -- photocatalyst grain both child 3 is combined -- metal particles 5, such as Ag and P t, are further fixed by the surface of photocatalyst particles 3.

it sets above -- as substrate 1 -- Ceramics, such as a tile, sanitary chinaware, and glass Any, such as The, resin, metal, wood, or its compound thing, may be sufficient.

Photocatalyst functions, such as an antibacterial function and a deodorization function, are exhibited in photocatalyst particles 3. They are the semiconductor particles which have sufficient band and A gap for that. Photocatalyst particles An electric shock is received by impressing the voltage more than predetermined as a reason for having antibacterial properties. The opinion of carrying out death is also a certain power. Active which generally arises at the time of that it is the same as that of a deodorization function, and light irradiation It thinks for sex oxygen. in order to generate active oxygen -- intermediary of a semiconductor when 1 of a Guiding belt expresses with a band' model, it is up from hydrogen generating potential -- and -- It requires that there is a upper end of a valence band below from oxygen generating potential. It is Full about this condition. In the semiconductor to do, it is T i0.₂S rT i0₃ZnO, S i C, gallium phosphide, Cd S, Cd S e, MoS₃There is etc. If it microatomizes, the position of a conducting zone will be moved up. Since it carries out, it is 1* : It is S n0 if it is the particulates about L 0 n m.₂W0₃F e₂0₃B i₂0₃Etc active oxygen can be generated. among these, you since it is chemically stable and cheaply active high particulates can be obtained -- 1 Ze type T i 0₂But -- especially, it is desirable.

moreover -- with electronic capture particles, the above-mentioned photocatalyst is irradiated and an electron and an electron hole generate it supplements with an electron at the time of It was -- what prevents the re-combination with an electron and an electron hole is said -- concrete -like -- Ag, Cu, P t, Pd, nickel, Co, F e, and Cu₂0th grade Power to be cited. It constitutes from the above-mentioned binder layer 6, for example, glaze, inorganic glass, thermoplastics, and Hitoshi Handa's thermoplastics. thus, with constituting a binder layer from thermoplastics, the Sprayco Tyng method etc. are simple and cheap on a binder layer are . a photocatalyst can be applied at normal temperature by a method -- again -- heat-treatment, substrate 1, binder layer 6, and photocatalyst layer 2 are firmly combinable -- it becomes advantageous on a manufacturing cost. it consists of multifunctional material which has a photocatalyst function concerning the present invention, and photocatalyst particles it is lamination on the sheet-shaped binder layer which consists a photocatalyst layer of thermoplastics -- or -- the -- A part is laid underground and it is constituted. About such sheet shaped multifunctional material, it is existing Thailand. If it heats after sticking on Nollet, sanitary chinaware, building materials, etc., it will be Prevention from after to ., the existing tile, etc. Functions, such as Odor, antifouling property, antibacterial properties, and antifungus, can be added.

It is greatly about the average particle diameter of photocatalyst particles 3 which constitute the above-mentioned photocatalyst layer 2, and specific surface area. In order to carry out and to improve photocatalyst activity, it is preferred to use less than 0.3.

As for the thickness of the above-mentioned photocatalyst layer 2, it is preferred that it is 0. l/i m*0. 9. 0. photocatalyst particles are locally embedded in binder layer 6 by less than 1 z m -- partial Force generation which cannot demonstrate multifunctional material surface top catalyst activity, and its portion -- a bacillus -- Stay -- especially since it becomes like, antibacterial properties get worse. if 0. 9 z m is exceeded, it will become large with the rose of thickness -- permeating a sample -- power -- < -- the time of adhering -- dirt -- omission -- A -- . Here, the thickness of a photocatalyst layer is the outermost surface of a photocatalyst thin film to glaze. In an implication and a concrete target, it is even about the portion currently embedded in the lower layer, E P MA (electron beam microphone mouth analyzer) etc. -- ultimate analysis is conducted -- main-ingredients origin which constitute a glaze layer the value of base increases -- finding the distance from the topmost part of the portion used as about 1 law to the outermost surface It measures by To.

The design effect is also acquired by changing the thickness of photocatalyst layer 2. namely, thickness -- 0. -- if less than 0. 4 m is used above, a photocatalyst layer film thickness part is received an iris love scene can be attached by the interferential action of Light -- again -- exterior substrate If only the color of the ground, patterns, or those combination are used and it excels Interferential action of the above-mentioned light Less than 0. 2^m or more than 0. 4 m may produce [ more than 0. l/z m that excepted the arising portion ] a photocatalyst layer film thickness part to less than 1 // m. This technique is Potency of photocatalyst particles, when combining with each other only by photocatalyst particles 3 applicable to extensive ranges, such as a tile, a washstand, a bathtub, a large and a chamber pot, a sink stand, and a kitchen counter. Char energy (adsorption) Or it must be based on sintering. However, photocatalyst particles When using a mutual sintering operation, it must sinter at high temperature considerably, on the other hand -- the case where it is based on adsorption -- the specific surface area of photocatalyst particles -- very -- large -- carrying out -- and restoration nature unity will not become enough if there is no comb -- a part for active point adsorption of photocatalyst particles -- To consume the multifunctional material which has To, etc. and sufficient catalyst activity and abrasion resistance -- manufacturing -- a method -- Restriction will be carried out.

In order to strengthen combination of photocatalyst particles 3, it is a gap of photocatalyst particles 3. If big particles are used, failing in [ being unable to acquire sufficient associative strength and accepting it ] -- multifunctional material table the photocatalyst particles exposed to a field will be covered partially -- the multifunctional material surface the portion which cannot demonstrate upper catalyst activity arises -- a bacillus will stagnate in the portion By that, antibacterial properties get worse remarkably.

The gap between photocatalyst particles here is the 1st. Like and photocatalyst particles 3 which are shown in 6 figures (a), the neck part between three, and the 1st The both sides of the stoma between like and photocatalyst particles 3 which are shown in 6 figures (b), and 3 are pointed out. therefore, photocatalyst particles here -- a gap -- particles 4 of particle diameter also with small Ri -- the neck part between photocatalyst particles, and mind between photocatalyst particles either of the holes -- particles smaller than the gap of more ones are said. Photocatalyst particles are combined. It is considered as the means to carry out and is The 1. As shown in 6 figures (b), case, it is an especially effective means. As small particles 4 with which the gap of photocatalyst particles 3 is filled up, it is the quality of the material fundamentally. Although not restricted, the thing excellent in adsorption power is good. With the quality of the material in which adsorption ability is extremely weak It is [ a crack and ] Absorption by achievement about the object of making photocatalyst particles combine mutually. It is the activity of a photocatalyst particle surface rather than arrival ability is inserted in a gap with the extremely strong quality of the material. The probability which covers a point is from large intermediary Cause. In view of this point, one desirable as the quality of the material of the particles with which the gap of photocatalyst particles is filled up is S n, T i, and A._gthey are metal or oxides, such as Cu, Z n, F e, P t, Co, Pd, and N i, -- Follow the zeolite currently used as an adsorption carrier from Come, activated carbon, clay, etc. -- good -- better There is no To. the point of having moderate adsorption ability among the above-mentioned metal or oxides -- good -- better that which is is tin oxide -- again -- metal or oxides, such as Ag and Cu, photocatalyst particles since it has antibacterial properties and deodorization nature uniquely in addition to making comrades combine mutually -- this -- It is assistance about an operation of a photocatalyst in case there is no irradiation of light also in the use which utilizes a function. It is desirable at the point of having a function to carry out. That is, the gap of the above-mentioned photocatalyst particles 3 is filled up. The above-mentioned metal particles 5 may be used as small particles 4 carried out.

The average particle diameter of particles 4 with which the gap of the above-mentioned photocatalyst particles 3 is filled up and a photocatalyst It is preferred that it is less than 4 / 5 of the average particle diameter of particles 3.

particles 4 which fill the gap of photocatalyst particles 3, and the present manufacturing method -- photocatalyst particles -- said -- It will adhere to some extent not only the gap of Samurai but on photocatalyst particles. and between if the particle diameter of the particles which fill spare time exceeds 4 A 5 of the average particle diameter of photocatalyst particles -- photocatalyst the direction of the probability of adhering to a photocatalyst particle surface rather than the gap of particles becomes high -- photocatalyst grain The joint intensity of child 3 comrades falls. the particles which fill a gap -- photocatalyst particles when large, photocatalyst particles will be covered partially -- multifunctional material surface top demonstrate catalyst activity -- and a portion arise -- a bacillus can stagnate now in the portion Especially by that, a possibility of getting worse remarkably also has antibacterial properties.

the average particle diameter of particles 4 with which the gap of the above-mentioned photocatalyst particles 3 is filled up -- 0.0 Being [ it / less than 1 m ] power specific surface area -- large -- it carries out -- moderate adsorption power is acquired It is desirable.

Particles 4, photocatalyst particles 3, and Sufficient with which the gap of the above-mentioned photocatalyst particles 3 is filled up It is 1 at the quantity to the total quantity of Charged particles 4, and a molar ratio. More than 0 % is 6. It is below 0 %. It is desirable. It heat-treats in the temperature range which sintering of photocatalyst particles does not produce, and is a substrate. The quantity of the particles which fill a gap is few Eggplant the case where a photocatalyst layer is fixed via a binder. To wish, the quantity of the particles which photocatalyst particles do not join together firmly but fill a gap on the other hand -- many -- If it passes the quantity of the particles which cover photocatalyst particles increases -- a multifunctional material surface top catalyst -- active the portion which cannot be demonstrated arises -- since a bacillus can stagnate now in the portion, and especially antibacterial properties get worse remarkably, a mentioned range is preferred.

moreover -- Agglomerate(ing) the particles with which and its steam pressure select a thing higher than the steam pressure of the substance which constitutes photocatalyst particles, and are filled up into the gap of and photocatalyst particles as a substance which constitutes particles 4 with which the gap of the above-mentioned photocatalyst particles 3 is filled up to the neck part between photocatalyst particles Because -- To -- it is desirable. This is profit and Light touch about combination of firmer photocatalyst particles. In order to raise the peel strength of Medium layer, the direction made you not only to to make it filled up, but to sinter He is The squid et al. high substance of such [ particles 4 which fill a gap ] steam pressure if it chooses, it will function also as a sintering aid -- sintering temperature can also be reduced. As a high substance of such steam pressure, they are tin oxide, bismuth oxide, and Oxide. Although there are a lead etc., tin oxide is preferred in respect of safety. As for the thickness of the layer containing particles 4 with which the gap of the above-mentioned photocatalyst particles 3 is filled up, it is preferred that more than 0 .1 m is. The thickness of this layer is a part in less than 0. They are photocatalyst particles-like. (and particles which fill a gap depending on a manufacturing method) The portion which is embedded in binder layer 6 and cannot demonstrate multifunctional material surface top catalyst activity arises, That since a bacillus can stagnate now in a portion -- especially -- antibacterial power -- < -- getting worse remarkably -- stripes obtaining -- . the thickness of the layer which contains here the particles with which the gap of photocatalyst particles is filled up -- the outermost surface from -- even the portion currently embedded in the lower layer of the binder is included -- each unevenness It is the leveled thickness.

the 1st An example of the manufacturing method of the multifunctional material which has a photocatalyst function which requires 5 figures for the present invention it is the explained figure -- if it is in the present invention -- first -- The 1 substrate 1 is prepared as shown in 5 figures (a) -- it is shown in the figure (b) -- as -- it is formation about binder layer 6 to the surface of substrate 1 It carries out. Material as binder layer 6 in which the apparent initial softening is lower than the apparent initial softening of substrate 1 What consists of charges is selected. if an example is given -- substrate 1 -- tile and hoe mouth 1 Up the case where It was is pottery -- as binder layer 6 -- a glaze layer or a printing layer -- That as -- it can use .

subsequently, the figure -- it is shown in (c) -- as -- binder layer 6 top -- T i 0₂Light touch, such as particles Photocatalyst layer 2 which consists of intermediation particles is formed. This time, photocatalyst layer 2 appears that it is also at the associative strength of the grade which does not fall from binder layer 6 in the case of next calcination in binder layer 6. Leave is good.

before [ or ] forming binder layer 6 in the surface of substrate 1 -- the figure (b) -- To indicate -- photocatalyst layer 2 is formed on binder layer 6 like -- this binder layer 6 It may be made to lay on substrate 1.

Then, it is 2 from the apparent initial softening of binder layer 6. 0. C is exceeded and it is 3. 2 The range of less than 0 °C It is heat-treating by high and ambient temperature lower than the apparent initial softening of substrate 1, the figure -- (d) or Drawing 9 thru/or The 1 as [ show / in 4 figure ] -- the inside of photocatalyst layer 2 -- the above the binder layer which the lower layer by the side of a binder layer fused -- the -- carrying out mosquito sedimentation in part -- binder layer the part concerned is buried with solidifying in a binder layer -- it is held firmly. Po of mutual [ particles / 3 / which constitute and the surface which touches the open air among photocatalyst layers 2 / photocatalyst ] sintering by the Teng Shal energy, an intermolecular force, or calcination -- The 1 the part is combined as shown in 6 figures (a) -- other portions again -- The 16 figure -- it is separated as shown in (b). That is, in a surface, the surface of photocatalyst particles is exposed outside substantially. It is carrying out.

Here, it is heat-treatment temperature from the apparent initial softening of binder layer 6 2 0"C is exceeded and it is 3. 2 It is highly at the range of less than 0"C. It carried out, it is less than 20 degreeC -- softening of a binder layer time is taken and maintenance of photocatalyst particle 3 a is not fully made -- on the other hand -- 3 20"C If it exceeds It is Burial into the binder layer of photocatalyst particles by rapid fusion of a binder layer. It is Desirable when a piece and a pinhole occur further, generating of a ball or a concavo-convex field, and. 40 degrees of more than Is C to spread and below 300 degreeC carry out.

the case where the specific gravity of 5 t and binder layer 6 is set to <5b for the specific gravity of photocatalyst particles 3 -- 0* 6t- db* 3. -- 0, preferably 0. 5* <5t -- It becomes a relation of 5b* 2. 0. It carries out for obtaining. It is Ba when the specific gravity difference of this, photocatalyst particles, and a binder layer is not much small. When a Inder layer is fused, it is perpendicular movement within the binder layer of photocatalyst particles. Speed becomes slow, photocatalyst particles exfoliate after calcination, and it is Ease, photocatalyst particles and by if specific gravity difference with a Nda layer is too large, To fill striped Fear has increase of movement speed with perpendicular photocatalyst particles, and most photocatalyst particles in a binder layer -- again -- it When it produces locally, it is for a bacillus to stagnate in a bottom and for antibacterial properties to fall.

It is <5t as the application technique of this gentleman method. -- It is 0* (t -- [ The binder layer of The 2 which is <5b* 3. 0 may be made to intervene. ]) between a binder layer and photocatalyst particles also by a case. It must be made 5b>3. 0.

<5t -- At the time of Sb< 0, if it pressurizes at the time of heat-treatment, it will be specific gravity difference 51. -- 5 b There is effect same with increasing. Therefore, H I P processing and Hot To Topless processing 0*5t -- (the same effect as the time of 5b* 3. 0 is acquired.)

The gap of the photocatalyst particles which constitute the portion exposed from binder layer 6 and concrete The neck part of photocatalyst particle 3 b shown in The 16 figure (a)-like, or The 1 Between photocatalyst particles 3 shown in 6 figures (b), It may be filled up with particles 4 (metal or oxides, such as Sn, Ti, Ag, Cu, Zn, Fe, Pt, Co, Pd, and nickel etc.) in which particle diameter is smaller than the gap concerned in order to combine photocatalyst particles.

As another manufacturing method of the multifunctional material which has a photocatalyst function concerning the present invention By which consists of thermoplastics on substrates 1, such as ceramics, resin, or metal Nda layer 6 is formed and it ranks next, They are photocatalyst particles 3 and particle diameter on this binder layer 6. The mixture which mixed small particles 4 in the state of the bull or the precursor is applied, and it is a photocatalyst. Layer 2 is formed, then -- softening the above-mentioned binder layer 6 -- lower layer of photocatalyst layer 2 a part is laid under the binder layer 6 -- it ranks next and may make it solidify

Particles 4 and Light touch which fill a gap beforehand while it is simple according to this method The mixture which mixed intermediation particles 3 in the state of sol or a precursor is applied, and it is a photocatalyst layer. Since it forms, the mixing ratio of photocatalyst particles 3 and particles 4 which fill a gap is controlled. It is convenient.

As another manufacturing method of the multifunctional material which has a photocatalyst function concerning the present invention On sheet-shaped binder layer 6 which consists of thermoplastics, they are photocatalyst particles 3 and particle diameter. The mixture which mixed small particles 4 in the state of sol or a precursor is applied, and it is Light touch. Medium layer 2 is formed, sheet-shaped binder layer 6 in which this photocatalyst layer 2 was formed -- Cerami it lays or sticks on substrates, such as A, resin, or metal, -- motorcycle the above [ next and ] * Hie carries out a Nda layer and it lays a part of lower layer photocatalyst layer under the binder layer -- ranking next -- Solid It may be made to change.

By which consists of thermoplastics on substrates 1, such as , ceramics, resin, or metal, as another manufacturing method of the multifunctional material which has a photocatalyst function concerning the present invention Nda layer 6 is formed and it ranks next, It consists of photocatalyst particles 3 on this binder layer 6. Photocatalyst layer 2 is formed, Then, the above-mentioned binder layer 6 is softened and a part of lower layer photocatalyst layer 2 is laid under the binder layer, subsequently, a binder layer is made to solidify -- further -- light It is the above by applying and heat-treating the solution which contains the small particles of the above-mentioned particle diameter in a catalyst bed. It may be made to fix small particles 4 of particle diameter to photocatalyst particles.

This method can be enforced comparatively simple, when the particles which fill a gap are oxides. A gap is filled when the comparatively porous photocatalyst layer which is How to do is created. Particles can be made to adhere so much.

As another manufacturing method of the multifunctional material which has a photocatalyst function concerning the present invention It consists of photocatalyst particles 3 on sheet-shaped binder layer 6 which consists of thermoplastics. Photocatalyst layer 2 is formed, Subsequently, sheet-shaped binder layer in which this photocatalyst layer was formed Ceramics, it lays or sticks on substrates 1, such as resin or metal, -- softening the above-mentioned binder layer 6 after this -- a part of lower layer photocatalyst layer 2 -- binder layer 6 -- Burial Carry out Establishment. subsequently, a binder layer is made to solidify -- Melting which contains metal particles 4 in a photocatalyst layer further liquid is applied -- it is fixation to photocatalyst particles 3 about the small particles of the above-mentioned particle diameter by heat-treating It may be made to change.

moreover As another manufacturing method of the multifunctional material which has a photocatalyst function concerning the present invention Ceramics, Substrates, such as resin or metal By which consists of thermoplastics on one Nda layer Form 6 and rank next. This binder layer They are photocatalyst particles on 6. It consists of 3. Photocatalyst layer 2 is formed, Then, the above-mentioned binder layer is * Made to turn, and it is a lower layer of a photocatalyst layer. A part is laid under the binder layer, Subsequently, a binder layer is made to solidify. It is further a photocatalyst. Metal particles small in a layer Solution containing ion of 4 is applied, Light which includes ultraviolet rays after this It glares, metal Iron is returned and it may be made to fix to photocatalyst particles. This gentleman method, When particles which fill a gap are metal, it can carry out comparatively simple. It is How to do. metaled fixation -- very -- short time. (several minutes) It can carry out. . The lamp used for an ultraviolet exposure, an ultraviolet-rays lamp, a B L B lamp, and A miser Any of a non lamp, a mercury lamp, and a fluorescent light may be sufficient.

As another manufacturing method of the multifunctional material which has a photocatalyst function concerning the present invention Light touch which consists of photocatalyst particles on the sheet-shaped binder layer which consists of thermoplastics Medium layer is formed, Subsequently, he is Serra about Si 1 A-like binder layer 6 in which this photocatalyst layer was formed. Mick, it lays or sticks on substrates 1, such as resin or metal, -- next and the above Soften binder layer 6 and lay a part of lower layer photocatalyst layer under the binder layer 6. subsequently, binder layer 6 is made to solidify -- further -- photocatalyst layer 2 -- small metal of the above-mentioned particle diameter the solution containing Iron of particles 4 is applied -- irradiating with the light which includes ultraviolet rays after this -- metal Iron is returned and it may be made to fix to photocatalyst particles.

By which consists of thermoplastics on substrates 1, such as , ceramics, resin, or metal, as another manufacturing method of the multifunctional material which has a photocatalyst function concerning the present invention Nda layer 6 is formed and it ranks next, It consists of photocatalyst particles 3 on this binder layer 6. Photocatalyst layer 2 is formed, It is Io of small metal particles 4 of the above-mentioned particle diameter to this photocatalyst layer 2. The solution containing A is applied, irradiating with the light which includes ultraviolet rays after this -- it is reduction about metal Iron it carries out and fixes to photocatalyst particles 3 -- * making the above-mentioned binder layer 6 turn further -- photocatalyst layer a lower layer part is laid under the binder layer -- it ranks next and makes a binder layer solidify -- as -- even if -- it is good. .

Since a heat-treatment process can be finished at once according to this method, productivity It improves.

As another manufacturing method of the multifunctional material which has a photocatalyst function concerning the present invention It consists of photocatalyst particles 3 on sheet-shaped binder layer 6 which consists of thermoplastics. Photocatalyst layer 2 is formed, It is the ion of small metal particles 4 of particle diameter to this photocatalyst layer 2. The included solution is applied, It irradiates with the light which includes ultraviolet rays after this, and returns a metal ion. It fixes to photocatalyst particles 3, Si 1 A-like binder layer in which photocatalyst layer 2 was formed It lays or sticks on substrates 1, such as ceramics, resin, or metal, then -- softening the above-mentioned binder layer 6 -- it is burial to a binder layer in a part of lower layer photocatalyst layer 2 it carries out -- it ranks next and may make it make a binder layer solidify

here, the above-mentioned photocatalyst particles are set to Z nO -- the gap of this photocatalyst particle is filled up Metal particles 4 -- Ag or Ag₂Being referred to as 0 is possible. Ag or Ag₂0 not only strengthening combination of the Z nO particles which are particles and a photocatalyst but Z nO a photocatalyst effect is March(ed) -- and it also has an effect of antibacterial properties and deodorization itself. Z nO -- light It comes out to cancel coloring by Ag Iron by choosing as a catalyst. it comes -- the color of the ground of a substrate, a pattern, or the design effect by those combination is improved Things are made.

It is insolubility between Iron of the metal with which the gap of the above-mentioned photocatalyst particles is filled up. It may be made to irradiate with the light which contacts a photocatalyst layer, cheats out of the solution containing the salts which form colorless or white salt, and includes ultraviolet rays and after this.

doing in this way -- ZnO, and Ag or Ag₂Even if not based on the combination of 0, the coloring depended for being based on the particles which fill and a gap can be canceled, and color of the ground of a substrate, a pattern, or the design effect by those combination can be improved. They are the above-mentioned photocatalyst particles 3 T i0₂it carries out -- in order to make binder layer 6 soften heat treatment temperature -- 8 0 0 -- the above -- 1 0 0 It is good also as 0 or less The. 8 0 More Than 0 °C In Order that Neck Part by Initial Sintering May Generate among T I 02 Particles, it is T I 0.₂Although the joint intensity of particles improves, when 1000"C is exceeded, it is Transfer to a middle sintering process. A line is carried out and it is Ti 0.₂since volume contraction of the photocatalyst layer accompanying Of solid phase sintering becomes remarkable -- A crack in a Cuca student, it becomes empty -- it becomes. ，

They are the above-mentioned photocatalyst particles Ti0₂it carries out -- the gap of this photocatalyst particle is filled up particles 4 are set to Ag -- the insoluble, colorless, or white salt between this Ag ion -- form the solution containing the salts which carry out Formation -- KI, KC1, and FeCl₃It is considered as halogenation thing solution of etc. The is also good. Ag is nothing at insolubility, such as Agl and AgCl, between alkali halide. Since a color or white salt is formed, improvement in a design by the color of the ground of a substrate, patterns, or those combination can be aimed at.

It is a distributed process as a previous process of the process of applying photocatalyst particles on a binder layer. When it has, the sol which should serve as photocatalyst particles in this distributed process -- or -- The dispersing agent for distributing a precursor in solution is made to soften a binder layer. It is more preferred than the heat treatment temperature of a sake to use only the ingredient evaporated at low temperature. that there was no deodorization nature in conventional technology at less than 32 CTC, and a distributed process -- it is -- Ti0₂the dispersing agent power adhering to a particle surface -- remaining, without fully evaporating and evaporating it can fold -- TiO₂a particle surface is not fully exposed to the substrate outermost surface -- photocatalyst function It is because it became insufficient. in addition -- as the dispersing agent evaporated at low temperature -- molecular weight the organic dispersing agent which is 10,000 or less, and a phosphoric acid system dispersing agent -- good -- better --

A concrete example is given to below.

(Example 1)

To the surface of the pottery tile substrate of 150 angles, it is Si0.₂-- A1₂0₃-- NaZK₂0 Off The binder layer which consists of Ritt is formed with spray and a coating method, and it dries. 15% of [ after It was and ] Ti0₂Sol solution is applied with spray and a coating method, and and film thickness are Ti0 of 0. 8 m.₂a layer is formed -- it ranks next -- a binder layer and Ti0₂A layer It is different If for every example about ambient temperature at a roller 1 Haas kiln in the laminated substrate. After carrying out To do it heating calcination, cooling solidification was carried out and multifunctional material was got.

It is here and is TiO.₂Sol solution is inside 100~20 (Anatase type Ti0 about [ which was acquired by hydrolyzing under the hydrothermal conditions of the range of TC ] crystal Child diameter 0. 007* 0. 2 m) of Fort Clave about TiCl.₂They are aqueous [, such as nitric acid and chloride, / acid ] at a sol state. To the inside of basic solution, such as liquid or ammonia, In order to have made it distribute several percent * tens of% and to raise and dispersibility, they are triethanol amine and A as a finishing agent. The organic acid salt of Trimethylolamine, and Ben evening Eli Trit and Trimethi roll pro Bread etc. are added in 0.5% or less of range. Ti0₂Particle diameter of sol By image processing of S EM observation, crystal Child diameter is powder. It calculated from the integration width of the X diffraction.

A coating method is Di although carried out with spray and a coating method. A' Cau The same result is expected as power profitable To be also with the Tyng method, and spin and a coating method. Evaluation about antibacterial properties and abrasion resistance was performed about the got multifunctional material. Bactericidal effect [ as opposed to / antibacterial properties / coliform bacillus (3110 shares of Escherichia coli W) ] It examined. Beforehand, it is fungus liquid 0 .15m l (X[ 1*5 ] 10) to the outermost surface of the multifunctional material sterilized by 70% ethanol.⁴CFU is dropped -- it puts on glass board (10 X 1 Ocm), and makes it stick to the substrate outermost surface -- it was considered as the sample. white light [ (3500 luxs) ] -- 3 After glaring for 0 minute, it is sterilization about the fungus liquid of the sample with which it irradiated, and the sample maintained under the shading condition. it wipes with gauze and collects to 1 10 m of physiological salines -- it asks for the probability of survival of a bacillus -- finger of evaluation carrying out -- Off^- o

They are a deed and appearance about the sliding wear which used the plastic eraser about abrasion resistance. Change was compared and evaluated.

It is Si0 to a pottery tile and a binder as a substrate in (table 1) of the following.₂-- A1₂0₃1NaZK₂0 Fritz The antibacterial properties accompanying change of calcination temperature when A is used, and abrasion resistance Change is shown.

(Table 1)

Substrate = an earthenware tile, Noinder = SiO₂-AI₂O₃-NaZK₂0 Fritz blue light catalyst = Ti0₂

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+ + Less than 10% of the probability of survival of + coliform bacillus

+ 10% of probability-of-survival Les of + coliform bacillus: It is less than 30% 1 top.

+ Less than 70% of the 30% or more probability of survival of coliform bacillus

On 70% of probability-of-survival Les 1 of coliform bacillus

O With no change to a 40 times round trip

O Cracks are Entering and Photocatalyst Layer (Ti0) by Ten to 40 Sliding.₂A film is * Separation.

Cracks are entering and a photocatalyst layer (Ti0) by sliding of △ 5-10 time.₂A film is * Separation.

X Cracks are entering and a photocatalyst layer (Ti0) by five sliding or less.₂A film is * Separation. S i0 used as a binder here₂-- A1₂0₃-- NaZK₂0 Frit As for specific gravity, when it applies, 2.4 and film thickness are 2. 0 0 m and an apparent initial softening are 6. 8 0. It is C and Oh. T i0 obtained in (table 1)₂About Is No. l*3 (4. specific gravity [ 3. specific gravity / It is a Anatase type. / is a rutile type about 9, No.4, and 5. ] being 2 Oh.)

it sets to (Table 1) -- No.1 -- calcination temperature -- the apparent initial softening of a binder -- 2 0. C Carry out. Since it is not high and the viscosity of the binder did not become low enough, it is a photocatalyst layer. Anatase type Ti 0 which constitutes the bottom of the heap₂It is [ in / particles are not laid enough underground into a binder layer and / , therefore an abrasion resistant test ] 5*1. By zero sliding, it enters and a crack carries out by having exfoliated. It waited. That it is a Anatase type which is excellent in photocatalyst activity about antibacterial properties and 3 0 0. More than C T i0₂T G of sol -- a D T A observation top organic ingredient -- almost -- having decomposed and evaporated -- T iO₂dispersing agents, such as a finishing agent adhering to the surface, are naturalized although understood as ing -- treatment temperature at 700 degreeC whose calcination temperature is far higher than it it is -- things -- + It became the outstanding value +.

although No.3*5 is a case where calcination temperature is more than 800 degreeC and below 1000 °C, it is not Re of endurance is not [ 40 sliding examinations or more ] changeful, either -- extremely outstanding thing Ivy. As this cause, it is Ti0 of the surface.₂Raw [ of the neck part accompanying initial calcination of particles ] Formation can be considered. 110 o^eHe is L'Ora Haar after cooling solidification the case where it processes by c. TiO of the multifunctional material surface taken out from Skill₂a layer -- crack power -- &lt; -- it had produced. This is Ti0.₂it judges from TMA measurement of test Beads -- Ti0₂Particles are remarkable. It is thought that it is based on middle sintering accompanied by volume contraction.

At No.4 and 5, all are [ antibacterial properties / -- and ] Noodle bad. In this, two causes are Thought. It is obtained. One is TiO.₂particles are carrying out the phase transition to the rutile type -- it is also -- it obtains and calcination temperature of one is higher exceeding 300 degreeC than exceeding the apparent initial softening of a binder -- Vine TiO which the viscosity of Da becomes low too much and constitutes a photocatalyst layer₂Particles are in a binder layer. Laying-underground power idea To be. It is here and is TiO.₂Particles are phases to a Lucinole type. It is unthinkable that it is because it has only transferred. Rutile type Ti0₂it is alike and also sets -- you -- 1 Ze type Ti0₂being alike -- since there is photocatalyst activity a little although it is inferior it is . For example, it is direct Ding 10 to a porous alumina substrate.₂the spray coat of the sol is carried out -- the antibacterial properties of the data which carried out cooling solidification the calcination back by 950"C were +. therefore, glow Nariatsu a degree is higher exceeding 300 degreeC than exceeding the apparent initial softening of a binder -- TiO which constitutes a photocatalyst layer that the viscosity of a binder becomes low too much₂Particles are laid underground into a binder layer. It is understood also as having kept making a cause.

Ti and Si (a part for Main character of a binder) by E PMA of the direction of a section of a sample, etc. the layer in which Ti and Si were intermingled is observed by ultimate analysis -- photocatalyst particles -- is there T i 0₂power -- &lt; -- laying-underground power -- &lt; -- it was checked.

the above Example 1 -- getting it blocked -- at least -- a photocatalyst -- Ti0₂A binder layer is Si0.₂-- A1₂0₃-- Na,K₂The following things were checked at the time of 0 fritto.

(1) Calcination temperature is 20 from the apparent initial softening of a binder.^eit is high exceeding C -- 300"C -- Yue Both antibacterial properties and abrasion resistance are [ time of obtaining and manufacturing multifunctional material on the conditions which are not high ] good. are . Multifunctional material can be manufactured. The cause is the viscosity of a binder in the above-mentioned temperature range. Power T i 0₂Ideas since it is adjusted to the value which may be moderately laid underground into a But' A cradle layer To be.

The multifunctional material produced by (2)(1), and Ti0₂when burial to the binder layer of particles is [ check Sorry (3) calcination temperature ] more than 800 degreeC and below 1000 degreeC, neither of abrasion resistance is [ and 40 sliding examinations or more ] changeful -- it became the extremely outstanding thing. Ti0₂It is thought that it is based on the firm combination accompanying the neck part generation between particles.

(Example 2)

Alumina substrate of 100X100X5 (96% of alumina purity) To the surface, it is S i0.₂-- A1₂0₃-- PbO Fritz They are spray and Cau Tin about the binder layer which consists of ♪. T i 0 of 15 % after forming by the A method and drying₂Sol solution (it is the same as Example 1) is applied with spray and a coating method, and film thickness is Ti0 of 0.₂a layer is formed -- it ranks next -- a binder layer and Ti0₂It is low Raher about the substrate by which Layer force lamination was carried out. Cooling solidification after changing ambient temperature for every example in Skill and carrying out heating calcination It carried out and got multifunctional material.

It is Si0 to alumina and a binder as a substrate in (table 2) of the following.₂-- Al₂0₃-- It is Show about the antibacterial properties accompanying change of calcination temperature when Pb 0 fritto is used, and a wear-resistant change. To.

(Table 2) Substrate = an alumina board (100x100x5) and a binder = Si0₂-AI₂0₃- PbO Fritz Photocatalyst =Ti0₂

No. 6 7 8 9 10 calcination temperature (degreec) -- 560 580 740 840 Difference () 20 with 860 apparent initial softening 40 200300 320 antibacterial-properties + + + + + + + + + + + abrasion resistance delta O O O O Here, Si0 used as a binder₂-- A1₂0₃-- PbO Fritz Softening temperature of ♪ As for 540degreeC and specific gravity, when applied, 3.8 and film thickness of the degree were 150 muiotaeta. Obtained TiO₂All Crystals types were Anatase types.

it sets to the abrasion resistant test of (Table 2) -- as for No.6, a crack enters by ten sliding or less -- although it has exfoliated, as for No.7 and 8, a crack does not enter at least ten sliding or more -- the good result that a crack does not enter at least 40 sliding or more, as for No.9 and 10 is obtained further It was.

A crack's not having entered at least 40 sliding or more by No.9 and 10 and calcination temperature are 8. Since it is more than 00"C, it is TiO.₂a neck generates among particles -- Ti0₂Particles Since it joined together firmly, it thinks.

that the crack has entered and exfoliated by ten sliding or less in No.6, and calcination temperature -- the apparent initial softening of binder -- 2 (TC -- Only -- it is not high -- Anatase type Ti0 which constitutes the bottom of the heap of a photocatalyst layer since there was nothing if the viscosity of a binder is fully low To)₂Particle power It thinks because it was not laid enough underground into the A cradle layer.

as opposed to it -- calcination temperature of what does not result in the temperature in which a neck part is generated that a crack did not enter at least ten sliding or more by No.7 and 8, and apparent initial softening of a binder a difference -- the viscosity of a binder -- Ti0₂Value which may be moderately laid underground into a But binder layer It is considered since it was adjusted.

it sets to antigenecity study [ on the other hand / (table 2) ] -- nualpha6~9 -- + + + or + + -- right -- the power which obtained the good result -- &lt; -- No.10 became +. this -- calcination temperature -- softening of a binder 320 C is also higher than temperature -- the viscosity of a binder becomes low too much -- photocatalyst layer Ti0 to constitute₂o considered because particles have been laid underground into a binder layer

(Example 3)

Si0₂-- A1₂0₃-- processing after carrying out the fusion * cooling solidification of the BaO fritto within a model carrying out -- 1X[ 00 ] 1 the glass sheet ofX[ 00 ] 1 is produced -- an it top -- 15% of 1^0₂sol solution (the same as Example 1) it applies by spray and the Co 1 Tyng method -- film thickness -- Ti0 of 0. 8 m₂The layer was formed. then, a glass sheet -- alumina putting on substrate (1 00 X 1 00 X 5) -- a Silico knitting furnace -- ambient temperature -- example every -- after making it differ and carrying out heating calcination, cooling solidification was carried out and multifunctional material was got.

The antibacterial properties accompanying change of the calcination temperature of the multifunctional material of the above [ / (table 3) / of the following ], and abrasion proof A sexual change is shown.

(Table 3) Substrate = an alumina board (100x100x5), Noise = Si0₂-AI₂0₃- BaO sheet Photocatalyst - tauiota*₂

<img file="WO9515816A1_D0002.tif" />

Si0 used as a binder here₂-- A1₂0₃-- Softening temperature of BaO fritto As for a degree, 620 °C and specific gravity are 2.8 and T i 0 on multifunctional material.₂As for the Crystals type, a you 1Ze type and No.14 were rutile types No.11-13.

it sets to the abrasion resistant test of (Table 3) -- a crack enters by ten sliding or less No.11 -- and the good result that, as for No.12, 10 times or more of sliding or cracks do not enter, and a crack does not enter No.13 and 14 further in at least 40 sliding or more although it has exfoliated -- profit Was done.

At No.13 and 14, since a crack's not having entered and calcination temperature are more than 80 CTC, at least 40 sliding or more is Ti0.₂a neck generates among particles -- Ti0₂Particles Since it joined together firmly, it thinks.

a crack enters by ten sliding or less by No.11 -- having exfoliated and calcination temperature 20 degreeC carrying out rather than the apparent initial softening of a binder -- power -- it is not high -- the viscosity of a binder -- enough -- Announcer evening 1 Ze type TiO which constitutes the bottom of the heap of a photocatalyst layer since it did not become low₂Particles are As. It thinks because it was not laid enough underground into the Inder layer.

as opposed to it -- that a crack did not enter at least ten sliding or more by No.12, and A net Calcination temperature of what does not result in the temperature in which a The part is generated, and apparent initial softening of a binder a difference -- the viscosity of a binder -- Ti0₂To the value which may be moderately laid underground into a But binder layer It is considered since it was adjusted.

it sets to antigenecity study [ on the other hand / (table 3) ] -- No.11*13 -- + + + or + although + and a good result were obtained -- No.14 -- 1 -- Noodle. This is Ti0.₂a But rutile type -- Ah 320 degreeC also has To and calcination temperature higher than the apparent initial softening of a binder -- binder TiO which constitutes a photocatalyst layer that viscosity becomes low too much₂Particles are in a binder layer. It is thought that it is based on two causes of having been laid underground.

It is TiO beforehand from the above thing to a binder.₂sticking particles on the application back and a substrate -- calcination it also sets to how to carry out and to get multifunctional material -- a binder is applied to the substrate surface -- after that T i 0₂It is Sure that the same effect as how to apply particles and to get multifunctional material is acquired.

6 -- &lt; -- Shinobu -- Lesomicron

(Example 4)

1 X[ 00 ] 1 Polyimi ofX[ 00 ] 5 To Surface of Substrate consisting of Do System Resin, it is Acrylics. 15 after Applying Resin Noinda % T I 0₂sol solution -- spray' coating it applies by a method -- film thickness -- Ti0 of 0. 8 m₂a layer is formed -- ranking next -- binder layer Ti0₂The substrate with which the layer was laminated is calcinated by 150 degreeC at a Nichrome furnace, and it is multifunctional material. It obtained.

The antibacterial properties accompanying change of the calcination temperature of the multifunctional material of the above [ / (table 4) / of the following ], and abrasion proof A sexual change is shown.

(Table 4) Substrate = polyimide resin and binder 1 = Acryl resin

Photocatalyst - Ti0₂Calcination temperature 150degreeC

<img file="WO9515816A1_D0003.tif" />

it sets (table 4) -- 15% 1^0₂The adjustment method of sol solution is as follows. It was made to change.

No.l 5 : 15%Ti0 of example 1 use₂Sol solution was used as it was.

No.16.: it is made to distribute without adjusting T i C 1 solution after [ ] hydrolysis, and nitric acid's adjusting output to pHO. 8 by 110in Wow 1 Toclave * 150 °C, and using a surface modification agent -- what ranked next and removed the condensation thing was used. In this case, spray and coating It carried out immediately after condensation object removal.

here -- Ti0₂Specific gravity is 3.9 and a crystallized type is a ratio of Anatase and an acrylic resin. The temperature which becomes the viscosity corresponding to 0.9 and glass softening temperature in a pile is 70degreeC.

If related with abrasion resistance, they are 10 times or more of Sliding also at either conditions of No.15 and 16. A crack did not enter by Motion, either. This is calcination temperature and *-ized temperature of a binder. The range of a difference is the viscosity of a binder Ti0₂It may be moderately laid underground into a But binder layer. It thinks because it was a value which can be adjusted to a value.

being related with antigenecity study on the other hand -- NO.15 and 1 -- Power and NO.16 -- + -- it is having obtained the good result -- 3 (the multifunctional material which has antibacterial properties in less than TC found out that manufacture was possible.) + This difference is DTA. -- In TG, it is Ti0 of NO. 15.₂T i 0 since it does not accept in NO .16 although there is an ingredient which decomposes and evaporates in 200*350 degreeC in sol₂The existence of a Cover organic ingredient is a cause and Summer. It is considered ing. Here, the specific gravity difference of Anatase and Acryl resin is a difference of this level, although it is 3. Ti0 which constitutes a photocatalyst layer if it is₂particles are laid underground into a binder layer -- things Having antibacterial properties with good To was also checked.

(Example 5)

100X free from which specific gravity differs for every operation on the surface of the alumina substrate ofX[ 100 ] 5 The binder layer which consists of Tuts etc. is dried the fabrication back by spray and the Co 1 Tyng method. Back 15% of 7^0₂It is sol solution by Splay and the Co 1 Tyng method Ti0 of film thickness 0.8₂a layer is formed -- ranking next -- a binder layer and Ti0₂It is Ro about the Is laminated(ed) substrate. It is ambient temperature at a 1 Lahrs kiln 750 After [ heating calcination ] cooling solidification is carried out as C. Multifunction material was got.

The antibacterial properties accompanying change of the calcination temperature of the multifunctional material of the above [ / (table 5) / of the following ], and abrasion proof A sexual change is shown.

(Table 5) Certain Material = an alumina board (100x100x5) and a photocatalyst = Ti0₂

<img file="WO9515816A1_D0004.tif" />It is related with antigenecity study and all of NO.17*20 are +. + + and a good result are obtained. It was. in any -- calcination temperature -- the apparent initial softening of a binder -- more than 30 degreeC -- 30 it is high in the range below o degreec -- the range of the difference of calcination temperature and the apparent initial softening of a binder -- the viscosity of a binder -- Ti0₂It was adjusted to the value which may be moderately laid underground into a But binder layer. It is considered a Oh sake with a value.

If related with abrasion resistance, in N0.17 and five sliding or less, it enters and a crack exfoliates. As for power NO.18*20 kept, a crack did not enter at least ten sliding or more. As the cause, the direction of the specific gravity of others, a difference, and a binder is TiO at N0.17.₂Anatase type TiO which constitutes the bottom of the heap of a photocatalyst layer since it is larger than Specific gravity₂Particles are As. It is laid enough underground into a Inder layer and considered the method sake of Summer.

Therefore, in the abrasion resistance of multifunctional material, it is Ti0.₂specific gravity with a binder -- influence it carries out -- the direction of the specific gravity of a binder -- Ti0₂It becomes clear that it will get worse if larger than Specific gravity. It carried out.

(Example 6)

It is Si0 to the surface of the earthenware tile substrate of 150 angles.₂-- A1₂0₃-- BaO Frit (apparent-initial-softening 620degreeC) from -- the becoming binder layer is formed -- an it top -- Ti0₂Sol and S n0₂The solution which mixed sol and was agitated was calcinated after an application and in 75 CTC with spray and a coating method, cooling solidification was carried out, and multifunctional material was got.

Ti0₂Sol concentration is 4*6wt %, and is NH.₃It is adjusted to PH 11 in solution, and they are and TiO.₂crystal Child diameter of particles is 0. 01 m -- Sn0₂Crystal Child of particles is 0. 0035 piiota.

In this way, it is Ti0 about the produced multifunctional material.₂Sn0₂Sn 0 to Total amount of₂quantity (molar ratio) The antigenecity study at the time of boiling many things and making it change, and abrasion resistant test The performed result is shown in following (table 6).

(Table 6) Substrate = an earthenware tile and binder Si0₂-AI₂0₃- BaO Fritz blue light catalyst = Ti0₂Gap particles = Sn0₂(0.0035 mu m)

<img file="WO9515816A1_D0005.tif" />

About an abrasion resistant test, it is Sn0.₂it improves with the increase in the amount of of -- 10% or more also setting to 40 sliding examinations by addition -- Wound force -- &lt;&lt; -- change also arises, without entering there is nothing -- Noodle.

if it is a range up to 20% or more about antigenecity study -- the time of additive-free -- the same -- + + It was +, and when becoming to 60%, it stopped at ++. It is a substrate when it adds more. Surface TiO₂the probability which covers particles becomes high -- antibacterial properties get worse -- 100% -- 1 It became.

Therefore, Sn0₂It is a molar ratio about the amount of Addition, and is Ti0.₂Sn0₂10% of Total amount of -- with -- if below upper 60 % uses more than 10 % and below 20 % preferably -- antibacterial properties The multifunctional material excellent also in abrasion resistance can be provided.

Abrasion resistance is Sn0 here.₂In the mechanism which shows improving with the increase in the amount of of below It depends. Namely, Sn0₂IsTi0₂also depending -- steamy pressure quantity was at the high temperature more than 600 degreeC Because -- if it is before sintering -- Ti0₂the interval of particle 3 b -- The 17 figure -- it is shown in (a) -- as -- L. It comes out and is a certain power and Ti0.₂on the surface with the positive curvature of particles 3, steam pressure is high -- negative the surface with curvature -- getting it blocked -- two Ti0₂The surface of a neck part where particle 3 b contacts Steam pressure becomes low. as a result, The 17 figure -- it is shown in (b) -- as -- a neck part -- T i0₂also depending -- Sn0 with high steam pressure₂a Enter lump and Drawing 17 -- it is shown in (c) -- as -- Condensation is carried out -- sintering is performed by evaporation 1 condensing mechanism. And evaporation -- When sintering is performed by the condensing mechanism, it is Ti0 after sintering.₂Particles Interval L₂Interval L in front of Is sintered. abbreviation -- since it is equal, cracks should occur -- , Thus, Noinda is passed to the substrate surface, and it is T i 0.₂compound part by which the particle layer was held it sets to material -- exposing to the outermost surface -- Ti0₂It is Sn0 to the gap of particles.₂It is filled up with particles and is 60. It is Ti0, without generating a crack, if it calcinates above 0"C.₂A net between particles Since a The part is combinable, an antiwear characteristic improves.

(Comparative example 7)

It is Si0 to the surface of the earthenware tile substrate of 150 angles like Example 6.₂-- A1₂0₃1BaO fritto (apparent-initial-softening 620degreeC) power -- a binder layer is formed -- the -- a top -- Ti0₂Sol and 310₂It is a spray . coatee about the solution which mixed sol and was agitated. It calcinated in application back and 750"C by the Tongue method, cooling solidification was carried out, and multifunctional material was got. T i 0₂Sol concentration is 4* 6 w t %, and is N H.₃it is adjusted to P H 11 in solution -- power Sn0 which is 0. O l^m like [ crystal Child diameter of particles ] Example 6₂Connection of particles Akiko used 0.008 and a little large particles.

In this way, the result which did antigenecity study and an abrasion resistant test about the produced multifunctional material, and was compared with and Example 6 is shown in following (table 7).

(Table 7) Substrate = an earthenware tile and a binder = Si0₂-AI₂0₃- BaO fritto Photocatalyst =Ti0₂Gap particles = SnO₂(0.0080 mu m), heat treatment 750degreeC

<img file="WO9515816A1_D0006.tif" />

As a result, Sn0 of 0. 008 m₂The effect of the wear-resistant improvement in particles is 0.0. Sn0 of 035₂it is weaker than the case where particles are used -- Ti0₂Sn0₂Total amount of the receiving molar ratio also sets to 40 sliding examinations at last at 60% or more -- a crack -- ON there is also no To -- it was it changeless arising

About antigenecity study, it is Sn0 of 0. 0035 m.₂It is the same as that of the case where particles are used. If it is a range up to 20% or more, it is + like the time of additive-free. + It is + and is 6. When 0% or less became, it stopped at ++. When added more, it is TiO on the surface of a substrate.₂particles the probability to cover becomes high -- antibacterial properties get worse -- at 100%, it became --.

Ti0 of power intermediary 0. 01 m carried out₂When particles are used, it is 0. 008m. S etatheta₂The multifunctional material which added particles and was excellent in antibacterial properties and abrasion resistance is provided. It is difficult. As this cause, it is SnO.₂If, as for the steam pressure of particles, a grain size becomes large Becoming small and Sn0 which remain without evaporating₂When particles are 0. 0035 m Ti0₂While it exists in the gap between particles and joint intensity might be improved, it is 0.00. At 8//m, it is Ti0.₂It compares with the gap between particles and is Sn0.₂Since the particles are large, it is Sn 0.₂particles do not put into a gap -- rather -- Ti0₂Intermediary To have with high probability of coming on particles It is considered a sake.

From the above thing to Ti0₂Sn0 which should fill the gap of particles₂The size of particles is T iO.₂It is 4 to the diameter of a particle. It is preferred that it is less than five.

(Example 8)

To the surface of the earthenware tile substrate of 150 angles, it is Sn0.₂-- Al₂0₃-- Ba07U (apparent-initial-softening 62CTC) power -- a binder layer is formed -- an it top -- Ti0₂Sol water Solution is calcinated in application back and 750"C by spray and the Co 1 Tyng method, and it is cooling solidification. To the combined member carried out, it is Sn0.₂Sol solution was heat-treated after [ ] an application and by 110 degreeC by the spray' Co 1 Tyng method, and multifunctional material was got. This time Ti0₂It carries out in sol solution. 0. 0035 / the m was used for SnO^ using the same thing as Example 6. in this way -- the produced multifunctional material -- the examination made from antibacterial properties, and an abrasion resistant test -- Result -- the following -- (-- it is shown in table 8). (Table 8) Substrate = an earthenware tile, Noinder = Si0₂-AI₂0₃- BaO Fritz blue light catalyst = Ti0₂Gap particle - SnO₂(0.0035ym), heat treatment 750degreeC/110degreeC<img file="WO9515816A1_D0007.tif" />

About an abrasion resistant test, it is SnO.₂it improves with the increase in the amount of of -- without a crack enters also in a sliding examination by addition of 20% or more of a molar ratio 40 times -- change It stopped arising.

if it is a range up to 20% or more about antigenecity study -- the time of additive-free -- the same -- + + It was +, and when becoming to 60%, it stopped at ++. if added more -- substrate the probability which covers T i 02 surface particles becomes high -- antibacterial properties get worse -- 100% 1 and Noodle.

At the final examination, it is SnO.₂Since sol is heat-treated at the low temperature 110degreeC, it carries out. Sintering by evaporation 1 condensing mechanism shown in Example 6 does not arise. Nevertheless, abrasion proof This is Ti0 although the sex improved.₂particle diameter is smaller than particles -- namely, specific surface area Sn0 which is greatly excellent in adsorption power₂Particles are Ti0.₂It is and Ti0 by having filled the gap of particles.₂Since combination of particles was strengthened, it thinks.

(Example 9)

To the surface of the earthenware tile substrate of 150 angles, it is Si0.₂-- A1₂0₃-- BaO Frit (apparent initial softening 620.) C) power -- a binder layer is formed -- an it top -- Ti0₂sol water calcinating solution in * 50"C after an application by Splay and the Co 1 Tyng method -- cooling solidification copper acetate solution is applied to the combined member carried out, and it is dried -- light which includes ultraviolet rays after that it fixes to a photocatalyst layer, glaring and returning a copper ion -- multifunctional material was got. Here The mercury lamp lamp was used for the irradiation lamp.

The size of the C u particles fixed to the photocatalyst layer here is average 0.0. 0 About four It was.

In this way, it is To go about antigenecity study and an abrasion resistant test about the produced multifunctional material. Result (table 9) It is shown.

(Table 9) Substrate = an earthenware tile and a binder = Si0₂-AI₂0₃- BaO fritto Photocatalyst = Ti0₂Gap particle =0^0.004, 750 degrees of heat treatment CZ light reduction

<img file="WO9515816A1_D0008.tif" />

about an abrasion resistant test, it improves with the increase in the amount of C u -- molar ratio 2 More than 0 % addition -- 4 without a crack enters also in zero sliding examination -- change -- raw -- Tooth became that there is nothing.

antigenecity study -- 2 if it is a range to more than 0 % -- the time of additive-free -- the same -- + + It was +. C In u, since it has antibacterial activity in itself, it is abundant To add. The antibacterial aggravation by To was not accepted.

However, when the amount of addition of C u is probably little, it is T i 0.₂Photocatalysis by a particle layer for is dominant, and when the amount of addition of C u is abundant, the operation by C u is dominant. Probably, it may be thought that it is. C the case where the operation of only u is expected -- C u -- inside of a fluid Short-life, as compared with the case where there is no photocatalyst, since it is gradually eluted when it uses When -- it thinks. If the amount of addition of C u becomes abundant, it will also become the part cost overrun. Therefore, it seems that it is meaningless to set up the amount of C u not much so much. It is S n0 by this example.₂of -- not only an oxide [ like ] but metal like C u It was checked that it can become the particles which fill the gap of T i 02 particle layer.

(Example 10)

To the surface of the earthenware tile substrate of 150 angles, it is Si0.₂--Al₂0₃-- BaO Fritz ♪ (apparent-initial-softening 620degreeC) from -- the becoming binder layer is formed -- an it top -- Ti0₂sol water calcinating solution in application back and 950"C by spray and the Co 1 Tyng method -- cooling solidification copper acetate solution is applied to the combined member carried out -- irradiating with the light which includes ultraviolet rays after that Returning copper Iron, it fixed to the photocatalyst layer and got multifunctional material.

a BL B lamp is used for an irradiation lamp at this time -- it glared for several minutes. Ti0₂The phase transition was carried out to rutile from Anatase at the process of Is heat treatment. T i 0₂of film thickness is sprayed. -- 'coatee It adjusted to 0. 4^m at the time of Tongue.

In this way, it is To go about antigenecity study and an abrasion resistant test about the produced multifunctional material. It was. which shows a result good in this temperature region also by additive-free about an abrasion resistant test. C Even if it adds u, also in 40 sliding examinations, a crack like the time of additive-free Change was not produced, without entering.

Antigenecity study is shown in The 18 figure. It is Ti0 at the time of additive-free.₂But rutile It is bad in sake +. The antibacterial properties which add Cu to it Increase(ed). And not only the time of BL B lamp radiation but while not glaring, the amount of Cu support is 0.

Antibacterial activity will be + if it becomes two or more. The amount of Tooth 11 support is [ + and ] 1. 2^gZcm.²Above Antibacterial activity will be + if it becomes. + It becomes +.

In order to provide the multifunctional material which was excellent in antibacterial properties and abrasion resistance from the above thing, the amount of Cu support is 0. 7 gZcm.²The above is [ good ] 1. 2 beta / cm more preferably.²The above is good.

By the way, the amount of C u support is a drying process before the B L B Rumble irradiation after a copper acetate solution application. If it puts in, it will improve by leaps and bounds. The relation is shown in The 19 figure. This They are ideas as since metal ion concentration in case the direction at the time of making it dry carries out optical reduction is high. To be.

The amount of C u support is the amount of applications the case of (The 20 figure and The 20 figure are the examples of Cu concentration lwt% of copper acetate) which becomes the maximum when the amount of C u applications is made the optimal, and this The 20 figure 0 .7 g/cm²For carrying out above, it is 0. 2mg A cm.²It is 2.7 mg/cm above.²Below, it is 1. 2 gZcm.²For carrying out above, it is 0. SmgZcm.²They are 2. 4m g and c m above.²Below may be used.

(Example 11)

To the surface of the earthenware tile substrate of 150 angles, it is Si0.₂-- Al₂0₃-- BaO Frit (apparent-initial-softening 680degreeC) from -- the becoming binder layer is formed -- an it top -- Ding 10₂sol water calcinating solution in application back and 950"C with spray and a coating method -- cooling solidification silver nitrate solution is applied to the combined member carried out, and it dries to it -- the light which includes ultraviolet rays after that -- Looking Having put and returning silver Iron, it fixed to the photocatalyst layer and got multifunctional material.

a BLB lamp is used for an irradiation lamp at this time -- it glared for several minutes. Ti 0₂The phase transition was carried out to rutile from Anatase at the process of Is heat treatment. Ti0₂of film thickness It adjusted to 0. 4^m at the time of spray and coating.

In this way, it is To go about antigenecity study and an abrasion resistant test about the produced multifunctional material. It was. which shows a result good in this temperature region also by additive-free about an abrasion resistant test. Even if it adds Ag, also in 40 sliding examinations, a crack like the time of additive-free Change did not arise, either without entering.

Antigenecity study is shown in The 70 figure. It is TiO at the time of additive-free.₂It was of But rutile Because -- it is as bad as 10. When Ag was added to it, antibacterial properties increased. And not only the time of BLB Rumble irradiation but while not glaring, the amount of A g support is 0. 05 gZc m.²Antibacterial activity will be + if it becomes above. The amount of Ag support is [ + and ] 0. l gZcm.²Antibacterial activity will be + if it becomes above. + It becomes +.

Therefore, in order to provide the multifunctional material excellent in antibacterial properties and abrasion resistance, the amount of Ag support is 0. 05 gZcm.²The above is [ good ] 0. l^gZc m more preferably.²The above is good.

however, if there are many amounts of Ag support, it will be colored black from brown -- with bad exterior appearance. However, the amount of Ag support is 1 gZcm.²If it becomes below, there will be no coloring.

The above thing to the amount of Ag support is 0. 05 gZcm Lhl gZcm.²Following It is [ good ] 0. 1 gZcm more preferably.²It is 1 g A cm above.²The following is good. (Example 12)

To the surface of the earthenware tile substrate of 150 angles, it is Si0.₂-- A1₂0₃-- BaO Frit (apparent-initial-softening 680degreeC) power -- a binder layer is formed -- an it top -- Ti0₂sol water calcinating solution in application back and 950"C with spray and a coating method -- cooling solidification silver nitrate solution is applied to the combined member carried out, and it dries to it -- the light which includes ultraviolet rays after that -- Looking Having put and returning silver Iron, it fixed to the photocatalyst layer and got multifunctional material.

a BLB lamp is used for an irradiation lamp at this time -- it glared for several minutes. Ti 0₂The phase transition was carried out to rutile from announcer evening-Ze at the process of Is heat treatment.

In this way, about the produced multifunctional material, it is Ti0.₂of film thickness is changed to various values. A Abrasion resistance examination, antigenecity study, and a contamination-resistant examination were done.

About an abrasion proof examination, each is good in the range within 2/m examined this time. Change also arises, without showing a result and a crack entering also in 40 sliding examinations. There was nothing.

About antigenecity study, it is + more than at +10 and 0.2//m above film thickness 0. l m. + It becomes +. Therefore, Ti0₂More than 0 .2 m of of film thickness is preferably [ more than 0. 1 m is good, and ] good.

(Example 13)

To the surface of the earthenware tile substrate of 150 angles, it is Si0.₂-- A1₂0₃-- BaO fritto (apparent initial softening 62 the binder layer which consists of (TC(s)) is formed on it zinc chloride solution or Ti0)₂Sol solution is applied with spray and a coating method, after [ ] dryness and silver nitrate solution are applied, and it irradiates with the light which includes ultraviolet rays after that, and returns a silver ion. It fixed to the photocatalyst layer, carrying out. More than 900 degreeC is 1000 after that.^eIt calcinates below by C. Cooling solidification was carried out and multifunctional material was got.

a BLB lamp is used for an irradiation lamp at this time -- it glared for several minutes. Ti 0₂The phase transition was carried out to rutile from announcer evening-Ze at the process of Is heat treatment. surface fixation Ag carried out is followed on heat treatment -- under calcination since it changed from the brownish black color white It is thought that it changed to silver oxide. However, adhesion fixation of Ag is made discretely. Inside [ most of growth of Ag particles before and behind calcination is admitted by a cage and observation ] One piece:₀

In this way, it is To go about antigenecity study and an abrasion resistant test about the produced multifunctional material. It was. About an abrasion resistant test, additive-free shows a good result in this temperature region. A even if it adds g, also in L and The, a crack starts 40 sliding examinations like the time of additive-free there are also nothings -- it was it changeless arising

About antigenecity study, it is The. It is shown in a figure. It is Ti0 at the time of additive-free.₂It was of But rutile Because -- + -- it is bad. When Ag was added to it, antibacterial properties increased.

(Example 14)

To the surface of the earthenware tile substrate of 150 angles, it is Si0.₂-- A1₂0₃-- BaO Frit (apparent-initial-softening 620degreeC) from -- the becoming binder layer is formed -- an it top -- Ti0₂Sol water They are the application back, more than 900"C, and below 1000 degreeC with spray and the Co 1 Tyng method about solution. To the combined member which calcinated and carried out cooling solidification, silver nitrate solution is applied -- after that -- ultraviolet rays it fixes to a photocatalyst layer, irradiating with the included light and returning silver Iron -- further -- the -- the upper -- K I solution of 0. lmo 1 / 1 -- 0. 1 c cZcm²It applied by Percentage, and also irradiated with ultraviolet rays about 5 seconds, and got multifunctional material. In that case, the amounts of support of Ag are 2 g / cm.²It carried out.

0. It is 0. 1 C C A C M about K I Solution of Lmo 1 A 1.²it applies by Percentage -- the multifunctional material which was a brownish black color by having irradiated with ultraviolet rays about 5 seconds further -- white -- it is decolorized -- exterior appearance improved.

(Example 15)

To the surface of the earthenware tile substrate of 150 angles, it is Si0.₂-- A1₂0₃-- BaO Frit (apparent-initial-softening 620degreeC) power -- a binder layer is formed -- an it top -- Ti0₂Sol water It is solution with spray and a coating method The application back and 820 calcinating in C -- cooling solidification the multifunctional material which obtained by carrying out is made to incline, and it arranges -- it is irradiation on multifunctional material about light including ultraviolet rays it is dropped continuously, circulating the bath water extracted on multifunctional material in the public bathhouse while carrying out -- change of bath water was observed. It is a photocatalyst because of comparison of the same device. It was dropped also on the substrate which has not provided the layer. observation 14 days after -- above-mentioned various functions The bath water dropped on material is dropped on the substrate which has not provided the photocatalyst layer. it compares with Bath water -- although there are no unique difference mosquito private seal Re in muddiness condition -- ditchwater The difference was observed in the smell. namely, -- being dropped on the substrate which has not provided *&lt;&lt;4 Medium layer a quite strong ditchwater smell can accept with the bath water which was -- again -- a substrate top -- Schley M-like Nume -- Ri -- and -- being dropped on the above-mentioned multifunctional material, while the organic system sediment was observed the bath water which was -- the any -- although -- it did not accept. Flooring of the artificial waterfall of a water cycle method, or a fountain which has this multifunctional material in a park, Desbats 1 A, etc. by the above simulation It is thought that it can use as a stone.

It is Through about the binder layer which consists of a material lower than the apparent initial softening of a substrate from the above explanation. Light touch which constitutes the layer part of a photocatalyst layer carrying out and especially fixing photocatalyst particles Since intermediation particles were kept from being buried in a binder layer, photocatalyst particles -- substantial -- That the surface will be in the state where it exposed outside -- it comes out to fully demonstrate a photocatalyst effect It cuts. the particles which constitute the lower layer of a photocatalyst layer among photocatalyst particles -- the part since it is laid underground in a binder layer, the holding power of a photocatalyst layer improves sharply -- exfoliation etc. power -- &lt; -- it becomes difficult to produce.

the 2nd 1 figure is a figure showing the manufacturing process of another example -- if it is in this example, the thermoplastic thing of inorganic glass, thermoplastics, etc. is used as substrate 1 -- this heat Photocatalyst layer 2 is directly formed in the surface of reversibility substrate 1.

namely, the 2nd as [ show / in 1 figure (a) ] -- thermoplastic substrate 1 is prepared -- it ranks next -- the figure -- it is shown in (b) -- as -- the surface of thermoplastic substrate 1 -- T iO₂photocatalyst particles, such as particles from -- becoming photocatalyst layer 2 is formed. then, the thing to heat-treat -- the figure -- as [ show / in (c) ] -- being buried with the lower layer by the side of the above-mentioned thermoplastic substrate sedimenting to a thermoplastic substrate among photocatalyst layers 2, and a thermoplastic substrate solidifying in a thermoplastic substrate -- firm -- Keep It has. Photocatalyst particles 3 which constitute the surface which touches the open air among photocatalyst layers 2 are combined by potential energy, a mutual intermolecular force, or sintering. It is.

About the desirable conditions about this example, it is the same as that of the above-mentioned example. A concrete example is described below.

(Example 1 6)

1 5 S I0 of Zero Angle₂-- A 1₂0₃-- NaZK₂0 Surface of Glass Board Material Which Consists of Composition 1 T I0 of 5 %₂sol solution is applied by spray and the Co 1 Tyng method -- film thickness -- T i0 of 0. 8 yt m₂A layer is formed, and it ranks next and is T iO.₂Gala by which Layer force lamination was carried out a A substrate is put in the good model of the mold-release characteristic made from ceramics -- roller Haas kiln After changing ambient temperature for every example and carrying out heating calcination, cooling solidification was carried out and multifunctional glass was obtained.

It is here and is Ti0.₂Sol solution is TiCl.₄Anatase type Ti0 about [ which was acquired by hydrolyzing under the hydrothermal conditions of the range of 100 in Fort Clave * 200 °C ] crystal Child diameter 0. 007 *0. 2 / m₂a sol state -- acid water, such as nitric acid and chloride What [ was distributed tens of several percent*% in basic solution such as solution or ammonia, ] so in order to raise dispersibility -- as a finishing agent -- Trier evening no Ramen -- and -- The organic acid salt of Trimethylolamine, and Ben evening Eli Trit, Trimethylolp mouth bread, etc. are added in 0.5% or less of range. Ti0₂Grain of sol By image processing of S EM observation, as for a path, crystal Child diameter is powder. From the integration width of an X diffraction to the total Calculation was carried out.

A coating method is Di although carried out by spray and the Co 1 Tyng method. A' Cau It is expected that the same result is obtained also by the Tyng method, and spin and the Co 1 Tyng method, and it is o.

It is To go about evaluation of One and The to OneL, Antimicrobial properties, and abrasion resistance in the obtained multifunctional glass. It was.

Bactericidal effect [ as opposed to / antibacterial properties / coliform bacillus (3110 shares of Escherichia coli W) ] It examined. Beforehand, it is bacillus liquid 0. 15m l (1*5X10) to the outermost surface of multifunctional glass sterilized by 70% ethanol.⁴CFU is dropped -- it puts on glass board (10x10 cm), and makes it stick to the glass board material outermost surface -- it was considered as the sample. the sample with which it irradiated after irradiating with white light (3500 lux) for 30 minutes, and sample maintained under the shading condition fungus liquid is wiped with sterile absorbent gauze, and it collects to 1 10 m of physiological salines -- in quest of the probability of survival of a bacillus, it was considered as the index of and evaluation.

They are a deed and appearance about the sliding wear which used the brass tic eraser about abrasion resistance. Change was compared and evaluated.

Following (table 10) Si0₂-- A1₂0₃-- NaZK₂0 It is business about the glass board material of composition. The antibacterial properties accompanying change of calcination temperature when it is, and a wear-resistant change are shown. (Table 1 o) Substrate =5₂-8 -- 1₂0₃-^/1&lt;₂Zero glass

Photocatalyst = Ti0₂

<img file="WO9515816A1_D0009.tif" />

+ + Less than 10% of the probability of survival of + coliform bacillus

+ Less than 30% of the 10% or more probability of survival of + coliform bacillus

+ Less than 70% of the 30% or more probability of survival of coliform bacillus

70% or more of the probability of survival of coliform bacillus

O With no change to a 40 times round trip

O Cracks are ON Li and Photocatalyst Layer (Ti0) by Ten to 40 Sliding.₂A film is * Separation.

Cracks are entering and a photocatalyst layer (Ti0) by sliding of delta 5-10 time.₂A film is * Separation.

X Cracks are entering and a photocatalyst layer (Ti0) by five sliding or less.₂A film is * Separation.

here -- Si0₂_Al₂0₃-- Na,K₂0 2.4 and the apparent initial softening of the specific gravity of the glass board material of composition were 680degreeC. Again (table 10) Ti0 produced by setting₂about Is No. 1~3, it is a Anatase type -- specific gravity -- 3.9, No. 4, and 5 -- One it is a rutile type if it is -- specific gravity was 4.2.

it sets to (Table 10) -- No.1 -- calcination temperature -- the apparent initial softening of a glass board material -- 2 0. C carrying out -- power -- it is not high -- the viscous power of a glass board material -- &lt; -- Anatase type T i 0 which constitutes the bottom of the heap of a photocatalyst layer since it did not become low enough₂particles -- the inside of a glass board material -- enough -- Burial is not carried out -- therefore, in an abrasion resistant test, the crack has entered and exfoliated in 5*10 times of * Motion. About antibacterial properties, it is 1^0 above that it is an announcer evening-Ze type which is excellent in photocatalyst activity, and 300 degreeO.₂Ding 0 of sol -- Zero-dish 8 observation top Organic formation a part -- it has decomposed and evaporated mostly -- Ti0₂Dispersing agents, such as a finishing agent adhering to the surface Although understood as having evaporated, calcination temperature is farther [ than it ] high at 700 degreeC. From it being treatment temperature, it is +. It became the outstanding value +.

neither of endurance is [ 40 sliding examinations or more ] changeful although No.3~5 is a case where calcination temperature is more than 800 degreeC and below 1000 °C -- extremely outstanding thing It became. As this cause, it is surface TiO.₂Neck part accompanying initial calcination of particles Generation can be considered. Ti0 of the multifunctional glass surface taken out from Laura after cooling solidification - Skill when it processed by 1100 degreeC₂a layer -- crack power -- &lt; -- producing It was. This is Ti0.₂it judges from TMA measurement of test Beads -- Ti0₂Particles It is thought that it is based on middle sintering accompanied by remarkable volume contraction.

At No.4 and 5, each antibacterial properties are [ 1 and ] Noodle bad. Two causes to this It thinks. One is TiO.₂it is that particles are carrying out the phase transition to the rutile type -- another -- calcination temperature -- the apparent initial softening of a glass board material -- 300 -- it is high -- glass board material T i 0 which viscosity becomes low too much and constitutes a photocatalyst layer₂Particles are Burial in a glass board material. It is possible that Establishment has been carried out. It is here and is TiO.₂Particles are Succession to a rutile type. It is unthinkable that it is because it is only moving. Rutile type TiO₂To -- even if it is -- Anatase type Ti0₂being alike -- since there is photocatalyst activity a little although it is inferior It is. For example, it is direct Ti0 to a porous alumina substrate.₂The spray coat of the sol is carried out and it is 9. The antibacterial properties of the data which carried out cooling solidification the calcination back by 50"C were 10. Therefore, calcination temperature It is 300 from the apparent initial softening of a glass board material. C -- it is high -- the viscosity of a glass board material becomes low it passes -- T i 0 which constitutes a photocatalyst layer₂Particles carry out by being laid underground into a glass board material, and it is a pine. It is understood as Was it making a cause.

Ti and Si (a part for Main character of a glass board material) by EPMA of the direction of a section of a sample, etc. the layer in which Ti and Si were intermingled is observed by ultimate analysis -- photocatalyst particles -- is thereTi0₂it Buried -- the thing power check was carried out.

the above Example 16 -- getting it blocked -- at least -- a photocatalyst -- Ti0₂The following things were checked when a glass board material was Si Oz-AUOs-Na/KzO composition.

①: It is also as antibacterial properties and abrasion resistance the time of calcination temperature being higher exceeding 20 °C than exceeding *-ized temperature of a glass board material, and manufacturing multifunctional glass on higher conditions than 300 °C. Good multifunctional glass can be manufactured. The cause is Gala in the above-mentioned temperature range. The viscosity of a A substrate is adjusted to the value with which T i 02 may be moderately laid underground into a glass board material. It is considered a sake.

②: Burial to the glass board material of TiO 2 particles checks the multifunctional glass produced by (1). It was carried out.

③: the case where calcination temperature is more than 800 degreeC and below 1000 degreeC -- any -- abrasion resistance 40 sliding examinations or more are not changeful, either -- it became the extremely outstanding thing. Ti 0₂It is thought that it is based on the firm combination accompanying the neck part generation between particles.

(Example 17)

Si0 of 100X100X5₂-- A1₂0₃-- Glass board material which consists of PbO composition To the surface, it is 15% of Ti0.₂Sol solution (it is the same as Example 16) Spray' Co 1 It applies by the Tyng method and film thickness is Ti0 of 0.8.₂a layer is formed -- it ranks next -- Ti0₂It is ON in the good model of the mold-release characteristic made from ceramics about the glass board material on which the layer was laminated. Ambient temperature is changed for every example in Re and a roller 1 Haas kiln, and it is heating calcination. After carrying out, cooling solidification was carried out and multifunctional glass was obtained.

Following (table 11) Si0₂-- A1₂0₃-- When the glass board material of PbO composition is used The antibacterial properties accompanying change of calcination temperature and a wear-resistant change are shown.

1) Substrate = Si0₂-AI₂0₃- PbO glass

Photocatalyst - Ti0₂

No. 6 7 8 9 Ten Calcination temperature (^) 560 580 740 840 a difference (degreec) with 860 apparent initial softening -- 20 40 200 300 320 antibacterial-properties + + + + + + + + + + + abrasion resistance delta O O O O here -- Si0₂-- A1₂0₃-- 540degreeC and the specific gravity of the apparent initial softening of the glass board material of PbO composition were 3.8. Ti0 obtained₂All Crystals types are Anatases. It was type.

it sets to the abrasion resistant test of (Table 11) .6 -- ten sliding or less -- a crack -- ON Ri and the power in which it has exfoliated -- &lt; -- as for No.7 and 8, a crack does not enter at least ten sliding or more -- good result that a crack does not enter at least 40 sliding or more further, as for No.9 and 10 It was obtained.

At No.9 and 10, since a crack's not having entered and calcination temperature are more than 800 degreeC, at least 40 sliding or more is Ti0.₂a neck generates among particles -- Ti0₂Particles Since it joined together firmly, it thinks.

. In ten sliding or less, it enters and the crack has exfoliated 6, calcination temperature only 20 is higher than the apparent initial softening of a glass board material -- the viscosity of a glass board material -- Sufficient a part -- since it did not become low, it thinks because announcer evening 1 Ze type T i 02 particles which constitute the bottom of the heap of a photocatalyst layer were not laid enough underground into the glass board material.

as opposed to it -- the calcination temperature of that to which at least ten sliding or more does not result in the temperature in which a crack's not having entered and a neck part are generated in No.7 and 8, and softening of a glass board material a difference with temperature -- the viscosity of a glass board material -- TiO₂It is moderately laid underground into a But glass board material. It is considered since it was adjusted to the value to acquire.

it sets to antigenecity study [ on the other hand / (table 11) ] -- No.6*9 -- + + + or + No.10 became + although + and a good result were obtained. this -- calcination temperature -- glass machine 320 °C is also higher than *-ized temperature of material -- T iO which constitutes a photocatalyst layer that the viscosity of a glass board material becomes low too much₂Since particles have been laid underground into a glass board material It thinks.

(Example 18)

Si0₂-- A1₂0₃-- Glass board material ofX[X/ 100 / 100 ] 5 which consists of BaO composition It is 15% of TiO upwards.₂sol solution (the same as Example 1) Splay and Co 1 Tin it applies by the A method -- film thickness -- Ti0 of 0. 8 m₂The layer was formed. Then, Ti 0₂The glass board material on which the layer was laminated is put in the good model of the mold-release characteristic made from ceramics, and they are and Sikonani. The cold after changing ambient temperature for every example and carrying out heating calcination at a A furnace Declining was carried out and multifunctional glass was obtained.

The antibacterial properties accompanying change of the calcination temperature of the above-mentioned multifunctional glass and a wear-resistant change are shown in (table 12) of the following.

(Table 12) Substrate = Si0₂-AI₂0₃- BaO glass

Photocatalyst - Ti0₂

<img file="WO9515816A1_D0010.tif" />here -- Si0₂-- Al₂0₃-- As for the apparent initial softening of the glass board material of BaO composition, 620degreeC and specific gravity are 2.8 and Ti0 on multifunctional glass.₂As for a Crystals type, No.11~13 is announcer. A Tha1Ze type and No.14 were rutile types.

it sets to the abrasion resistant test of (Table 12) -- No.l 1 -- five sliding or less -- a crack -- ON Good result that 10 times or more of sliding or cracks do not enter Ri, the power in which it has exfoliated, and No.l 2, and a crack does not enter No.13 and 14 further in at least 40 sliding or more It was obtained.

That a crack did not enter at least 40 sliding or more by No.13 and 14, and calcination temperature Since it is more than 800 °C, it is T i 0.₂A neck generates among particles and it is T i 0.₂particles -- said -- Samurai joined together firmly -- it is considered a sake.

Having Wound force(ed), &lt; entered and exfoliated in ten sliding or less No.11, and glow Nariatsu A degree is 20 from the apparent initial softening of a glass board material.^eonly C is high -- viscosity of a glass board material Anatase type TiO which constitutes the bottom of the heap of a photocatalyst layer since it did not become low enough₂It thinks because particles were not laid enough underground into the glass board material. as opposed to it -- Soft temperature of the calcination temperature of that to which that at least ten sliding or more did not have Wound force ON No.12 does not result in the temperature in which a neck part is generated, and a glass board material a difference with a degree -- the viscosity of a glass board material -- TiO₂It may be moderately laid underground into a But glass board material. It is considered since it was adjusted to the To value.

it sets to antigenecity study [ on the other hand / (table 12) ] -- No.11~13 -- + + + or + No.14 became -- although + and a good result were obtained. This is Ti0.₂But rutile That it is type and Ti0 which constitute a photocatalyst layer that 320 °C also has calcination temperature higher than the apparent initial softening of a glass board material, and the viscosity of a glass board material becomes low too much₂Particles are Galas. It is thought that it is based on two causes of having been laid underground into a A substrate. (Example 19)

1 from which specific gravity differs for every exampleX[ 00 ] 1 To the surface of the glass board material ofX[ 00 ] 5, it is Ti0 of 15 %.₂It is sol solution by spray and a coating method Ti0 of film thickness 0. 8^m₂a layer is formed -- it ranks next -- Ti0₂the Is laminated(ed) glass board material -- product made from ceramics it puts in the good model of a mold-release characteristic -- a roller 1 Haas kiln -- ambient temperature -- 75 It was referred to as 0, after [ heating calcination ] cooling solidification was carried out, and multifunctional glass was obtained.

it follows on change of the glass board material specific gravity of the above-mentioned multifunctional glass at (table 13) of the following -- anti- -- Fungosity and a wear-resistant change are shown.

(Table 13)

Photocatalyst =Ti0₂

No. 15 16 17 18

Glass board material kind Si0₂-AI₂0₃-PbO Si0₂-AI₂0₃-PbO

Glass board material specific gravity 5.3 3.8 2.8 2.4

Ti0₂Specific gravity 3.9 3.9 3.9 3.9

Glass board material apparent initial softening 480 540 620 680

Calcination temperature (The) 750 750 750 750 Antibacterial properties + + + + + + + + + + + It is related with wear-resistant X O O O antigenecity study, and all of No.15*18 are +. + + and a good result are obtained. It was. Also in any, the calcination temperature of more than 30 degreeC is 3 from the apparent initial softening of a glass board material. It is high in the range below 00"C, and the range of the difference of calcination temperature and the apparent initial softening of a glass board material is the viscosity of and a glass board material T i 0₂It adjusts to the value which may be moderately laid underground into a But glass board material. It thinks because it was the value carried out.

If related with abrasion resistance, in No.15 and five sliding or less, it enters and a crack exfoliates. As for power No.16*18 kept, a crack did not enter at least ten sliding or more. As the cause, the direction of the specific gravity of others, a difference, and a glass board material is Ti 0 at No.15.₂Announcer evening 1 Ze type Ti 0 which constitutes the bottom of the heap of a photocatalyst layer since it is larger than Specific gravity₂It thinks because particles were not laid enough underground into the glass board material.

Therefore, in the abrasion resistance of multifunctional glass, it is Ti0.₂specific gravity with a glass board material it influences -- the direction of the specific gravity of a glass board material -- Ti0₂This worsening if larger than Specific gravity power -- &lt; -- it became clear.

(Example 20)

Si0 of 150 angles₂-- Al₂0₃-- BaO composition (apparent initial softening 620.) C) Or and others -- Ga the surface of the Russ substrate -- Ti0₂Sol and Sn0₂It is the solution which mixed sol and was agitated with Sp Leh and a coating method After an application and * 5 (it calcinated in TC, cooling solidification was carried out, and multifunctional glass was obtained.)

T i 0₂Sol concentration is 4* 6 w t %, and is N H.₃It is adjusted to p H 11 in solution, and is and Ti0.₂crystal Childish kidney of particles is 0. 01 m -- Sn0₂Crystal Child diameter of particles is 0. 0035 m.

In this way, it is TiO about the produced multifunctional glass.₂SnO₂Sn 0 to Sum of₂quantity (molar ratio) The antigenecity study at the time of boiling many things and making it change, and abrasion resistant test The performed result is shown in following (table 14). (Table 14) Substrate =5₂-8 -- 1₂0₃-830 glass

Photocatalyst = Ti0₂Gap particles = SnO₂(0.0035 mu m)

<img file="WO9515816A1_D0011.tif" />

About an abrasion resistant test, it is Sn0.₂it improves with the increase in the amount of of -- 10% or more Change also arises by addition, without a crack entering also in 40 sliding examinations. there is nothing -- Noodle.

If it is a range up to 20% about antigenecity study, it is + like the time of additive-free. + It will be +, if it is + and becomes to 60%. It stopped at +. It is a glass machine when it adds more. Ti0 on the surface of material₂the probability power which covers particles -- &lt; -- it becomes high -- antibacterial properties get worse -- 100% 1 and" -- Ivy.

Therefore, Sn0₂It is a molar ratio about the amount of Addition, and is Ti0.₂Sn0₂10% of Total amount of -- with -- Below upper 60 % can provide multifunctional glass excellent in antibacterial properties and abrasion resistance, if more than 10 % and below 20 % are used preferably.

Abrasion resistance is SnO here.₂It is a basis to above-mentioned The 17 figure to improve with the increase in the amount of of. It is based on the mechanism which gave About explanation.

Thus, a glass board material is passed to the glass board material surface, and it is T i 0.₂a particle layer is held it sets to Composite member -- exposing to the outermost surface -- T i 0₂It is SnO to the gap of particles.₂It is filled up with particles. It is Ti0, without generating a crack, if it carries out and calcinates above 600 degreeC.₂Particles Since the neck part of a between is combinable, an antiwear characteristic improves.

(Comparative example 21)

It is Si0 of 150 angles like Example 20.₂-- A1₂0₃-- BaO composition (apparent-initial-softening 6 20"C) from -- the surface of the becoming glass board material -- Ding 10₂Sol and 5110₂It is the solution which mixed sol and was agitated with spray and a coating method The application back and 750 It calcinates in C. Cooling solidification was carried out and multifunctional glass was obtained.

T i 0₂Sol concentration is 4* 6 w t %, and is N H.₃Power Sn0 which is 0. 01 m like [ it is adjusted to p H 11 in solution, and / and crystal Child diameter of particles ] Example 5₂Particles Crystal Child diameter used 0. 008 m and a little large particles.

In this way, they are antigenecity study and an abrasion resistant test about the produced multifunctional glass. The result compared with the deed and Example 5 is shown in following (table 15).

(Table 15) Substrate =5₂-8 -- 1₂0₃- BaO crow

Photocatalyst = Ti0₂Gap particles = SnO₂(0.0080 m), heat treatment 750degreeC<img file="WO9515816A1_D0012.tif" />

As a result, Sn0 of 0.008₂The effect of the wear-resistant improvement in particles is 0.0. Sn0 of 035//m₂it is weaker than the case where particles are used -- Ti0₂Particles and Sn0₂particles The molar ratio to the sum total also sets to 40 sliding examinations at last at 60% or more. Get hurt -- there are also nothings -- it was it changeless arising

About antigenecity study, it is Sn0 of 0. 0035 m.₂It is the same as that of the case where particles are used. If it is a range to 20%, it is + like the time of additive-free. + It was +, and when becoming 60% or less, it stopped at ++. When added more, it is Ti0 on the surface of a glass board material.₂particles the probability to cover becomes high -- antibacterial properties get worse -- 100% -- 1 and Noodle.

Therefore, Ti0 of 0. 01 m₂When particles are used, it is Sn0 of 0. 008 zm.₂The multifunctional glass which added particles and was excellent in antibacterial properties and abrasion resistance is provided. It is difficult to carry out. As a cause, it is Sn0.₂the steam pressure of particles -- particle diameter power -- large -- Becoming small if it becomes, and SnO which remains without evaporating₂It is TiO when particles are 0. 0035 m.₂it exists in the gap between particles -- while joint intensity might be improved -- 0 .008 m -- Ti0₂It compares with the gap between particles and is Sn0.₂Since the particles are large, they are and SnO.₂particles do not put into a gap -- rather -- Ti0₂Intermediary with high probability of coming on particles It thinks because it is.

From the above thing to Ti0₂Sn0 which should fill the gap of particles₂The size of particles is T iO.₂as opposed to the diameter of a particle -- it is preferred that it is less than 4/5.

(Example 22)

Sn0 of 150 angles₂-- A1₂0₃-- BaO composition (apparent-initial-softening 620degreeC) from -- becoming Ga the surface of the Russ substrate -- TiO₂Sol solution is applied by the spray' Co 1 Tyng method. It is Sn0 to the combined member which in the back calcinated in 75 CTC and carried out cooling solidification.₂It is Sp about sol solution. Leh . coatee which heat-treated by application back and 110"C by the Tongue method, and obtained multifunctional glass. This time Ding*0₂the same thing as Example 5 is used for sol solution -- Sn0₂To sol 0. 0035 m was used.

In this way, they are the examination made from antibacterial properties, and an abrasion resistant test about the produced multifunctional glass. The performed result is shown in following (table 16).

(Table 16)

Substrate = Si0₂-AI₂0₃- BaO glass

Photocatalyst = tauiota*₂Gap particles = SnO₂(0.0035ym), 750 degrees of heat treatment C 110"C

No. 29 30 31 32 33

Sn0₂quantity (mol%) -- 0 10 20 60 100 antibacterial-properties + + + + + + + + + + + -- improving with the increase in the quantity of SnO 2 about a wear-resistant O O O O O abrasion resistant test It is also change 20% of a molar ratio, without a crack entering also in a sliding examination by the above addition 40 times. It stopped arising.

If it is a range up to 20% about antigenecity study, it is + like the time of additive-free. It was ++, and when becoming to 60%, it stopped at ++. It is a glass machine when added more. TiO on the surface of material₂the probability which covers particles becomes high -- antibacterial properties get worse -- 100% 1 and Noodle.

At the final examination, it is SnO.₂Since sol is heat-treated at the low temperature of 110 The, it carries out. Sintering by evaporation 1 condensing mechanism shown in Example 5 does not arise. Nevertheless, abrasion proof This is Ti0 although the sex improved.₂particle diameter is smaller than particles -- namely, specific surface area Sn0 which is greatly excellent in adsorption power₂Particles are Ti0.₂It is and Ti0 by having filled the gap of particles.₂Since combination of particles was strengthened, it thinks.

(Example 23)

Si0 of 150 angles₂-- A1₂0₃-- BaO composition (apparent-initial-softening 620degreeC) from -- becoming Ga the surface of the Russ substrate -- TiO₂Sol solution is applied by spray and the Co 1 Tyng method. The back and 750^eapplying copper acetate solution to the combined member which calcinated in C and carried out cooling solidification -- Drying is carried out -- while irradiating with the light which includes ultraviolet rays after that and returning a copper ion -- photocatalyst layer it fixes -- multifunctional glass was obtained. the mercury lamp lamp was used for the irradiation lamp here the size of Cu particles fixed to the photocatalyst layer here -- average 0. 004 im grade it was .

in this way -- the produced multifunctional glass -- antigenecity study and abrasion resistant test the performed result -- (-- it is shown in table 17).

(Table 17) Substrate =5^₂-8 -- 1₂0₃-830 crows

Photocatalyst = tauiota*₂Gap particle =^ (0.004), heat treatment 750 light reduction

<img file="WO9515816A1_D0013.tif" />

about an abrasion resistant test, it improves with the increase in the amount of Cu(s) -- 20% or more of molar ratio without a crack enters also in 40 times of * Dynamic test by addition -- change -- raw -- Tooth became that there is nothing.

if it is a range up to 20% or more about antigenecity study -- the time of additive-free -- the same -- + + It was +. In Cu, since it has antibacterial activity in itself, it is abundant To add. The antibacterial aggravation by To was not accepted.

However, it is TiO when the amount of addition of Cu is probably little.₂Photocatalysis by a particle layer When the amount of addition of Cu is abundant, the operation by Cu is dominant, and it is [ that for is dominant and ] Ah. Probably, To may be considered. using Cu in a fluid the case where the operation of only Cu is expected since it is gradually eluted at the time of It was -- a photocatalyst -- comparing with L and a case -- a life -- short L and Thought It is obtained. If the amount of addition of Cu becomes abundant, it will also become the part cost overrun. it carried out To -- it seems that it is meaningless to set up the amount of C u not much so much.

It is Sn0 by this example.₂of -- not only an oxide [ like ] but metal like Cu -- TiO₂It was checked that it can become the particles which fill the gap of a particle layer.

(Example 24)

Si0 of 150 angles₂-- A1₂0₃-- BaO composition (apparent-initial-softening 620degreeC) from -- becoming Ga the surface of the Russ substrate -- TiO₂It is sol solution with spray and the Co 1 Tyng method After application and 95 (having irradiated with the light which applies copper acetate solution to the combined member Cooling solid^: carried out by calcinating in TC, and includes ultraviolet rays in it after that [ ], and returning copper Iron, it fixed to the photocatalyst layer and obtained multi- functional glass.)

a B L B lamp is used for an irradiation lamp at this time -- it glared for several minutes. Ti0₂It is Succession from Anakuse to rutile at the process of Is heat treatment. It carried out. T i 0₂of film thickness is sprayed. It adjusted to 0. 4 / zm at the time of 1' coating.

In this way, they are antigenecity study and an abrasion resistant test about the produced multifunctional glass. It carried out. Result [ about an abrasion resistant test, additive-free is good in this temperature region ] It is shown. Even if it adds Cu, it also sets to 40 sliding examinations like the time of additive-free. Change was not produced, without a crack entering.

Antigenecity study is shown in The 22 figure. It is TiO at the time of additive-free.₂But rutile It accumulates and is as bad as 10. When Cu was added to it, antibacterial properties increased. And not only the time of B L B lamp radiation but while not glaring, the amount of Cu support is 0. 7^g/c m.²Antibacterial activity will be + if it becomes above. The amount of Cu support is [ + and ] 1. 2 g/z.²Antibacterial activity will be + if it becomes above. + It becomes +.

the multifunctional glass which was excellent in antibacterial properties and abrasion resistance from the above thing -- providing -- the amount of Cu support -- more than 0. -- it is good -- desirable -- 1. 2 beta g/cm²The above is good.

By the way, the amount of Cu support is a drying process before the B L B Rumble irradiation after a copper acetate solution application. If it puts in, it will improve by leaps and bounds. The relation is shown in The 23 figure. This They are ideas as since metal ion concentration in case the direction at the time of making it dry carries out optical reduction is high. To be.

In (The 24 figure is an example of Cu concentration lwt% of copper acetate) which becomes the maximum when the amount of Cu applications is made the optimal, and this The 24 figure, the amount of Cu support is the amount of support 0

/cm²For carrying out above, it is 0. 2mgZcm about the amount of applications.²It is 2.7 mg/cm above.²Below, it is 1. 2 gZcm about the amount of support.²For carrying out above, it is 0. 3mg A cm about the amount of applications.²It is 2. 4mgZcm above.²Below may be used.

(Example 25)

1 Si0 of 50 Angles₂-- A1₂0₃-- BaO composition (apparent initial softening 680.) C) Or and others -- Ga the surface of the Russ substrate -- TiO₂it is an application with spray and a coating method about sol solution silver nitrate solution is applied to the back and the combined member which calcinated in 950"C and carried out cooling solidification, and it dries to it -- while irradiating with the light which includes ultraviolet rays after that and returning silver Iron -- a photocatalyst layer -- Solid Multifunctional glass was obtained probably.

a BLB lamp is used for an irradiation lamp at this time -- it glared for several minutes. Ti 0₂The phase transition was carried out to rutile from Anatase at the process of Is heat treatment. Ti0₂of film thickness Spray . coatee It adjusted to 0.4 at the time of Tongue.

In this way, they are antigenecity study and an abrasion resistant test about the produced multifunctional glass. It carried out. Result [ about an abrasion resistant test, additive-free is good in this temperature region ] It is shown. Even if it adds Ag, it also sets to 40 sliding examinations like the time of additive-free. Change did not arise, either without a crack entering.

Antigenecity study is shown in The 25 figure. It is TiO at the time of additive-free.₂It was of But rutile Because -- it is as bad as 10. When Ag was added to it, antibacterial properties increased. And not only the time of BLB Rumble irradiation but while not glaring, the amount of Ag support is 0. 05 g Z c m.²Antibacterial activity will be + if it becomes above. The amount of Ag support is [ + and ] 0. l gZcm.²Antibacterial activity will be + if it becomes above. + It becomes +.

Therefore, in order to provide multifunctional glass excellent in antibacterial properties and abrasion resistance, the amount of Ag support is 0. 05 gZcm.²The above is [ good ] 0. l^g cm more preferably.²The above is good.

however, if there are many amounts of Ag support, it will be colored black from brown -- with bad exterior appearance. However, the amount of Ag support is 1//gZcm.²If it becomes below, there will be no coloring.

The above thing to the amount of Ag support is 0. 05 gZcm.²It is 1 igZcm above.²The following is [ good ] 0. 1 gZcm more preferably.²It is 1^gZcm above.²The following It is and is ..

(Example 26)

Si0 of 150 angles₂-- Al₂0₃-- BaO composition (apparent initial softening 680.) C) Or and others -- Ga the surface of the Russ substrate -- TiO₂Sol solution is applied by spray and the Co 1 Tyng method. The back and 950^esilver nitrate solution is applied to the combined member which calcinated in C and carried out cooling solidification, and it dries to it -- while irradiating with the light which includes ultraviolet rays after that and returning silver Iron -- a photocatalyst layer -- Solid Multifunctional glass was obtained probably. a B L B lamp is used for an irradiation lamp at this time -- it glared for several minutes. The phase transition of T i 02 was carried out to rutile from Anatase at the process of heat treatment.

In this way, about the produced multifunctional glass, it is Ti 0.₂of film thickness is changed to various values. It carried out and did an abrasion proof examination, antigenecity study, and a contamination-resistant examination.

At the range within film thickness 2// m examined about the abrasion proof examination this time, it is all good. A good result is shown and it is 4. It is also change, without a crack entering also in zero sliding examination. It did not produce.

About antigenecity study, it is film thickness 0.1. It is + or more in 111. It is + 0. 2 / above + and m. + It becomes +. Therefore, T i0₂More than 0 .2 / m of of film thickness are preferably [ more than 0. l m is good, and ] good.

It is light especially fixing photocatalyst particles to a thermoplastic substrate from the above explanation. The photocatalyst particles which constitute the layer part of a catalyst bed are kept from being buried in a thermoplastic substrate. It is that of It was, The state where the surface exposed photocatalyst particles outside substantially, and Light touch The intermediation effect can fully be demonstrated. the inside of photocatalyst particles -- photocatalyst layer the particles which constitute a lower layer -- the -- since a part is laid underground in a power &lt;&lt;thermoplasticity substrate -- photocatalyst the holding power of a layer improves sharply -- it becomes difficult to produce exfoliation etc.

The 2nd 6 figures and The 2 7 figures are key maps of a basic profile when the direction of a section of multifunctional material is observed by E P M A (electron beam micro analyzer). These As shown in a figure, photocatalyst layer 2 consists of the surfaces which touch the open air for a while. The field where the concentration of an ingredient is almost constant constitutes a continuation (A field) and its crepuscular-rays catalyst bed. An ingredient decreases. the ingredient which constitutes amorphous layer (binder layer) -- the surface -- To it is few in How -- concentration increases, so that it goes to an inside. And up to a certain film thickness (B field) which will become almost constant [ ingredient concentration ] if it comes. A field was defined as the photocatalyst layer and the amorphous layer and C field of middle was defined for B field as the middle class here. however, The 2 6 figures are key maps on expedient of explanation to the last -- actual -- The 2 it is shown in 7 figure -- as -- The 2 6 figures -- concentration -- change of the concentration which arises for the reasons of a manufacturing process into the portion it was explained that was fixed It follows in many cases. in this case, The 2 as [ show / in 7 figure ] -- a fixed field -- To correspond the portion which reaches the minimum of the concentration of Area (A 'field and B' field) -- respectively -- the boundary of A 'field and C' field and B 'field and C' field -- all -- the bottom. Here, the thickness of a photocatalyst layer is the thickness of A field or A' field, and the middle class's thickness is the thickness of C field or C' field.

Movement speed into the amorphous layer which this middle class's thickness and photocatalyst particles soften It can be made to change by controlling the time which can move. Movement speed It controls by the specific gravity difference of photocatalyst particles and an amorphous layer, calcination temperature, atmosphere pressure, etc. It can do. the time which can move -- amorphous material power -- &lt; -- retention time in the temperature to soften It can be made to change by making it change.

When this middle class's thickness is made or more [ of the thickness of a photocatalyst layer ] into 1Z3, it is Increase about adhesion nature more. Surely is made.

Below, a concrete example is described.

(Example 27)

1 It is Si0 on Alumina Substrates of 0 Cm Angle.₂-- A1₂0₃-- NaZK₂Amorphous layer of zero system It forms with spray and a coating method, and is 1^0 of dry calcination back and average-particle-diameter 0. 01 m.₂sol solution is applied with spray and a coating method -- this -- 8 changing retention time and calcinating it by 50"C, -- you of film thickness 0. 2 mupiiota and 0. 5 mutaueta^1 m -- 1 Ze type Ti0₂The thin film was formed. Subsequently, this Anatase type Ti0₂copper acetate solution is applied to a thin film with spray and a coating method -- next -- optical reduction (the source of optical is 20 Watt B L B lamp, distance 1 0 cm [ from a light source to a sample ], and irradiation time 30 seconds) It carried out and obtained the sample. Element of the section according to E PMA about the obtained sample The film thickness measurement by analysis (Ti, Si), antibacterial properties, and abrasion resistance were evaluated. About antimicrobial evaluation, it is coliform bacillus. (E s c h e r ic h i a c o l i W)

3 1 1 It examined using zero share. multifunctional part beforehand sterilized by ethanol 70% the outermost surface of material -- fungus liquid 0.1 5m l (1*50000 C FU) is dropped -- glass Put on the board (1 00X 1 00), and it was made to stick to the substrate outermost surface, and was considered as the sample. the fungus liquid of the sample which irradiated with white light (3500 luxs) after irradiation for 30 minutes -- sterile absorbent gauze wiping -- physiological saline 1 it collects to 0m 1 -- it asks for the probability of survival of a bacillus -- made into the index of evaluation. About a valuation basis, it is the same as that of the case of the . above-mentioned (table 1).

A result is summarized to (table 1 8), and is shown. About antibacterial properties, it is + altogether. + It was +. Abrasion resistance also indicated the good result to be O or O. It is especially the middle class's thickness and photocatalyst layer. Ratios with thickness are c and Noodle altogether at 1/3 or more samples.

(Table 1 8)

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(Comparative example 28)

Ti0 of average-particle-diameter 0. 01 m₂the ammonia dispersion liquid of sol -- Al of 10 cm angle it applies with spray and a coating method on the Mina board -- this -- 850. It calcinates by C. Announcer evening 1 Ze type Ti0 of The film thickness 1₂The thin film was formed. Subsequently, this you Ze type TiO²copper acetate solution is applied to a thin film with a spray' coating method -- this -- Crepuscular-rays reduction (light sources are a 20 ♪ BLB lamp, distance 10 c m from a light source to a sample, and irradiation time 30 seconds) It carried out and obtained the sample. the obtained sample -- antibacterial properties -- and -- Abrasion resistance was evaluated.

as a result -- antibacterial properties -- + + as good as + -- Oh -- abrasion resistance -- △ and non-Sufficient a part -- it was .

From the above explanation, a photocatalyst layer is held via an amorphous layer on the substrate surface, Photocatalyst layer is exposed so that the upper levels may touch the open air -- and a photocatalyst layer -- particles Mutually the multifunctional material which has the photocatalyst function boiled and combined -- Les, The, and amorphous layer A photocatalyst layer has the middle class from whom the concentration of both ingredients changes continuously [ in the meantime ]. by carrying out for obtaining, the adhesion nature of a photocatalyst thin film and a substrate is increased -- fissility-proof -- Toward It was able to be made to stage. When the above-mentioned middle class's thickness was made or more [ of the thickness of a photocatalyst layer ] into 1/3, adhesion nature was able to be increased more.

Next, the case where photocatalyst layer 2 is formed by sintering is described. Drawing 1 (a) is the conventional TiO.₂figure showing the state before sintering of particles, (b) -- the state after sintering -- Show it is a To figure -- The 1 figure -- it is shown in (a) -- as -- the surface of substrate 1 -- TiO₂particles 3 are included sol is applied -- in order to raise film strength, it is heat treatment about this (sintering) If it carries out, as shown in Drawing 1 (b), it will be easy to generate crack 2 a.

the phase transition to this cause and a rutile type -- volume contraction (density becomes high) It starts. others -- if it is before sintering -- TiO₂The interval between particles 101 is L. thing power which came out and existed the interval between particles becomes short with L (Li&lt;L o) by volume diffusion to the other party after sintering with a rutile type -- as the result -- crack power -- &lt;&lt; -- it is thought that it produces.

Then, TiO combined by sintering₂It is SnO to the neck part of particles 3.₂It is made to condense, and a neck part are made thick, and it is Ti0.₂It is [ strength and ] film strength as a result about combination of particle 3 comrades. It is made high.

In order to form the above photocatalyst layers 2, it is T i 0.₂It is S nO to sol.₂it is [ ] mixture about sol -- it agitates and applies on substrate 1 -- it is heat treatment at the predetermined temperature range (sintering) It carries out.

Ding 10₂It is considered as about 4*6wt%, and sol concentration is NH.₃it is adjustment to pH 11 with solution it carries out -- Ding 10₂an average of 1 of particles -- order grain Monster is taken as 0. 01 mupiiota (10 nm) -- Sn0₂It is considered as about abbreviation 1 Owt%, and sol concentration is NH.₃solution adjusts to pHl 1 -- Sn0₂Particles Primary average particle diameter is taken as 0. 0035^m. The primary average particle diameter shown here is XRD (X diffraction). It is crystal child size (primary particles) for which it asked from the half breadth of the diffraction line.

here -- Sn0₂IsTi0₂also depending -- if it is before sintering since steam pressure is high -- Ti 0₂the interval of particles 3 -- The 17 figure -- it is shown in (a) -- as -- L. It comes out and is a certain power. Titanium oxide grain On the surface with child's 3 positive curvature, as for the surface in which steam pressure has negative curvature highly, and the surface of a neck part where it is got blocked and two titanium oxide particles 3 contact, steam pressure becomes low. as a result, Drawing 17 -- it is shown in (b) -- as -- a neck part -- titanium oxide -- steam pressure 5110 [ high ]₂a Enter lump and Drawing 17 -- as shown in (c), it condenses -- Evaporation -- condensation Sintering is performed by the mechanism.

And when sintering is performed by evaporation 1 condensing mechanism, it is Ti0 after sintering.₂Particles Interval L₂Interval L in front of Is sintered. abbreviation -- since it is equal, cracks do not occur. It is TiO before and after like and the above-mentioned sintering.₂A deer is also photoactive [ as a photocatalyst tunic ], without [ ] changing the interval of particles substantially. (R)₃₀It is Drawing 2 in order to consider it as 50% or more. It is Sn0 as shown in 8.₂ofTi0₂It is alike and makes receiving rate (inside ratio) 20~70%. There is necessity.

The weight ratio of the solid content contained in the sol of a combination rate and each is shown. It is Exclusion rate a deed and 30 minutes after light irradiation by evaluation of and optical activity, and decomposition of methyl Merca butane. (R)₃.) -- was made into the index. In detail, it is a photocatalyst tunic in the glass container of 11 L. It is light source (BLB fluorescent light 4W) power about the formed 150 angle tile, , distance of 8 cm it arranges -- methyl Merca butane gas is set to 3~5 p pm -- as -- it is pouring in a container it carries out -- the fluorescent light after checking that there is no adsorption at the time of dark is turned on -- gas Chromatography Concentration change was temporally measured by Rafi.

It is here and is R.₃₀= (x.) 1 X₃₀/x. X 100%

However, chi₀= Initial concentration [ppm] x₃₀= Concentration of 30 minutes after [ppm]

Evaluation of film strength performs sliding wear which used the plastic eraser, and is outside. Change of the view was compared and evaluated. About standard O of evaluation, O, △, and X, it is the same as that of the above-mentioned (table 1).

Drawing 29 -- heat treatment temperature and light -- it is a graph which shows an active relation -- Ti0₂When organic stabilizer is added to sol, optical activity falls, but it is any smell. Heat treatment temperature also sets The to 300*850 degreeC. The heat treatment temperature of this is a 300 degreeC sheep. It is Ti0 when 850 degreeC is exceeded that it is hard to produce activity in Full.₂Structure is from Anatase. It is because it changes to rutile.

the above explanation -- a titanium oxide particle and this titanium oxide -- steam pressure power -- high thing the sol containing quality is applied to a tile etc. -- sintering at a predetermined temperature, evaporation 1 since tunic formation was made to be performed by sintering by a condensing mechanism -- sintering order -- it is -- the interval of titanium oxide particles is abbreviation -- it is hard to generate a crack equally. Oxidization In the neck part between titanium particles, it is SnO.₂in order to Equal strength &lt; condense -- the peel strength of a tunic -- high -- To -- .

In particular, it is S n0.₂The amount of addition of etc (T i 0)₂When -- inner -- a ratio -- 2 0*7 considering it as 0 % -- , film strength, and light -- active both sides can be satisfied -- again -- 3 0 more than 0 °C -- 8 5 Optical activity sufficient by heat-treating in the range below 0 °C can be obtained.

By the way, it is R at gas chromatography.₃₀With the method of measuring, it is a measuring device. Only one sample can be measured about being expensive and one device, but it is inefficient. They are metal, such as P t, T i 0₂Improving [ optical activity ]-by making it for it to be alike and support power Gas Absorption by metal if it is in the photocatalyst thin film of such a structure although known It is hard to judge net optical activity in what thing for the influence of wearing.

It is formed in the surface once constructing a tile etc. as a wall surface. The activity of a Photocatalyst thin film cannot be measured by a gas chromatograph. It is a photocatalyst as a valuation method of the optical activity which does not use a gas chromatograph. Although the method of investigating the probability of survival after the light irradiation of the bacteria which therefore become extinct is also considered, more than a gas chromatograph -- that operation is troublesome and the photocatalyst thin film which supported metal again -- Buddy since bacteria become extinct also by the antibacterial activity of The and the metal itself -- net optical activity -- seal probably -- being hard . then, This which applies the activity measurement method of the following photocatalyst thin films Both -- it is possible.

T i 0 formed in the substrate face as the 1st method₂photocatalyst thin film made into a subject the surface -- halogenation Al power Li solution, such as iodination power Rum or chlorination power Rium it is dropped -- ranking next the dropped alkali halide solution is irradiated with ultraviolet rays for a predetermined period -- difference of p H of halogenation Al power Li solution before irradiation, and p H after irradiation , -- the active size of a photocatalyst thin film is judged.

T i 0 formed in the substrate face as the 2nd method₂photocatalyst thin film made into a subject the surface -- halogenation Al power Li solution, such as iodination power Rium or chlorination power Rium the mixed-solution which added the p H indicator is dropped -- ranking next the dropped mixed-solution is irradiated with ultraviolet rays for a predetermined period -- size of an intermediary photocatalyst thin film also with an active change of the color of the mixed-solution It judges.

T i 0 formed in the substrate face as the 3rd method₂photocatalyst thin film made into a subject an activity measurement film is stuck on the surface -- this state -- the activity measurement philharmonic M concerned it irradiates with ultraviolet rays for a predetermined period -- the active size of a photocatalyst thin film is judged that change of the color of an activity measurement film is also.

the 3rd 0 figures are figures explaining the activity measurement method of The 1 and The 2 -- this substrate 1 surface -- Ti 0₂photocatalyst layer 2 made into a subject is formed -- light like this photocatalyst It is also possible to apply the activity measurement method of a catalyst thin film.

T i 0 formed in the substrate face as the 1st method₂photocatalyst thin film made into a subject the surface -- halogenation Al power Li solution, such as iodination power Rum or chlorination power Rium it is dropped -- ranking next the dropped alkali halide solution is irradiated with ultraviolet rays for a predetermined period -- difference of p H of halogenation Al power Li solution before irradiation, and p H after irradiation , -- the active size of a photocatalyst thin film is judged.

T i O formed in the substrate face as the 2nd method₂photocatalyst thin film made into a subject the surface -- halogenation Al power Li solution, such as iodination power Rum or chlorination power Rium the mixed-solution which added the p H indicator is dropped -- ranking next the dropped mixed-solution is irradiated with ultraviolet rays for a predetermined period -- size of an intermediary photocatalyst thin film also with an active change of the color of the mixed-solution It judges.

T i 0 formed in the substrate face as the 3rd method₂photocatalyst thin film made into a subject an activity measurement film is stuck on the surface -- this state -- the activity measurement film concerned it irradiates with ultraviolet rays for a predetermined period -- the active size of an intermediary photocatalyst thin film is judged also by change of the color of an activity measurement film.

the 3rd 0 figures are figures explaining the activity measurement method of The 1 and The 2 -- this substrate 1 surface -- Ti 0₂photocatalyst layer 2 made into a subject is formed -- this photocatalyst layer 2 -- Light activity For confirming whether there is any sex the surface of photocatalyst layer 2 -- Jo-ized potassium Some it is -- alkali halide solution 3, such as potassium chloride, 0 is dropped -- ranking next Dropped alkali halide solution 3 It is ultraviolet-rays lamp 4 to 0. It is predetermined time by 0. It irradiates with ultraviolet rays and judges the active size of photocatalyst layer 2 from the difference of p H of alkali halide solution before irradiation, and p H after irradiation.

The 3rd 3 figures are graphs which show the relation between ultraviolet exposure time and the amount of change of p H, and are To. Halogenation Al power Li solution 3 The concentration of 0 is 0.1 mol/l., As ultraviolet-rays lamp 4, it is B L B fluorescent light 2. Using 0W, the distance of photocatalyst layer 2 and ultraviolet-rays lamp 4 is 2 O cm. Irradiation time examined as 60 minutes.

The Anatase type, the metal support type, and rutile type any which are understood from this figure He is Ha until the irradiation time of ultraviolet rays becomes 30 minutes, even if it is in photocatalyst layer 2 of evening A. The pH of Rogen-ized Al power Li solution 30 becomes high. [ like ]

Thus, the pH of alkali halide solution 30 by irradiation of ultraviolet rays Oxidation reaction and reduction reaction of the following [ become / high ] are OH' (Hydroxy acid ion) by a cause and a reduction reaction simultaneously. It is because it produces.

Oxidation reaction: 2 I -+2 h⁺= I 2

Reduction reaction: 0₂+2H₂0+4 e - If the pH of alkali halide solution 30 becomes high by -40H-, therefore irradiation of ultraviolet rays, it can be said that the photocatalyst layer 2 has optical activity.

Drawing 34 R₃₀It is a graph which shows a relation with the amount of change of pH. It is here and is R.₃₀Gas which decreased in after [ Is ultraviolet irradiation ] 30 minutes (methyl Merca butane etc.) It is rate (%) and is R from this figure.₃₀That there is positive correlation with the amount of change of pH It understands. That is, the amount of change of pH serves as an index of the existence of optical activity.

if it is in the method of The 1 -- the amount of change of p H -- p H meter or p H measurement See Power performed by A 5 if it is in the 2nd method, the mixed-solution which added the pH indicator in halogenation Al power Li solution 30 is dropped at the photocatalyst layer 2 surface -- ranking next It is dropped. Mixed liquid is irradiated with ultraviolet rays for a predetermined period, and the active size of photocatalyst layer 2 is judged that change of the color of the mixed-solution is also.

Since p H before the ultraviolet exposure of halogenation Al power Li solution 30 is [ pH after abbreviation 4.5 and an ultraviolet exposure ] 5.5~6.5 as a pH indicator, it is Methylle. A do is suitable.

It is if it is in the above-mentioned method of The 1 and the method of The 2, the photocatalyst layer 2 surface Power which trickles into alkali halide solution 30 or alkali halide solution 30 the mixed-solution which added the p H indicator a spread of the fluid dropped for every substrate -- Up fixed liquid thickness is not securable by Chimichi -- reaction area may differ for every substrate. the method shown in The 31 figure cancels this -- if it is in this gentleman method glass after halogenation Al power Li solution 30 etc. are dropped at the surface of photocatalyst layer 2 Transparent plates 6, such as a board, 0 -- halogenation Al power Li solution 3 0 is suppressed -- fixed It has prevented drying, while using thickness.

Halogenation Al power Li solution 3 The surface of substrate 1 is level and the fluid of the 0th grade is Ah. Photocatalyst formed in vertical planes and ceiling surfaces, such as an established wall surface, since To became conditions It is difficult to judge the activity of a thin film.

canceling this -- The 3 it is a method shown in 2 figure -- if it is in this gentleman method basis activity measurement film 7 is stuck on the surface of photocatalyst layer 2 formed in the board 1 surface, and the activity measurement film 7 concerned is irradiated with ultraviolet rays in this state -- he is trying to judge the active size of intermediary photocatalyst layer 2 also by change of the color of activity measurement film 7 Here, it is activity measurement film 7. 0 is potassium iodide or salt to an organic binder. Mixed-solution which added halogenation Al power Li solution and p H indicators, such as-izing power Rum It is obtained by drying and fabricating in the shape of a film.

Next, it considers per rate of a stoma of photocatalyst layer 2. here -- the rate of a stoma -- open pore a rate is good -- the rate of a stoma -- 1 more than 0 % -- 4 less than 0 % -- desirable -- 1 more than 0 % -- 3 Below 0 % carries out.

In this case, the diameter of a crystal of photocatalyst particles of less than 0. 1 mu m is 0.0 preferably. It is good to make it be below 4 m. the diameter of a crystal grain -- smallness -- per L and degree unit volume -- anti- -- since it thinks for Effective area to increase -- the film thickness of a photocatalyst layer -- 0.

A grade may be sufficient. solid phase sintering of the photocatalyst particles is carried out -- making a neck part form To, in raising layer intensity, the diameter of a crystal increases more than 0 .1 m -- since the reaction usable area per unit volume decreases, film thickness is made more than 0 .5 m, preferably more than 0 .6 m.

It is diameter 0.0 of a crystal among the photocatalyst particles which constitute the photocatalyst layer formed in the substrate surface. Less than 1 m is 0.0 preferably. 0 which may add the particles below 8// m. This which fills the gap between photocatalyst particles such by carrying out particle power addition a mosquito -- &lt; -- it can do -- raising-smooth nature of particle filling factor and the surface power -- &lt; -- it can do -- it The film strength to shear stress can be raised. On a surface smooth disposition Dirt can be made hard to attach. in this case, the pore diameter laid underground and here although reduction of the rate of a stoma is caused -- diameter 0.0 of a crystal less than 1 z m -- desirable -- 0.0 0 it is a size containing the particles below 8 m -- size of gas (number A) comparing -- a large -- Deodorization nature is not affected by that of Like.

here -- diameter 0.0 of a crystal less than 1 m -- desirable -- 0.0 0 Eight or less particle a kind -- although it is good fundamentally, and also it fills the gap of photocatalyst particles anything -- a part -- the surface since there is also a possibility of covering, photocatalyst activity is not spoiled -- T i O₂S n0₂ZnO, S rT i 0₃F e₂0₃B i₂0₃W0₃The oxide semiconductor of etc or Ag, Cu, etc. Metal is preferred. Diameter 0.0 of a crystal Less than 1/m, preferably 0.0 0 What kind of method may be fundamentally sufficient also as the addition method of the particles below 8 m. for example, hydrothermal A which generated such an ultrafine particle by processing etc. and was distributed with suitable dispersion liquid Le is applied on a photocatalyst layer with spray and a coating method -- grain growth does not arise It may heat-treat at the low temperature of a grade, and may evaporate an organic dispersing agent. Alkoxide organometallic salt is applied and heat-treated on a photocatalyst layer -- a diluent, an organic ingredient, etc. -- evaporation -- To do it is also good.

the pore diameter of the photocatalyst layer formed in the substrate surface -- it is fixation about So small metal particles It may carry out. metal particles are being fixed -- the electronic capture effect -- light photocatalyst activity improves as compared with the time of a catalyst bed independent -- deodorization nature becomes better If the kind of metal particles is a substance which can catch an electron, it is [ anything ] good here. Metaphor The, Cu, Ag, P t, etc. are raised.

the size of metal particles -- average particle diameter -- average pore diameter Using on the surface of a photocatalyst layer -- small thing It is required. The rate of a stoma of average Stomai on the surface of a photocatalyst layer is 1. More than 0 % is 4. By the sample of less than 0 %, if it observes by an electron microscope, it etc mostly with the diameter of a photocatalyst particle in general. It is and to be smaller than the diameter of a photocatalyst particle is demanded from things. Preferably it is a starting material. The one smaller than the diameter of a photocatalyst particle is good. The starting material of a photocatalyst layer is generally 0.0. Since the materials below 5 m are used, it is 0.0. It is good that it is below 5 m. The concrete example about the rate of a stoma is given to below.

(Example 2 8)

Diameter 0.0 of a crystal Ding 10 of 1/m₂It is the ammonia Peptization type suspension of sol 1 The amount of applications is changed to the tile board of 5 c m angle with spray and a coating method, and it applies to it. This was calcinated above 700 degreeC and by below 900 degreeC, and the photocatalyst layer was formed. It is obtained. It is AnataseTi0 about Sample.₂The diameter of a crystal of particles, the rate of an open pore on the surface of a layer, deodorization nature , abrasion resistance, and fissility-proof were evaluated.

Evaluation of deodorization nature is R.₃₀(L) It evaluated by Measure(ing). R₃₀(L) What's -- the thing of the extraction ratio after light irradiation -- concrete -- 11 Ri the inside of the glass container of Toru -- trial the field in which the photocatalyst thin film of the charge was formed -- distance of light source (BLB fluorescent light 4W) to 8 cm Arrange. methyl Merca butane gas is set to initial concentration 3 p pm -- as -- inside of a container it pours in -- it is obtained by measuring concentration change when light irradiation is carried out for 30 minutes. abrasion resistance performs sliding wear which used the brass tic eraser -- change of appearance it compares -- it evaluated. The evaluation index is the same as that of the above, and is shown below.

O : With no change to a 40 times round trip

O: Crack Enters by Less Than 40 Sliding 10 Times or More -- Photocatalyst Layer (Ti0)₂film is [ ] exfoliation -- a crack enters by less than ten sliding 5 times or more -- photocatalyst layer delta: (Ti0)₂They are entering Wound force &lt; and a photocatalyst layer by sliding below film power &lt;&lt;exfoliation X5 time. : (Ti0)₂Film power exfoliation

A fissility-proof examination is severer in conditions of an abrasion resistant test. It is the done examination. Plus. Sand eraser to which big shearing force is added by a substitute of the Chick eraser (L I ON TYPEWR I TERERAS ER 502) It uses. concrete method of evaluation the sample surface is rubbed 20 times by equivalent power with a method and a sand eraser -- a correlation sample and crack It carries out by comparing an ON Ivy state visually. A valuation basis is shown below. O : completely with no change

O: Optical Degree -- Small -- Change Check

△: A slight change check

X : a glance -- a change check

A result is shown in The 35 figure * The 37 figure.

Drawings 35 are a rate of a stoma, and deodorization nature the time of setting thickness of a photocatalyst thin film to 0. 8 m. And the wear-resistant relation is shown. deodorization nature increases with the increase in the rate of a stoma, and surpasses 50% at and 10% -- at 30%, it reaches to 80% or more. Conversely, set to △ or X when O and it were surpassed at 40%, although abrasion resistance was [ 30% ] O. For producing the member which combines the deodorization characteristic and abrasion resistance from the above thing, it is Light touch. It is a rate of a stoma of an intermediation thin film preferably 10% or more and less than 40% 10% or more and 30% or less It is necessary to carry out.

Crystal of the photocatalyst particles from which Drawing 36 constitutes rate of stoma 20-30% of photocatalyst thin film The film thickness dependence of deodorization nature when changing a path is shown. The diameter of a crystal is R at 0. 1 m.₃₀(L) of film thickness dependence is seen -- when it became thin, deodorization nature fell. 0.04 [ however, ] -- below, film thickness dependence is not accepted -- film thickness 0. 1 m -- right -- The good deodorization characteristic was shown. The diameter of a crystal of the above thing to photocatalyst particles is [ less than 0. ] a photocatalyst thin film by things making it be below 0. 04 m preferably. Even if you thin-film-ize to about 0.1 film thickness, be alike to be able to secure the good deodorization characteristic. To became clear.

Thread of photocatalyst particles with which Drawing 37 constitutes the photocatalyst thin film of 20*30% of the rate of a stoma; pietabeta Deodorization nature when changing a path and a combined state, and film thickness dependence of fissility-proof It is shown. if the desired value of mechanical strength goes up to a fissility-proof examination level -- A net have a The part -- it was set to △ or X by L and a sample. Photocatalyst particles 0 .04 / m of growth of photocatalyst particles is insufficient for forming sufficient neck combination mechanically by solid phase sintering, it is required to grow up to a 0. 1 zm grade, and it is Ah. Ivy. However, coming to have deodorization Sexual power film thickness dependence, if photocatalyst particles are grown up to a 0. 1 m grade, deodorization nature will increase, so that film thickness is thick. Are concrete. It is film thickness 0.5 um and is R.₃₀(L) Surpass 50% of But and it is Reach to 80% or more at 0. 6 m. It carries out. carrying out solid phase sintering of the photocatalyst particles from the above result -- between particles -- neck part it is made to generate -- if grain growth is carried out until the diameter of a crystal becomes more than 0. 1 m -- intensity of a thin film It can be made to fully improve. In this case, the diameter of a crystal is increase of more than 0. 1 zm. Since the reaction usable area per unit volume decreases by carrying out a large, it is film thickness It is necessary to carry out to 0.6 or more preferably above. 0.

(Example 29)

Ti0 of diameter of crystal 0. 01 m₂the ammonia Peptization type suspension of sol -- 15 cm angle it applies to a tile board with spray and a coating method -- this -- 750. With C It calcinated and formed the photocatalyst thin film. T i 0 of this stage₂The rates of a stoma of a thin film are 45% and Ding*0.₂The diameters of a crystal of particles were 0. 02 / m. The diameter of a crystal is different on it. To 3110₂sol is applied with spray and a coating method, respectively -- it dried by 110"C and obtained the sample. o which evaluated deodorization nature and abrasion resistance about the obtained sample

A result is shown in The 38 figure. And it is Sn0. [ deodorization nature ]₂It is a diameter of a crystal of sol 0.00 Even if it makes it change from 35 im to 0. 01 / m, it is a good result which is not almost changeful. It was shown. As for abrasion resistance, an effect when it adds 30% of the weight or more is Sn 0 to it.₂It changed with diameters of a crystal of sol. namely, particles below 0. 008 / m although it improves to O or O when it adds -- 0. 01 m -- the addition effect -- private seal Because -- , -- Re -- there was nothing.

It is a seal by adding the particles below 0. 008^m preferably less than 0.01 Crystal monster among photocatalyst particles from the above thing that abrasion resistance improves. It revealed.

(Example 30)

Ti0 of diameter of crystal 0. 01 zm₂It is 15 cm angle about the ammonia Peptization type suspension of sol. The amount of applications was changed to the tile board with Splay and a coating method, it applied to it, and this were calcinated by 850 degreeC, and the photocatalyst thin film of film thickness 0. 2 m was formed. the following There copper acetate solution is applied to this photocatalyst thin film with spray and a coating method -- next -- optical reduction (a light source is 20-W BLB Rumble, distance 10 cm [ from a light source to a sample ], and irradiation time 10 seconds) It carried out and obtained the sample. The particle diameter of 2 / g cm That of the quantity of the copper supported at this time was number nm*lOnm. Crystal of photocatalyst particles The path was 0. l m. Deodorization nature and abrasion resistance are evaluated about the obtained sample. As a result, R₃₀(L) 89% of Is and abrasion resistance were O. Therefore, it is R by having supported copper as compared with the The 36 figure.₃₀(L) From 18% of But to 89% It acted as Kougami by leaps and bounds.

From the above explanation, the photocatalyst thin film whose rates of a stoma are 10% or more and 30% or less preferably 10% or more and less than 40% was formed in the substrate surface. The member which combines the deodorization characteristic and abrasion resistance can be provided. Next, the gap generated by the photocatalyst layer is filled up with particles smaller than the gap concerned. An example is described. the crevice between the particles estranged with the gap as used in the field of this example -- and -- The both sides of the crevice of a neck part are put.

A photocatalyst layer and the more precise one are the points of the difficulty of attaching of film strength and dirt, excelling the temperature in which Roots makes a photocatalyst layer form generally becomes high -- the quality of the material of a substrate -- Limit according to constant this application which fills up particles with a back process into this gap since it is carried out -- gap Particle addition There may be a rate of a stoma of the photocatalyst layer in front of Addition of more than 10 %. 1 More than [ 0 % ] Since the film of the rate of a stoma is excellent in deodorization nature, the multifunctional material excellent in both sides of antifouling property and deodorization nature can be provided by adjusting fill volume.

This which consists of a material of particles smaller than the gap with which a gap is filled up, and inorganic crystalline material power -- &lt;&lt; -- it is desirable -- T i since it has photocatalyst activity preferably 0₂S n0₂ZnO, S rT i 0₃F e₂0₃B i₂0₃W0₃A Of oxides semiconductor is good. they are a size of particles smaller than a gap, and the average value of a pore diameter generated fundamentally Ri -- it may be small. It is the point that the difficulty of attaching of and dirt and improvement in film strength can be aimed at by the improvement in the surface smoothness by decreasing the particles adhering to the particle surface which has reduction and the photocatalyst function of a gap, and reduction of a surface defect, Specifically, it is 0.0. Less than 1 / 2 m are 0.0 preferably. 0 The small particles below 8 m are good. However, T i 0₂At you―Ze, a thin film is 8 5 (from things to T i 0 particle Diameter [ Carrying out an average pore diameter, the diameter of a T iO particle, etc. in general. being, when it heat-treats below by TC, it fixes on a substrate and it observes by an electron microscope . ] if small Yo). T i 0 which has photocatalyst activity₂The starting material of a thin film is generally 0.0. Since the materials below 5 / ^m are used, it is 0.0. It is good that it is below 5// m.

The rate of a stoma of the surface of the layer which has here the photocatalyst function which filled up the gap with particles is 2. It becomes more difficult to attach dirt than it carries out as [ be / it / less than 0 % ]. The Open The maximum width of a stoma is 0.0. Four It is desirable that it is the following.

here, the rate of a stoma means the rate of an open pore on the surface of a substrate -- between two particles by which the maximum width of the open pore was adjoined of the particles which have a photocatalyst function which constitutes the substrate surface The maximum (average value +3 X standard deviation) of the distance of a crevice They are things.

It is a rate of a stoma of the layer which has the photocatalyst function before filling up the above-mentioned gap with particles 1 When the thing near the 0 % is used, the rate of a stoma is 1. Although it decreases to less than 0 %, here -- burial -- a To be pore diameter -- diameter 0.0 of a crystal it is a size containing the particles of less than 1 m -- gas -- a large -- Tears (number A) Rate 1 of a stoma which did not affect deodorization nature and was beforehand produced by comparing since it was large T i 0 more than 0 %₂This holding the deodorization characteristic equivalent to a thin film It can do.

They are mainly the photocatalyst particles of crystalline material about the layer which has the formed photocatalyst function. Dirt is With at a firm adhesion form so that glass may adhere [ Ms. dirt ] by carrying out. Even if it will not wear and carry out and adheres, it can wipe off comparatively easily. the time of using for a place equipped with a water supply -- it is -- it is effective in an alga becoming difficult to spring up. Here, the photocatalyst particles of crystalline material are 5 O k V about the photocatalyst particles removed from the member. -- Maximum peak of a crystal when an X diffraction is carried out (for example, , T i 0) 3 It is powder at the conditions of 0 O m A. ₂it sets to particles -- Anatase -- 2 6 = 2 5 .3 ° and rutile -- 2 = 2 7 .4 ° power -- &lt; -- they are the crystallized photocatalyst particles to such an extent that it is detected. as a method of filling up the above-mentioned gap with particles, metal Alkoxide, organometallic salt , sulfate, etc. are used -- it forms by performing an application, dryness, and Heat. Metaphor It is suitable Diluent about the process using The and metal Alkoxide, and metal Alkoxide. After-application dry heat treatment is carried out, and the solution mixed with Hydrochloric acid is performed to the outermost surface of a photocatalyst layer. Suitable diluents are Arco 1, such as ethanol, Blopanol, and methanol, here. Although Le are preferred, it is not limited to it. However, water is Including as much as possible. It is better for there to be Up as for nothing. if water is contained -- hydrolysis of metal Alkoxide -- explosive -- it is promoted -- it is because a cause of crack generating is made. adding chloride -- the time of , dryness, and heat treatment -- crack power -- &lt; -- it is for preventing entering. metal alkoxy the power of usually performing the coating method of Do by flow' coating -- &lt; -- Also limited to it It is not that. It is preferred to perform flow and coating in dry air. usual air (atmosphere) if it coats -- it is hydrolysis at moisture in the air -- promotion -- Control of Have been and film thickness becomes difficult. One application may be sufficient as coating and several applications may be sufficient as it. The restoration nature of the photocatalyst layer before an application determines it. When it is neglected several minutes in dry air after that, the film in which the gap of the photocatalyst layer was filled up with particles is a form. It accomplishes.

if a layer and restoration particles before applying restoration particles are used as the same material here the point which can form the film excellent in mechanical strength since a coefficient of thermal expansion is the same -- Desire -- better it is -- .

It is Addition about explanation further about the thing using Ti Alkoxide as an example. It obtains. Ti Alkoxide is further applied to the photocatalyst layer surface -- A which carries out dry heat treatment like -- it sets -- the amount of Ti Alkoxide applications per time, and Ti0₂It is alike, it converts and is 10 mu gZcm.²It is 100 c m above.²It was made to be the following. there is too little quantity Efficiently, since there is nothing if the number of times of an application is made to Add and it is Mustache, if there is too much quantity conversely, the film thickness per application will become thick too much, and a crack will enter at the time of dryness and heat treatment. from -- it is .

it sets at the above-mentioned process of carrying out dry heat treatment -- heat treatment temperature -- more than 400 degreeC 800degreeC -- with -- It was made to be the bottom. 400 It is Amorphous T I 0 in Less Than °C.₂Is anatase type T i 0₂it is alike and does not crystallize -- rapid grain growth arises above 800"C -- does optical activity fall? , -- it is .

The amount of chlorides to Ti Alkoxide in coating liquid is ten-fold [ more than per % of the weight ]. It was made to be below quantity %. At less than 1 % of the weight, the crack prevention effect should show up enough. Since chloride is usually 36% solution when To and 10 % of the weight are surpassed, moisture enters so much. It is because hydrolysis is promoted too much and a crack generates. The quantity of chloride has a good way also with many diluent at many L and the time. It is because a diluent controls hydrolysis. the ratio -- chloride (moisture -- except) : -- a diluent -- 1 : 100*1 : About 1000 are good. Further the layer which has a photocatalyst function is formed -- gap generated on the surface of the layer the layer with which particles smaller than spare time were filled up in the meantime -- further -- an it top -- at least one sort of metal in C u, Ag, Z n, F e, Co, nickel, Pd, and P t -- fixation -- Being done -- it may be made like. By having such composition, it is a photocatalyst function. Since the above-mentioned metal occupies beforehand the site of the layer which it has where adsorbent is high, it is this portion. This which the Al power Li metal in a dust ingredient, calcium, etc. adhere, and loses photocatalyst activity There is nothing. It is One although carried out. The antibacterial action by a photocatalyst is hard to be spoiled, and it is adhesion of fungi. The dirt to twist can also be prevented. Ag, Cu, and Zn are used as the above-mentioned metal. Dirt according to adhesion of fungi more since Leave and these metal itself have antibacterial properties It can prevent effectively. It is Light activity of a photocatalyst layer by the electronic capture effect of these metal. A sex improves.

Sai with adsorbent [ high ] of the size of the metal fixed, and a photocatalyst layer Occupy A beforehand. it is large to such an extent that it obtains -- power and One -- the smaller one is good to such an extent that high activity is maintained. This view Number nm[ from a point ] *: An L0 nm grade is preferred.

As a method of fixing the metal above-mentioned here, they are optical reductionism, heat treatment method, and a spa. Although the Buddha method, a CVD method, etc. can be used, large-scale equipment is not required, but it is the comparatively simpler one. Optical reductionism is desirable at the point which is a method and can be fixed firmly. process using optical reduction solution containing Ag, Cu, Zn, Fe, Co, N i Pd, and at least one sort of metal Iron of P t is applied -- it carries out by irradiating with light including ultraviolet rays. In solution containing at least one sort of metal ions of Ag, Cu, Zn, Fe, Co, N i, Pd, and P t, Copper acetate, silver nitrate, carbonic acid copper, copper sulfate, and Chloride 1 copper, the second copper of chlorination, platinum chloride acid, a palladium chloride, nickel chloride, zinc nitrate , a cobalt chloride, ferrous chloride, ferric chloride, etc. are raised. These metal salt The coating method of solution is spray' Kothe although what kind of method it may be fundamentally used. The Ting method, or A dip and a coating method is simple. the both -- Compare and Quantitative force of the solution to be used -- &lt;&lt; -- it being few and ending, that it can apply uniformly, and film thickness control Shabby -- it is possible not to attach to things and the back Spray and the Co 1 Tyng method are more preferred by a reason. light including ultraviolet rays the light source with which it irradiates just irradiates with light including ultraviolet rays -- concrete -- an ultraviolet-rays lamp, a BLB lamp, a xenon lamp, a mercury lamp, and a fluorescent light -- someday -- it may be . Light should hit at right angles to the irradiation method of light including ultraviolet rays, and an irradiation side. It is preferred to arrange a sample. It is because irradiation efficiency is most excellent. Irradiation time About 10 second * 10 minute is preferred. When irradiation time is too short, it is adsorbent [ of a photocatalyst layer ]. Since the above-mentioned metal kind does not fully adhere to a high site, it is the alkali money in a dust ingredient. Genus, The cause by which calcium etc. adhere and it loses photocatalyst activity, and time are too long. It is for the above-mentioned metal kind to adhere too much, for light to become fully difficult to reach a photocatalyst layer, and for photocatalyst activity to fall. the distance from the light source of a sample -- 1 cm*30 cm -- good -- better -- There. if distance is too short, the whole sample side will not be irradiated with almost uniform illumination -- the upper -- it becomes easy to produce variation in adhesion of an account metal kind -- if distance is too long, it will glare since the illumination of light becomes small in inverse proportion to the square of distance -- a metal kind -- firm -- To adhere becomes difficult.

The gap generated by the photocatalyst layer below is filled up with particles smaller than the gap concerned. The concrete example of a thing is given.

(Example 31)

Ti0 of diameter 0.01 of a crystal₂the ammonia Peptization type suspension of sol -- 15 cm angle it applies to a tile board with a spray' coating method -- this -- 750 degreeC calcinating -- Anatase type T i 0₂The thin film was formed. T i 0 of this stage₂Stoma of a thin film Rates are 45% and Ti0.₂The diameter of a crystal of particles was 0.02. Next, it is Connection on it. S n 02 sol from which Ghost differs is applied with spray and a coating method, respectively. It carries out and is 11 O.^eIt dried by C and obtained the sample. They are deodorization nature and abrasion proof about the obtained sample. The difficulty of attaching of a sex and dirt was evaluated.

Evaluation of deodorization nature is R.₃₀(L) It evaluated by Measure(ing).

Abrasion resistance is a deed and change of appearance about the sliding wear which used the brass tic eraser. It compared and evaluated. An evaluation index is shown below.

O : With no change to a 40 times round trip

O: Crack Enters by Less Than 40 Sliding 10 Times or More -- Ti0₂A layer exfoliates.

delta: Cracks are entering and Ti0 by 5 times or more less than ten sliding.₂A layer exfoliates.

X : a crack enters by less than five sliding -- Ti0₂A layer exfoliates.

It is a line in thick black Magic, Inc. on evaluation of the difficulty of attaching of dirt, and the substrate surface. The dirt condition after wiping off ink by the ethanol after influence and dryness estimated. An evaluation index is shown.

O : marks disappear completely.

O: faint -- Trace power.

△ : The marks of copenhagen blue remain.

X : black marks remain.

A result is shown in The 39 figure * The 46 figure.

Drawing 39 is SnO.₂The difficulty of dirt of attaching to the amount of Addition is shown. It is Sn here. The amount of addition of 02 is T i 0.₂S nO₂The weight sum of the amount of of is received. S etatheta₂It is a table at the rate of weight. It is carrying out. 3 0% or More of Sn0₂By addition, dirt is To for attaching by leaps and bounds. I am tired. It is understood as this reason being three lower Yourself. It is Sn0 in the first place.₂3 0% or more adds. (The 40 figure) which is because the rate of a stoma decreased with less than 20% by Was it. The second Sn0₂It is because the stoma with a big pore diameter decreased by Addition. The 4th 1 figure is S n 0.₂Power SnO which shows the maximum width of the open pore to the amount of addition₂The amount of Addition is 3. Quite as small at 0% or more intermediary To have as 0.04. It is Sn0 to the third.₂Attachment It is understood also as that the surface rough degree improved by Addition having influenced.

Drawing 42 is SnO.₂The deodorization characteristic and abrasion resistance to the amount of Addition are shown.

And it is Sn0. [ deodorization nature ]₂It is a diameter of a crystal of sol from 0. 0035 / m 0.0 Even if it made it change to 1/m, the good result was shown not almost changeful. S n 0₂To the amount of of, it is R at 50% or less.₃₀The good result was indicated to be 80% or more of But. The 3rd SnO of 9 figure₂As compared with the relation between the amount of Addition, and the rate of a stoma, it is Sn0.₂At more than amount of Addition 40 %, and 50% or less, it is rate 1 of a stoma. Less than 0% of deodorization nature is good but. Relation between the rate of a stoma in case this tendency does not add the particles which fill a gap, and deodorization nature (The 35 figure) A different result is brought. The reason is considered as follows. To. That is, the rate of a stoma is 1 in this case. Although it decreases to less than 0%, Since the diameter of a crystal of the particles which the stoma about 0. 02 mu m remains in addition, and fill a gap is also larger as compared with 0. 0035 mupiiota and size (number) of gas than as compared with Drawing 41, he has no grain growth. It is because the phenomenon in which the passage of gas is closed does not arise on these conditions.

And it is SnO. [ abrasion resistance ]₂The effect at the time more than amount of Addition 30 % is S nO.₂Sol It changed with diameters of a crystal. that is, the particles below 0. 008 m were added although a case improves to O or O, the addition effect is accepted in 0. 01 / zm -- it has Power and Ivy.

This experiment showed the following things above.

(1) It is Ti0 to a substrate.₂a film is formed -- particles smaller than meantime spare time in the gap generated on the surface of the thin film (Sn0)₂If sol is added, it will become difficult to attach dirt.

(2) SnO₂The amount of Addition is T i 0.₂S nO₂It is at 30 % of the weight or more to Total weight of. If it is, abrasion resistance will also improve that it is hard to attach dirt. (3) Sn0₂The amount of Addition is Ti0.₂Sn0₂It is at 50 % of the weight or less to Total weight of. If it is, deodorization nature can be maintained while it has been good.

(4) if the maximum width of an open pore is made below into 0. 04^m for the rate of a stoma less than 20% -- Dirty -- A -- .

(Example 32)

It is Anatase type T i 0 to Useless L of the light of San'a of a chamber pot, and a flank part.₂the film was formed The usual announcer evening -- a thing is installed -- a practical test is done for two weeks -- Ze type Ti0₂A film is formed. It compared with what is not carried out. As a result, the yellow stain to which both originate in fungi and Urinary stone adhered. However, a stain in the grade rubbed in San'a of the usual toilet bowl While not falling, it is Anatase type Ti0 to a flank part.₂At the thing in which the film was formed, it is This. When carried out, the yellow of the stain stopped being almost conspicuous.

San'a side piece (this result since This is not irradiated with light is the announcer evening -- Ze type T i 0)₂Membranous not a photocatalyst effect but straw-mat stain are ToL and Completion of crystalline material for adhering firmly. Na evening -- Ze type Ti0₂Since the film was formed in the surface, it is understood.

(Example 33)

15 It is Si0 to Surface of Earthenware Tile of Cm Angle.₂-- A1₂0₃-- NaZK₂0 Frit is applied -- ranking next -- the surface -- Ti0 of diameter of crystal 0. 01 / m₂Ammoni of sol Peptization type suspension is applied with spray and a coating method -- 750"C -- 2:00 it calcinates in between -- Ti0₂Three kinds, 0. 2 m, 0. 4 m, and 0., were produced by the film thickness of the thin film. TiO of this stage₂The rates of a stoma of a thin film are 45 % and Ti0.₂Connection of particles Crystal diameter was 0. 02 m. It is Chinese 1 Tetera further to the cooled above-mentioned sample. 10 of Ethoxide, 36% chloride, and ethanol : 1 : 400 (weight ratio) Mixture which applied and dried liquid with flow and a coating method by making dry air into a carrier. The amount of applications is Ti0.₂It comes out and is 40~50 mu g cm.²It carried out. It calcinated for 10 minutes by 500 degreeC after that. This Ti Alkoxide application process was repeated 1*5 times. profit a Was done sample -- the difficulty of attaching of deodorization nature, antibacterial properties, abrasion resistance, and dirt -- criticism Value was carried out.

It examined using coliform bacillus (E s c he r i c h i a -- c o l -- i W31 10 share) about antibacterial properties. the multifunctional material beforehand sterilized by ethanol 70% -- the maximum -- fungus liquid 0. 15m l (1~50000 CFU) is dropped at the surface -- it puts on glass board (1 00X 100), and makes it stick to the substrate outermost surface -- it was considered as the sample. the fungus liquid of the sample which irradiated with white light (35 00 lux) the irradiation back for 30 minutes is wiped with sterile absorbent gauze, and it collects to physiological saline 1 Om 1 -- it asks for the probability of survival of a bacillus -- + which is an index of evaluation + About ++10, 10, and 1, it is the same as that of the above.

Deodorization nature is R even if it sets on which conditions of the above.₃. 80% or more and antibacterial properties are + at (L). + It was +.

The difficulty of attaching of dirt (The 44 figure) And abrasion resistance (The 45 figure) If it attaches, they are the number of times of a T i Alkoxide application, and TiO.₂It was dependent on film thickness. The number of times of Ti Alkoxide application When making [ many ] it, the difficulty of attaching of dirt and abrasion resistance improved. Ti0₂Film thickness It is the difficulty of attaching of dirt, and abrasion-resistant at such the small number of times of Ti Alkoxide application that it is thin. Abrasion improved. It is Ti Alkoxide application as one of the reasons of the above thing. ToTi0₂Reduction of the rate of a stoma on the surface of a layer can be considered. It is Ti0 to Drawing 46.₂Mind on the surface of a layer The rate of a hole, the number of times of a T i Alkoxide application, and T i 0₂A relation with film thickness is shown. T i 0₂They are a decrease a few, power, and One, so that the rate of a stoma on the surface of a layer and the number of times of Ti Alkoxide application are increased. It is T i 0 again.₂The degree is decreasing by the same number of times of a T i Alkoxide application, and and this relation are [ Film thickness force thin and ] the number of times of Ti Alkoxide application, and Ti0.₂It is To for being stained with film thickness and dirt. And it corresponds well with the relation with abrasion resistance. especially -- the difficulty of attaching of dirt -- if it is -- the case of Example 31 -- the same -- less than 20% of the rate of a stoma -- any -- O and It was.

(Example 34)

15 It is Si0 to Surface of Earthenware Tile of Cm Angle.₂-- Al₂0₃-- Na/K₂0 Frit is applied -- ranking next -- the surface -- 1^0 of diameter of crystal 0. 01 zm₂Ammoni of sol Peptization type suspension is applied with spray and a coating method, and it is * 50.^eIt calcinated by C for 2 hours. TiO of this stage₂Film thickness 0. 4 zm of a thin film and the rate of a stoma are 45% and T i0.₂The diameter of a crystal of particles was 0. 02 m. It is further Chita to the above-mentioned sample which ? Declination carried out. 10 of Nate tetraethoxide, 36% chloride, and ethanol : 1 : 400 (weight ratio) Dry air is made into a carrier for the mixed-solution, and it is Paint with flow and a coating method. Cloth was carried out and it dried. The amount of applications is Ding 10.₂It comes out and is 40~50._￡;111²It carried out. After that 5 It calcinated for 10 minutes by 00 °C. This T i Alkoxide application process is repeated 3 times. It was. 1% of the weight of silver nitrate solution is further applied on a sample after that -- optical reduction (light sources are a 20 Wat B L B lamp, distance 10 c m from a light source to a sample, and irradiation time 3 0 second) It carried out and obtained the sample. The quantity of the silver supported by the sample surface here is 0. * n._gThe particle diameter of /cm 2 and silver was an average 40 nm grade. They are antibacterial properties about the obtained sample. It measured about a sex and the antibacterial properties after long-term use.

About the antibacterial properties after long-term use, it examined as follows. trial obtained first ethanol etc. may be sufficient and it washes the surface of a charge -- it was made to dry by 50"C next, it sterilized the bathtub water extracted in the public bathhouse is put into a beaker -- the sample was made immersed into it and it was neglected for one month. A sample is taken out after that and it is the maximum table of the washing back and multifunctional material at ethanol etc. The field was sterilized by ethanol 70%. subsequently, fungus liquid 0. 15m l (1* 50000 C F U) of coliform bacillus (3110 shares of E s c h e r_i c h i a c o l i W) is put on glass board (X[ 100 ] 100), and it is made to stick to the substrate outermost surface -- it was considered as the sample. the fungus liquid of the sample which irradiated with white light (3500 luxs) after irradiation for 30 minutes is wiped with Sterilization Ga - Ze, and it collects to 1 10 m of physiological salines -- it asks for the probability of survival of a bacillus -- index of evaluation It carried out. The evaluation index is the same as that of the antigenecity study of Example 3.

It examined also about the sample used in Example 33 for comparison.

As a result, the sample produced in this example about early antibacterial properties and Example 3 Both the samples produced by 3 are also +. + Although it became +, in 1 power and antibacterial properties of the previous month, they are both. The difference was produced in between. That is, by the sample produced in Example 33, antibacterial properties get worse to 10. At the sample produced in this example although carried out, it is +. + which showed the value which is not different from + and the first stage. This is TiO.₂When silver occupies the site on the surface of a layer where adsorbent is high, it is understood for preventing dust etc. from adhering to Cyto with adsorbent [ high ] while in use. the layer which has a photocatalyst function is formed in the substrate surface from the above explanation -- table of the layer Since the gap generated to the field was filled up with particles smaller than the gap the conventional Light touch the quantity and the size of a gap which exist in the surface rather than an intermediation thin film become small -- and the surface Since smooth nature becomes good film strength is improved, maintaining deodorization nature and antibacterial properties -- and -- the polymers which constitute a dirt ingredient, dust, fungi, etc. can make it hard to adhere the case where the low material of the melting points, such as To, next soda glass, is used as a substrate -- One Are and it states. namely, -- the case where a photocatalyst thin film is formed in the low melting point substrate surface -- this -- it is photocatalyst thin film formation temperature, and *-ization of a substrate already starts -- the formed photocatalyst thin film is buried into and a substrate -- therefore -- light does not reach a photocatalyst layer -- a photocatalyst function -- Depart The fault that Vienna cannot be carried out will be produced.

So, in such a case, it is S i 0.₂Layer in which the melting point is higher than substrates, such as a coat It passes and fixes photocatalyst particles to a substrate. A concrete example is described below.

(Example 3 5)

Before performing titanium oxide and coating to soda glass, it is on the soda glass surface. Silica and Co 1 Tyng was given.

1 By the method of the following [ on the soda glass surface of 0 c m angle / silica and coating ] It went. First, tetra-ethoxy Silane and 3 They are 6 % chloride, pure water, and ethanol 6 : 2 : 6 : 8 It mixes by 6 (weight ratio). Since it generates heat at this time, it is 1-hour Ho. Abandon is carried out. It acted to soda glass as Florco 1 Tyng of this.

Next, coating solution is produced. Coating solution is Chita Ney -Totet Laethoxide and ethanol 1 : 9 (weight ratio) To the mixed thing, 3 receiving titanate tetra-Ethoxide in 6 % chloride -- 1 o which was added 0% of the weight and produced -- 3 added here the quantity of 6 % chloride receives titanate tetra-Ethoxide -- more than 1 % of the weight 3 0 % of the weight or less -- desirable -- more than 5 % of the weight 2 0 % of the weight or less -- L, A crack is prevented from entering at the time of dryness of a back process, and calcination by addition of a proper quantity of chlorides. It can carry out. namely, -- if there is too little quantity of chloride -- crack prevention -- enough -- it cannot attain -- if there is too much quantity of chloride, hydrolysis of titanate tetra-Ethoxide will be accelerated by the increase in the quantity of the water contained in a chloride reagent -- a homogeneous coat -- difficult -- It becomes.

Next, it is flow Coating to the soda glass substrate surface about this solution in dry air. A is carried out. Dry air puts air with little moisture here as compared with the not a meaning but usual air called the air which does not contain moisture at all. At this time, it is Apply in a drying process. When it is and coats in the usual air, it is titanate Tetrae at moisture in the air. Hydrolysis of Toxido is accelerated, 1 time of the amount of coats increases too much, and it is Dry of a back process. A crack enters easily at the time of Dry and calcination. What hydrolysis is accelerated for Control of the amount of coats becomes difficult. For crack prevention, 1 time of the amount of support of titanium oxide is 1. 0 0 g A c m²It is preferred that it is the following. It is oxidization Chita this time. 1 time of the amount of support of A is 4. 5 mu g Z c m²It carried out.

It is 1*1 in dry air after that. A titanium oxide film is a form by carrying out a drying process for 0 minute. It accomplishes. In the principle which shows below that titanium oxide is obtained at the process so far To. Chinese 1 Totetrae whose starting material is a kind of titanium Alkoxide here (even if it uses other titanium Alkoxide, same thing arises theoretically) which is Toxido. This titanate tetra-Ethoxide is mainly Florco 1 tee. A hydrolysis reaction is carried out to the water in dry air at the time of Tongue, and titanium hydroxide is generated. To et al. a drying condensation reaction is produced at the time of dryness -- formless titanium oxide generates on a substrate. The titanium oxide particles generated at this time are 3*1. 5 It is high purity in 0 n m grade. the -- a sake -- this titanium oxide -- others -- comparing with the titanium oxide obtained by the process -- it is sintering at low temperature There is the feature to carry out.

It is the combined member obtained by the described method Further 3 0 0*5 0 It calcinates by 0 °C. Multifunctional material was got. It calcinates from the coat of titanate tetra-Ethoxide if necessary. The process of until was repeated and titanium oxide was thick-applied.

Thus, it is One to the deodorization characteristic, an antiwear characteristic, and the antibacterial characteristic about the obtained sample. It evaluated by being. The result is shown in (table 1 9).

(Table 1 9)

<img file="WO9515816A1_D0015.tif" />

About the deodorization characteristic, the initial concentration of methyl Merca butane is adjusted to 2 p p m. Diameter 2 6 c m X height 2 A sample is installed into the cylindrical vessel of 1 c m, 4 B L [ ] of W -- Turnip -- Tongue Extraction Ratio Methylmel of 30 Minutes after at the time of Carrying Out 8 Cm Separation of the B Fluorescent Light from Sample, and Irradiating with Light (R)₃. (L)) and Methylmel of 30 minutes after at the time of covering light -- a turnip -- tongue extraction ratio (R)₃. It evaluated by measuring (D).

performing sliding wear which used plastic eraser . about the antiwear characteristic -- outside change of a view is compared -- it evaluated. Evaluation index O at that time, O, △, and X are the above. It is the same.

It examined using coliform bacillus (E s ch e r i c h i a -- 110 shares of c o 1 i W3) about the antibacterial characteristic. multifunctional material beforehand sterilized by ethanol 70% fungus liquid 0. 15m l (1*50000CFU) is dropped at the outermost surface -- it puts on glass board (X[ 100 ] 100), and makes it stick to the substrate outermost surface -- it was considered as the sample. the sample which irradiated with white light (5 200 lux) the irradiation back during 30 minutes, and trial which maintained under the shading condition the fungus liquid of a charge is wiped with sterile absorbent gauze, and it collects to physiological saline 1 Om 1 -- the probability of survival of a bacillus it asks -- it was considered as the index of evaluation. Evaluation index + + It is the same as that of the above, and ++10, 10, and -- are Aho.

It is R although a good result is indicated to be O by sliding examination in calcination temperature 30 CTC.₃. (L) was 0%. this -- you from formless titanium oxide -- crystallize to 1 Ze It is and it is thought that it is based on things.

In a synthetic experiment At 400 °C which Anatase can check now in X-rays, it is Sliding. It is R although Dynamic test also indicates a good result to be O.₃. (It acted as Kougami also of the D to about 60%.) Antibacterial properties also became +. A sliding examination is as good as O similarly also at 500 The. It is R although a result is shown.₃. (L) is improving to about 60%.

When temperature is made to increase, modification of the soda glass of a substrate is raw at 550 degreeC. Tooth and multifunctional material were not able to be manufactured.

(Example 36)

It is a metal grain in order to further raise the photocatalyst characteristic of the sample obtained in Example 35. The child was supported. The reduction reaction is also performing the photocatalyst simultaneously with oxidation reaction. if -- reduction if a reaction does not progress, an electron will not be consumed but particles will be charged -- oxidation reaction does not progress, either To. It is Example 1 and is R.₃. (L) stopped to 60% -- this power -- &lt; -- it results When -- it is considered. In order to prevent this, titanium oxide particles may be made to support metal particles, an electron may be missed, and electrification may be prevented.

Support of metal particles is I got it by the following methods. He is Flo to a photocatalyst about the solution of metal salt. It coated one time and irradiated with BL B fluorescent light 20W in distance 20 cm for 1 minute. It is a silver place in the case of copper support in metal salt solution about the lwt% ethanol solution of copper acetate. The 1 w t % Etah Nor -Reno water = 1 Z1 mixed solution of silver nitrate was used for Synthesis. After irradiation It washed and dried. Melting which contains ethanol without using metal salt solution here The metal salt solution to having used liquid and a sample is damp, and a sex is based on a good thing.

It is [ sample / which was obtained in this way ] criticism about the deodorization characteristic, an antiwear characteristic, and antibacterial properties. Value was performed. The result is shown in (table 20). calcination temperature -- 500 degreeC -- profit Only the Was done sample was used.

(Table 20)

<img file="WO9515816A1_D0016.tif" />

The sliding examination indicated the good result to be O. R₃₀(L) Are as fast as 98% of Is. It improved. Antibacterial properties are also +. + It became +.

(Comparative example 37) it sets in The Example 35 -- Silica 1 tee Tongue -- Apply L and except It was made the same. That is, it is a titanium oxide' coatee to the soda glass of 10 cm angle. Tongue It carried out. the result -- (-- it is shown in table 21).

(Table 21)

Calcination temperature () abrasion resistance R30 (L) R30 (D) antibacterial-properties (L) antibacterial properties (D)

300 O 0% 0%

400 O 0% 0%

500 O 0 % 0 % (Table 2 1) from -- 3 0 0 °C and 4 0 0 °C and 5 0 0 °C -- Both -- Sliding Examination -- O -- Right -- although Good Result is Shown -- R₃. (L) is a glow from the coat of titanate tetra-Ethoxide. It is a process to Formation 1 Even if repeated 0 times, it was 0 %. Each antibacterial properties are 1. It was.

3 0 0 °Cr, R₃. (L) a thing with bad power, and titanium oxide -- yet -- formless titanium oxide from -- you -- it thinks because it is not crystallizing to 1 Ze.

-- A way and 4 0 0 °Cs 5 0 At 0"C, it is already the announcer evening from formless titanium oxide. -- To Ze It is crystallizing and is R at the reason for the above.₃. (L) cannot explain a bad thing. this -- A 1 Dagallas of the substrate softened the cause -- an oxidization Chi evening A film is burial in glass to a sake it carried out -- it is considered a sake

Even if it is a substrate of a low melting point more nearly comparatively than the above explanation, it is quantity Fusion between photocatalyst layers. By passing the layer of a point, manufacture of the multifunctional material which has deodorization nature and antibacterial properties was attained. Next, in order to give a photocatalyst effect to the surfaces, such as tic [ inferior to heat resistance / brass ] The example which carries out suitable is described.

Tic [ not only / inferior to the quality of the material of a substrate and heat resistance / brass ] but pottery, ceramics , metal, glass, or its compound thing is [ anything ] fundamentally good.

what kind of thing may be sufficient also as the shape of a substrate -- the thing of the complicated shape of the thing of the simple shape of board-shaped objects, such as a spherical thing and pillar thing, a cylinder thing, tile , wall material, and a flooring material, etc. or sanitary chinaware, a washstand, a bathtub, a sink stand, a toilet seat sheet, etc. is also available. Substrate table A field may be porous or the quality of precise may be sufficient as it.

The kind of binder, the quality of inorganic glass, thermoplastics, and Hitoshi Handa's thermoplastics But thermosetting materials, such as a fluoro-resin, Shiroki Sun resin, and silicon resin, are also. It is and is .. However, since it irradiates with the light which includes ultraviolet rays at a back process, it is an optical corrosion resistance material. Things are preferred. 3 0 (being [ it / the material which can be hardened below by TC ] power desirable .) the case where only heat treatment of 00 or less The can be performed -- this application -- an owner -- thermoplastics since especially the for nature is high -- 3 Material which may be softened below in 0 CTC a thermosetting material -- 3 As a material which fulfills these conditions, they are a fluoro-resin and Shiroki Sun resin with thermoplastics at quality of boric acid system glass, solder, an acrylic resin, etc. and a thermosetting material. Silicon resin etc. are mentioned.

As a method of applying these binder layers on a substrate, it is business about thermoplastics. When it is, they are spray and a coating method, a roll' coating method, and Di. A and coatee Although there are the Tongue method etc., the any may be used -- it carries out -- other than this -- A method may be used. A binder component is not necessarily Vine at the time of member completion. It does not need to be in agreement with Da 1 composition. for example, the quality of Binder &lt; inorganic glass -- from a To case -- quality of inorganic glass, such as the application thing, a grain, the shape of fritto, mass, and powder the suspension of a constituent may be sufficient -- it carries out -- the mixed-solution of the salt containing a composition metallic component may be sufficient. By Also the case where Nda is resin, the solution of resin of the composition may be used and it is the more nearly other one. A method may be used.

it is dryness about the binder layer applied before applying photocatalyst particles on a binder layer it carries out -- moisture etc. may be evaporated. There are the method of heating with the drying method in this case, method according to room temperature neglect, and a substrate, etc.

binder layer applied before applying photocatalyst particles on a binder layer it is lower than the apparent initial softening of a substrate -- a binder layer is change to the binder composition at the time of member completion it carries out -- it may heat-treat at the temperature moreover softened. According to this method, he is Vine. Since a binder layer becomes smoother beforehand when forming photocatalyst particles on a Da layer, and the photocatalyst particles to apply can demonstrate effect sufficient also in a small quantity. mixing a binder with a hardening agent, when heat hardening material is used -- a substrate -- To apply a diluent is added to How to do, for example, thermosetting resin, -- it ranks next and carries out by applying to the substrate surface the mixed-solution which added and obtained the hardening agent.

Increase viscosity -- 1 0 more than 5 p o i s e -- 1 0 7 using less than 5 p o i s e -- Desire better -- There. 1 Photocatalyst Particles are Applied after Using High Viscosity Value more than 05 P 0 I S E. Things, state where photocatalyst particles are not completely buried into a binder layer burial becomes possible -- again -- 1 0 7 using less than 5 p o i s e -- Light touch an intermediation particle layer -- as for a bottom-of-the-heap part, the part may be laid under the binder lower layer at least It is because it becomes obtaining.

It is a starting material to the method of applying the above-mentioned photocatalyst particles to the binder layer surface, and a basic target. It carries out by applying on a binder layer what performed suitable processing. Although the sol suspension of the quality of a photocatalyst constituent is desirable as a starting material, in addition to this, it is light. The suspension of the particulates of catalyst composition, etc. can be used. In which case, it is uniform. In order to carry out a coat, finishing agents, such as a dispersing agent, are added, and it is photocatalyst composition in suspension. It is necessary to make it a thing not condense. An application of a up to [ a binder layer ], spray and a coating method, the roll 'coating method and Di A' coating method, etc. Although it is, the any may be used and the other method may be used. Or more [ 1 Z ] 4 burial of the burial thickness to the binder layer of a photocatalyst layer, and the thickness of a photocatalyst layer It is desirable on joint intensity with a carrying-out power substrate. It is the thickness of a photocatalyst layer here. Ingredient ultimate analysis which constitutes the photocatalyst particles of the direction of a section by E P MA etc. It asks, the upper levels whose amount of ingredient elements which constitutes photocatalyst particles is about 1 law, and photocatalyst grain Ingredient origin which constitutes a binder from the depth in which the amount of ingredient elements which constitutes a child begins to decrease base -- quantity consists of a burial part between the depth which begins to become fixed.

the finishing agent adhering to a photocatalyst -- mainly -- sol of the starting material of photocatalyst particles In order to distribute, it consists of an ingredient added. being concrete and pen Taeri Tori power, such as A , Trimethi roll propane, Triethanolamine, Trimethi mouth 1Ramen , silicon resin, and Alkyl chlorosilane, -- &lt; -- it is mentioned.

3 9 It is 1 .* mW/ C M about Light of Wavelength below 0 N M.²As the light source of the light included above A B L B fluorescent light, an ultraviolet-rays lamp, a germicidal light, a xenon lamp, a mercury lamp, etc. are Behavior. To be. 3 9 It is 1 .7 mW/ C M about Light of Wavelength below 0 N M.²above Contains -- it can kick a certain amount of [ dispersing agent ingredients, such as a reason which is not if it is The, and silicon resin, ] optical corrosion resistance -- an owner -- It is for not decomposing, if there is no ultraviolet-rays intensity of this level in order to carry out. under the present circumstances -- although disassembly of a dispersing agent is so quick that and an ultraviolet wavelength are short -- kind of binder there is a possibility of also disassembling a binder -- and it is harmful also to a human body. This to 2 5 The way which is more than 0 n m is . Illumination is also 3 mW/ c m.²A grade is Looking. Since it seldom contributes to improvement in catabolic rate even if it makes illumination increase by more than it although catabolic rate speeds up with the increase in a degree, it is 3 m WZ c m.²Below is enough. It is The 4 about the above process. It is typically shown in 7 figure. Binder layer 6 is passed on substrate 1. Photocatalyst layer 2 lays a lower layer part under the binder layer 6, and is formed in it. 6 a is a layer which consists of a finishing agent etc. which check photocatalyst activity. U V is 3. 9 It is 1 .7 mWZ c m about the light of the wavelength below 0 n m.²The light included above is shown.

next, layer which becomes the substrate surface mainly from photocatalyst particles 3 and thermosetting resin 6 it forms and irradiates with ultraviolet rays similarly -- that to which the photocatalyst layer was exposed -- opinion Ming is carried out. (Refer to The 4 8 figure) Photocatalyst particles 3 are firmly fixed to a substrate also by this gentleman method by thermosetting resin, and it is 3. 9 It is 1 .7 mW/ c m about the light of the wavelength below 0 n m.²irradiating with the light included above -- the light irradiation portion of a photocatalyst particle surface -- Light touch an intermediation reaction arises -- the thermosetting resin which exists in a finishing agent and the direction of a light source -- preferential -- part a solution -- it is evaporated -- acquiring sufficient photocatalyst activity, since photocatalyst particles are exposed in the open air To is made.

the formation method of the layer which mainly consists of photocatalyst particles and thermosetting resin -- comparing the photocatalyst sol suspension distributed with sufficient The -- thermosetting resin, a diluent, and a hardening agent -- this -- the mixed-solution added and obtained in turn is applied to the substrate surface -- it heat-treats and forms. here -- the sol in photocatalyst sol suspension -- diameter 0.0 of a crystal below 5 m -- good -- better To -- 0.0 Below 1 m is good. crystal Strength -- &lt; -- since photocatalyst activity is so high that it is small It is. single-distributing-as much as possible-sol in photocatalyst sol suspension A desire better -- There. It is because the uniform coat is so possible that dispersibility is good.

As opposed to the thermosetting resin, the white light, and the ordinary fluorescent light level light which are used here It is more desirable for there to be optical corrosion resistance. Because it excels in the endurance at the time of that power &lt; use It is. Shiroki Sun resin and especially a fluoro-resin are preferred in the meaning.

The viscosity of the mixed-solution which consists of photocatalyst sol and thermosetting resin is reduced, and a diluent is a basis. It adds in order to make the mixed-solution easy to apply to the material surface. Therefore, here If the diluent to be used is a solvent which can achieve this object, it is [ anything ] fundamentally good. For example, water, ethanol, Blopanol, etc. can be used.

coating method [ to the substrate of the mixed-solution ], spray' Co 1 Tyng method, and roll - the Co-- Tyng method and dip '-- there are a coating method, spin , a coating method, etc. the any may be used -- it carries out -- the other method may be used.

It is common to use heat treatment, an electric furnace, gas kiln, a vacuum furnace, a pressurization furnace, etc. It is not restricted to it.

It is thermosetting resin to the substrate surface about the layer which mainly consists of photocatalyst particles and thermosetting resin. It may be made to form via a layer or photo-setting resin layer (middle class: C). (Refer to The 4 9 figure).

according to this method, allotting in the middle of a substrate and a photocatalyst layer, even if a substrate has unevenness etc. before applying a photocatalyst layer by the Thermosetting property resin layer or a photo-setting resin layer -- very -- Because -- The -- since a smooth field can be formed, a photocatalyst layer can be formed uniformly easily. Again The thermosetting resin layer or photo-setting resin layer allotted in the middle of a substrate and a photocatalyst layer Since Join with a substrate is fully made, It is Light touch even when irregular on the surface of a substrate. While being able to form thinly the layer which consists of intermediation particles and thermosetting resin, it is near the surface of a substrate. 3 which is a back process since photocatalyst particles can be centralized 9 Below 0 n m It is 1 .7 mW/ c m about the light of a wavelength.²It is more about the process of irradiating with the light included above for a short time. It can finish. layer which becomes the upper surface from photocatalyst particles and thermosetting resin intensity sufficient since it exists to be decomposed and evaporated at the time of a back process and use -- an owner -- the thermosetting resin layer which allots the ultraviolet rays to carry out in the middle, or a photo-setting resin layer Until -- attainment Since it does not carry out, about the thermosetting resin of this portion, it can choose arbitrarily. For example, low Co In order to also choose a cheap epoxy resin for strike-izing and to give design nature Coloring resin may be used.

the formation method of the thermosetting resin layer allotted in the middle of a substrate and a photocatalyst layer here -- comparing a diluent is added to A thermosetting resin -- the mixed-solution which ranked next, and added and obtained the hardening agent -- basis it applies to the material surface -- it is made to solidify by heat treatment or neglect, and forms. Photocatalyst When the layer allotted in the middle of a layer is a photo-setting resin layer, it is Including about ultraviolet rays instead of heat treatment. It irradiates with Light. the viscosity of a diluent and the mixed-solution is reduced here -- the substrate surface It adds in order to make the mixed-solution easy to apply. Therefore, it is used here. If a diluent is a solvent which can achieve this object, it is [ anything ] fundamentally good. For example, water, ethanol, Blopanol, etc. can be used.

the 5th 0 figures (a) as [ show / in (b) ] -- a described method -- the substrate surface Particles smaller than the gap in the gap formed in the exposed photocatalyst layer (gap particle : 4) you make it filled up -- things, desirable, since Kougami of the abrasion resistance can be carried out further the size of particles smaller than a gap, and Stomai generated fundamentally -- or concave it may be smaller than convex average value -- the quantity of particles smaller than a gap, and surface Openness It is desirable to add to such an extent that the rate of a hole will be less than 20%. Dirt is To for adhering. To⁷It is by the power to depend.

A concrete example is given to below.

(Example 38)

10 Surface of Alumina Substrate of Cm Angle -- Oxidization Titanium of Average-Particle-Diameter 0. 01 M Le (what Gave Distributed Processing with Amin System Dispersing Agent) Into 10% of the weight of Shiroki Sun applying the mixed-solution which added and obtained resin and the diluent, and the hardening agent in this turn -- 15 it calcinates by 0 The -- the comparison sample was obtained. This sample is irradiated with various light sources for a predetermined period. The sample was obtained. It is deodorization characteristic R at the time of light irradiation about the obtained sample.₃₀(L) Rate. It was.

It is deodorization characteristic R at the time of light irradiation here.₃. (L) and 11 A rice Inside of the glass container of Toru a sample side -- light source (8 carrying out eight fluorescent light 4^) power -- it arranges in the distance of 8 cm -- Methylmer Captangas is poured in into a container so that it may be set to initial concentration 3 p pm -- 30-minute Mitsuteru It is the concentration rate of change after putting.

A result is shown in (table 22).

(Table 22)

Light source ultraviolet-rays intensity (WZcm)²irradiation time (Sun.) -- R30 (L) (%) -- nothing -- 30

It B Carries out and is B 0.3. 7 32

It B Carries out and is B 1.69. 5 52 Ultraviolet-rays lamp 2.0 3 74 Ultraviolet-rays lamp 3.0 1 82 Ultraviolet-rays intensity is 1. 69 mWZ c m the result.²Above the deodorization characteristic surpasses 50% and it is 2 mWZ cm.²Above, the deodorization characteristic is R.₃. Good which has (L [ good ]) for 70% The good result was shown. Ultraviolet-rays intensity is 1. 69 mW / cm here.²above good a photocatalytic reaction arises in the light irradiation portions of that the result was shown and a photocatalyst particle surface, and the thermosetting resin which exists in a finishing agent and the direction of a light source is disassembled and evaporated preferentially -- Light touch intermediation particles were exposed to the open air -- it is understood as a sake.

(Example 39)

10 It is Attach about Diluent and Hardening Agent to Shiroki Sun Resin in Surface of Alumina Substrate of Cm Angle. Solution Which Carried Out Addition is Applied, room temperature -- the abbreviation 6-hour dryness back and oxidization of average-particle-diameter 0. 01 m Titanium sol (what gave distributed processing with the Amin system dispersing agent) Into 10% of the weight of Si It is an application about the mixed-solution which added and obtained Loki Sun resin and the diluent, and the hardening agent in this turn. it carries out -- it calcinates by 150"C -- the comparison sample was obtained. It is predetermined time about the light source of versatility [ sample / this ]. It glared and obtained the sample. It is deodorization characteristic R at the time of light irradiation about the obtained sample.₃. (L) was evaluated.

A result is shown in (table 23).

(Table 23)

<img file="WO9515816A1_D0017.tif" />As a result, ultraviolet-rays intensity is 1. 69 mWZ cm.²Above the deodorization characteristic surpasses 60% and it is 2 mWZ cm.²Above, it is deodorization characteristic R.₃₀(L) 80% of But is surpassed -- good are . The result was shown. Ultraviolet-rays intensity is 1. 69 mWZ cm here.²Above good Connection A photocatalytic reaction produces that Result was shown in the light irradiation portion of a photocatalyst particle surface, it the light irradiation side of the photocatalyst particle surfaces which cannot be evaporated and decomposed by heat treatment -- With the finishing agent worn and carried out can be made to decompose and evaporate preferentially -- as a result, photocatalyst particles were exposed to the open air -- it is understood as a sake.

(Example 40)

10 It is Attach about Diluent and Hardening Agent to Shiroki Sun Resin in Surface of Alumina Substrate of Cm Angle. Solution Which Carried Out Addition is Applied, room temperature -- the abbreviation 6-hour dryness back and oxidization of average-particle-diameter 0. 01 m Titanium sol (what gave distributed processing with the Amin system dispersing agent) 10% of the weight of Si It is an application about the mixed-solution which added and obtained Loki Sun resin and the diluent, and the hardening agent in this turn. it carries out -- 150. It calcinated by C. The particle gap on the surface of a member in this stage was averaged, and was a 0. 1*0. 2;/m grade. Then, ultraviolet-rays intensity is 2 m WZ cm.²Light of (purple outside line lamp) After the irradiation during three days, R₃₀(L) it checked surpassing 80% of But receiving titanium oxide in the back and the tin oxide sol of average-particle-diameter 0. 0035 / m -- 70-fold it applies to the quantity % surface -- it dried by 110"C and obtained the sample. Also in this sample, it is R so. (L) indicated the good result to be 81%. moreover -- using a plastic eraser the sample which did not add tin oxide when the Sliding examination was done -- less than five sliding a crack enters -- the sample which added tin oxide although titanium oxide exfoliated -- 10 times -- with -- Change also of the upper sliding was lost. While being formed in the surface of a member from the above thing By making spare time fill up with tin oxide particles smaller than the gap, it is abrasion resistance. Improving was checked.

Layer which has the photocatalyst operation processed at the low temperature of less than 300 The from the above explanation The member which has Then and good photocatalyst activity by the case where it forms can be provided. Next, it is 30 at a means which is different although it is the same object as exposure by UV irradiation. Even if it calcinates at the low temperature of less than 0 °c, the multifunctional material which has sufficient photocatalyst operation is provided. A method is described below.

The titanium oxide sol produced by this method, the hydrothermal method, or the sulfuric acid method is distributed. Before adding finishing agents, such as an agent and a surface-active agent, it is oxidization Titanium about metal particulates. The Le surface is made fixed.

As for metal particulates, light is Looking to titanium oxide here the case where it supports to titanium oxide. Metal particulates which can catch an electron when it puts and an electron and an electron hole generate It is and specifically says Ag, Cu, P t, Pd, N i, F e, C o, etc.

The method of fixing metal particulates on the titanium oxide sol surface and optical reductionism are simple. It is. the titanium oxide sol used here -- a hydrothermal method or a sulfuric acid method -- Made power -- &lt; -- although it is desirable, it is not limited to it. Here, a sulfuric acid method is a synthetic method of the titanium oxide performed in the procedure shown below.

Willem night ore is made to react with sulfuric acid first, and it is water-soluble sulfuric acid about T i, F e, etc. It changes into salt, it extracts with water, and produces the sulfate solution of main ingredients T iF e. Next, S i 0 The insoluble suspension thing of the 2nd grade is removed. Next, 1 0*1 It cools to 5 °C and is ferrous sulfate. It is made to deposit and separation removal is carried out. Next, the titanyl sulfate in solution is hydrolyzed and it is hydrous acid. -izing titanium is made to generate. the obtained hydrous titanium oxide -- Wow--Toku Loew's etc. pressure using a device -- the bottom of high-temperature-high-pressure underwater (generally more than 1 1 0 °C under the Saturated vapor atmospheric pressure of less than 2 00 °C) hydrothermal processing is carried out and it crystallizes -- titanium oxide sol is obtained.

A hydrothermal method is a titanium source of titanium tetrachloride, titanium sulfate, etc., Wow--Toku It hydrolyzes by carrying out hydrothermal processing using pressure devices, such as Loew, under [ ] high-temperature-high-pressure underwater (generally 1 1 0 above 2 0 0 saturated vapor pressing down of the following), and is oxidization Chi evening A. It is the method of obtaining sol. Metal particulates to the titanium oxide sol surface by optical reductionism It carries out to a fixing method concrete target by the method shown below.

First, it is Acidic about the titanium oxide sol suspension produced by hydrothermal method or a sulfuric acid method. It was is made into alkalinity. the isoelectric point of titanium oxide is P H 6. 5 -- neutrality It is because it is easy to condense. moreover -- in order to adjust to the Al power Li nature -- ammonia using power -- it is desirable. N It is With firmly to alkaline metals, such as a and K, and titanium oxide. That it wears and is easy to carry out, when these metal occupies the active point of titanium oxide previously, it is photocatalyst activity. While making it decrease, A g, C u, P t, P d, N i, Fe, C o, etc. are acid. It is because it blocks adhering to the active point of-izing titanium.

next, titanium oxide sol suspension -- almost -- P H -- the same -- the metal salt solution carried out -- oxidization Chita it mixes to Sol suspension -- it irradiates with light including ultraviolet rays, and fixes metal. required , -- The -- a superfluous metal is settled and it removes from solution. here -- metal salt solution -- oxidization The case where it supported to titanium, titanium oxide was irradiated and the electron and the electron hole generated. Come and go -- saying the solution consisting of the salt containing the metal which can catch an electron, and a solvent more concrete To -- it consists of the salt and the solvent containing A g, C u, P t, P d, N i, F e, C o, etc. Solution is said. A as the salt containing g, C u, P t, P d, N i, F e, C o, etc. -- silver nitrate, copper acetate, carbonic acid copper, copper sulfate, a cuprous chloride, the second copper of chlorination, platinum chloride acid , a palladium chloride, nickel chloride, a cobalt chloride, ferrous chloride, and ferric chloride etc. -- it is mentioned. As a solvent, water, ethanol, propanol, etc. are Use. Although for can be carried out, it is good to use the kind same if possible as titanium oxide sol suspension. A P H adjustment agent is added to a solvent if needed. As a P H adjustment agent by the side of acid, it is Nitrogen. Acid, sulfuric acid, chloride, etc. are used. As a P H adjustment agent by the side of alkali, it is Ammonium. Nia is used.

Irradiation of light including ultraviolet rays is performed with careful attention to the point shown below. Light sources are ultraviolet rays first. An ultraviolet-rays lamp, a B L B lamp, a xenon lamp, a mercury lamp, a fluorescent light, etc. are specifically mentioned that it may be what irradiates with the included light. Light including ultraviolet rays Although an irradiation method is not asked fundamentally, either, the way with which it irradiates in the first place from the container upper part It is and is .. It is because there is no absorption of ultraviolet rays with a container. Distance of the second light source and a container A number c m* number 1 O c m grade is good. the heat which will be emitted from a light source if too near -- sample there is a possibility that the upper surface of solution may get dry -- it is because illumination will fall if too far. Irradiation time is an one several second * number, although it changes with illumination of a light source. Metal will be light if it glares about 0 minute. It adheres to catalyst particles firmly.

Next, it is a basis about the thin film which applies the above-mentioned metal support titanium oxide sol, and it heat-treats. The multifunctional material which is formed in the material surface and has a photocatalyst operation is formed.

Calcination among the atmosphere or auto crepe using heat treatment, an electric furnace, gas kiln, etc., etc. Although usually based on the used hydrothermal processing, it is not restricted to it. Average grain of the titanium oxide particles in the titanium oxide film obtained by such a method As for a path, it is preferred that it is one or less. At the particle diameter beyond it, it is reduction in specific surface area. It is because catalyst activity falls.

They are an application and Warmth about the sol indicated to Claim 1 in the member which has a photocatalyst operation. The thin film which carries out Reason was formed in the substrate surface via the binder. Adhesion nature with a substrate can be raised by passing a binder. or [ using a thermoplastic binder for the concrete method and a binder ] -- motorcycle thermosetting It differs by whether Nda is used. Next, although each one embodiment is shown, it is Full about the above-mentioned composition. If it does, it cannot be overemphasized that it is good by other methods. It is motorcycle thermoplasticity here. As Nda, they are specifically nothing, such as thermoplastic binders, such as Acryl resin, and glaze. The quality of machine glass, solder, etc. are mentioned. As a thermosetting binder, it is H. Motoki fat, an epoxy resin, Shiroki Sun resin, etc. are mentioned.

Hand which shows below the member which has a photocatalyst operation when using a thermoplastic binder It produces in order. A thermoplastic binder is first applied to the substrate surface. next, it top the titanium oxide sol which supported metal particles is applied -- it heat-treats. heat treatment is lower than and the heat-resistant temperature of a substrate here -- higher moreover than the softening temperature of a thermoplastic binder It carries out at temperature. Metal particles were supported by heat-treating at such a temperature. A part of lower layer titanium oxide layer is laid underground in a binder layer, and, thereby, they are a substrate and gold. The titanium oxide thin film which supported Genus particle can be combined firmly. The member which has a photocatalyst operation when using a thermosetting binder is below. It produces in the shown procedure. first -- a substrate -- a thermosetting binder -- a diluent and a hardening agent -- one by one -- the mixed-solution added and produced is applied -- it hardens by methods, such as heat treatment. Next, That They are thermosetting agent resin, a diluent, and a hardening agent to the titanium oxide sol which supported metal particles upwards. The mixed-solution which was added one by one and produced is applied, and it hardens by methods, such as heat treatment. An optical hardenability binder can be similarly used as a substitute of a thermosetting binder. To

Thus, titanium oxide sol produced by methods, such as a hydrothermal method or a sulfuric acid method Before setting and adding finishing agents, such as a dispersing agent and a surface-active agent, they are metal particles, such as A g, C u, P t, P d, N i, F e, and C o, T i0₂the sol surface -- fixation -- To -- since the active site of titanium oxide sol is beforehand covered by things by metal particles, such as A g, C u, P t, P d, N i, F e, and C o They are a dispersing agent and a boundary at a back process. Even if it adds finishing agents, such as a field active agent, those substances are the activities of titanium oxide sol. are . It sticks to a site and does not lose activity. therefore, a dispersing agent and a surface-active agent etc. -- work of a finishing agent can distribute photocatalyst sol stably -- a substrate surface top -- Uniformity At the same time it can form A quality membrane 3 0 Active Sai of Photocatalyst Particle Layer by Which Finishing Agents, Such as Dispersing Agent and Surface-active Agent, were Formed in Substrate Surface even if Calcinated at Low Temperature of Less Than 0 The Fall of Photocatalyst Operation by Adhering to ♪ Can be Prevented, and it is Acid. A G, C U Which Occupy Active Site of-izing Titanium Sol, P Photocatalyst activity improves according to the electronic capture effect of metal particles, such as t, P d, N i, F e, and C o.

A concrete example is given to below.

(Example 41)

By carrying out hydrothermal processing of the liquefied thing which added and obtained water in the cold bath tub to titanium tetrachloride by 140 degreein Fort Clave C, it is the announcer evening. -- Ze type titanium oxide sol was obtained. The obtained announcer evening -- Ze type titanium oxide sol was distributed in nitric acid. P H of these dispersion liquid was 0.8. copper sulfate solution of 3~5w t % which adjusted PH with nitric acid mostly into this 0.8 is added -- it irradiated with the light which includes ultraviolet rays from the container upper part. the B L B lamp of 4 W is used for a light source that time -- from solution, abbreviation 10 cm Separation was carried out and light irradiation was carried out for 15 minutes. the dispersing agent which becomes this solution from organic acetate is added -- it is stabilization about sol It carried out. this sol is applied on the tile substrate of 15 cm angle -- it is heat treatment at 150"C It carried out and obtained the sample. It is deodorization characteristic R at the time of light irradiation about the obtained sample.₃. (L) Your The Antibacterial characteristic was measured.

Deodorization characteristic R at the time of light irradiation₃. the inside of (L) and an 11-liter glass container -- sample side it arranges in the distance of 8 cm from light source (BLB fluorescent light 4W) -- methyl Mercaptan gas is poured in into a container so that it may be set to initial concentration 3 p pm -- light irradiation was carried out for 30 minutes It is a next concentration rate of change.

About the antibacterial characteristic, it is coliform bacillus. (E s che r i c h i a c o l i)

It examined using W3110 share. the above beforehand sterilized by ethanol 70% It is dropping to the outermost surface of a sample about fungus liquid 0. 15m l (10000~50000 C F U). it carries out -- it puts on glass board (X[ 100 ] 100), and makes it stick to the substrate outermost surface -- considering it as a sample It was. the fungus liquid of the sample which irradiated with white light (3500 luxs) the irradiation back for 30 minutes -- Extinction it wipes with bacillus gauze and collects to 1 10 m of physiological salines -- it asks for the probability of survival of a bacillus -- evaluation It was considered as the index. Valuation basis + +10 and + +10 and 1 are the same as that of the above.

As a result, R₃₀(L) 85% of Is and antibacterial properties are +. + The good result was indicated to be +.

(Comparative example 42)

Anatase type titanium oxide sol was obtained by carrying out hydrothermal processing of the liquefied thing which added and obtained water in the cold bath tub to titanium tetrachloride by 140 degreein Fort Clave C. The obtained Anatase type titanium oxide sol was distributed in nitric acid. P of these dispersion liquid H was 0.8. the dispersing agent which becomes this solution from organic acetate is added -- sol It was made to stabilize. this sol is applied on the tile substrate of 15 cm angle -- 150"C It heat-treated and obtained the sample. It is deodorization characteristic R at the time of light irradiation about the obtained sample.₃. (L) And the antibacterial characteristic was measured.

As a result, R₃. (L) of antibacterial properties was insufficient in -- 5%. (Example 43)

you―Ze type titanium oxide sol was obtained by carrying out hydrothermal processing of the liquefied thing which added and obtained water in the cold bath tub to titanium tetrachloride by 140 degreein Fort Clave C. The obtained you―Ze type titanium oxide sol was distributed in nitric acid. P H of these dispersion liquid was 0.8. 3*5w t% of the copper sulfate solution which adjusted PH with nitric acid mostly into this 0.8 is added -- it irradiated with the light which includes ultraviolet rays from the container upper part. the BLB lamp of 4 W is used for a light source that time -- carrying out abbreviation 10 cm Separation from solution -- 15 -- part light irradiation was carried out. the dispersing agent which becomes this solution from organic acetate is added -- it is stabilization about sol It carried out. Next, it is a diluent to Shiroki Sun resin beforehand in the alumina substrate surface of 10 cm angle. The mixed-solution which added one by one and produced propanol and a hardening agent is applied, and it is 100. the sol produced by the above-mentioned method on the member dried by C -- the amount of titanium oxide receiving -- 20% of the weight of Shiroki Sun resin, Blopanol, and a Hard agent -- one by one -- addition the mixed-solution which produced by carrying out is applied -- it calcinated by 150"C and obtained the sample. Obtained trial It is deodorization characteristic R at the time of light irradiation about a charge.₃. (L) was measured.

As a result, R₃₀(L) The good result was indicated to be 80% of Is.

(Comparative example 44)

It is the liquefied thing which added and obtained water in the cold bath tub to titanium tetrachloride 140 in Fort Clave Anatase type titanium oxide sol was obtained by carrying out hydrothermal processing by C. The obtained Anatase type titanium oxide sol was distributed in nitric acid. P H of these dispersion liquid was 0.8. the dispersing agent which becomes this solution from organic acetate is added -- sol It was made to stabilize. Next, it is to Shiroki Sun resin beforehand to the alumina substrate surface of 10 cm angle. On the member which applied the mixed-solution which added one by one and produced Propano 1 Le and the hardening agent of the diluent, and was dried by 100 degreeC, the sol produced by the above-mentioned method -- oxidization Chita as opposed to the amount of A -- 20% of the weight of Shiroki Sun resin, propanol, and a hardening agent -- order the mixed-solution which was added following and produced is applied -- it calcinated by 150"C and obtained the sample. profit a Was done sample -- deodorization characteristic R at the time of light irradiation₃. (L) was measured. As a result, R so (L) brought 22% and an insufficient result.

Titanium oxide produced by methods, such as a hydrothermal method or a sulfuric acid method, from the above explanation In sol, They are Ag and Cu before adding finishing agents, such as a dispersing agent and a surface-active agent, P Be on the titanium oxide sol surface about metal particles, such as t, Pd, N i, Fe, and C o. The member which has sufficient photocatalyst operation even if it calcinates at the low temperature of less than 300 degreeC on the substrate which does not have heat resistance by making it fix, for example, plastics material, can be provided, and it is 0.

The above example is mainly Anatase type Ti0.₂Although attached [ it was alike and ] and stated, below, it is. Rutile type TiO₂It attaches [ it is alike and ] and states.

Drawing 51 is rutile type Ti0.₂Plock which shows the manufacturing process of the used multifunctional material it is a figure -- the present invention -- first -- substrate faces, such as a tile, -- rutile type Ti0₂A thin film is formed. It carries out. Rutile type Ti0₂As a formation method of a thin film, it is Ti0 as materials.₂sulfate of sol, Ti Alkoxide, and Ti, the chloride solution of Ti, etc. are used -- a substrate top -- Paint Cloth is carried out and it is because the stress relief heat treatment is performed.

Ti0₂It is Ti0 when using sol.₂Potential points, such as of, are [ pH 6.5 and ] neutrality mostly. From a certain thing, it applies on a substrate using solution dispersed with acid or alkali. If it carries out, it will apply uniformly, and it is Bullshit. From a corrosion-resistant viewpoint to A when a substrate is metal at this time Lucari dispersion liquid are preferred. As acid, sulfuric acid, chloride, acetic acid, phosphoric acid, organic acid, etc. are mentioned. Hydroxy acid which contains ammonia and an alkaline metal the case of alkali Ammonium since a metal contaminant does not generate after heat treatment although a ghost etc. are mentioned Especially Nia is preferred. It is distribution of organic acid and a phosphoric acid system further to the dispersion liquid of these. An agent, a finishing agent, and a surface-active agent may be added. in addition -- if particle diameter is small -- the first stage sintering arises at low temperature more -- the photocatalyst thin film which was excellent in peel strength at a low temperature can be obtained that -- TiO₂Below 0. Ol/zm of the average particle diameter of sol is [ below 0. 05 / m ] preferably good.

As a coating method to a substrate, they are spray and coating about the above-mentioned materials, Di A and Co 1 tee Roll and Tongue and Co 1 tee Tongue, spin and Co 1 Tyng, and C VD special equipment is not needed as compared with electron beam vapor deposition, sputtering, etc. -- cheap -- It is desirable at the point in which a coat is possible.

Calcination among the atmosphere or auto crepe using heat treatment, an electric furnace, gas kiln, etc., etc. The used hydrothermal processing can be used.

-- A way, Cu, Ag, F e, Co, P t, N i, Pd, Cu₂the inside of 0 -- few -- Both -- a kind of solution (solution containing a metal ion) it prepares -- this -- rutile Type Ti0₂It applies on a thin film. here -- the application of metal salt solution, and the back of a substrate up to -- in the surroundings, metal salt solution should just be Crowded and a method. Melting in metal salt solution power, such as liquid, water, and ethanol, -- &lt; -- it can use. the case where water is used -- sacrifice oxidizer it carries out -- it is also effective to add alcohol, unsaturated hydrocarbon, etc. generating of using solution as an ethanol solution, for example, * Facial expression by a metal base, The point that do not become a cause but a drying rate becomes quick again, ether, acetone, and methanol etc., compared with other solvents, it is desirable at a harmless point.

Subsequently, the above-mentioned metal salt solution is made to dry by a room temperature * 110"C grade in order to raise support efficiency, metal salt is irradiated with the lighting containing the wavelength below 39 Onm, a metal ion is returned, and it is rutile type TiO.₂The metal concerned is deposited and fixed in a thin film. Here, Rumble used for irradiation are ultraviolet-rays Rumble and B L B (black rye Tobrew).

A lamp, a xenon lamp, a mercury lamp, a fluorescent light, etc. are used. Under the present circumstances, in order to raise irradiation and irradiation efficiency, it is good for an irradiation side to make it light hit perpendicularly. A concrete example is given to below.

(Example 45)

TiO of average-particle-diameter 0. 01 m₂the ammonia dispersion liquid of sol -- A of 10 cm angle it applies with spray and a coating method on a lumina board -- this -- 900. It calcinates by C. It carries out and is rutile type Ti0.₂The thin film was formed. Subsequently, this rutile type Ti0₂a thin film -- vinegar Acid copper solution is applied with spray and a coating method -- it reduction [ optical ] (a light source is 20 Watt BLB lamp, distance 10 cm [ from a light source to a sample ], and irradiation time 10 seconds) carried out after this, and obtained the sample. It is photoactive [ A ] about the obtained sample. (L) was evaluated. photoactive [ A ] (L) and gas concentration -- the Y-axis -- reaction time the time of taking to the X-axis -- anti- -- The absolute value of inclination when Adjacent curve is approximated linearly is shown. That is, it can set at time t. If concentration is set to X t,

X t = Xo and 10 -"" t (1)

It becomes. therefore, the photocatalyst in which a certain cracked gas was irradiated with light including ultraviolet rays -- thin -- Observe reduction of through and the cracked gas concentration at the time of time t progress on a film. To be reached. Methylmel power which is a bad smell ingredient also in this experiment at cracked gas A evening A is used, Diameter 2 for which the initial concentration of methyl Merca butane was adjusted to 2 p pm A sample is installed in the cylindrical vessel of 6 cmx height 21 cm, 8 of 4 \\ -- carrying out -- eight fluorescent lights The methyl Mercap evening A concentration at the time of 8 c m separating from a sample and irradiating with light is time. It asked by observing change.

The obtained result is shown in The 52 figure and The 53 figure. The 52 figure and The 53 figure are Cu concentration in solution, and photoactive [ A ] here. It is a graph which shows a relation with (L), Among these, The 52 figure carries out optical reduction, after drying the sprayed copper acetate solution. Copper acetate solution in the state where a It was case is not dried with Drawing 53 spraying The case where optical reduction is carried out is shown.

It is optical reduction about copper acetate solution in the state where it is not made to dry with Drawing 53 spraying. When it carries out, it is increase of 0.001 % of the weight to 0. 1 % of the weight about Cu concentration in solution. It is A even if it carries out Addition. (L) isX[ 3 ] 10. --⁵it is changeless at a grade -- it is saturated. It is Light reflex after drying the copper acetate solution which Drawing 52 sprayed to it. When it is a value almost comparable as the case where it is not made to dry about byX[ 2 ] 10 to five, at 0.001 % of the weight when former is carried out, but it is made to increase to 0.1 % of the weight, it is 1X10_.²Grade It is A by leaps and bounds. Signs that (L) improved were observed.

(Example 46)

It is rutile type T i 0 to floor tiling and a wall tile like Example 45.₂a thin film -- form it accomplishes -- this rutile type Ti0₂Cu is fixed by optical reduction in a thin film. (after a copper acetate aqueous liquid application and dryness) It is the concentration and bad smell extraction ratio R of a metallic component in solution the case where it carries out.₃₀The result of having investigated connection of is shown in The 54 figure and Drawing 55.

carrying out optical reduction processing, after making it dry from these figures -- metal in solution If ingredient concentration is large to some extent, a substrate can remove a bad smell ingredient also tile material. To is known. (Example 47)

Average particle diameter 0.01 7^O of 111₂It is the evening of 15 cm angle about the Vanmona dispersion liquid of sol. It applies with spray and a coating method on a A ring board, and calcinates this at various temperature. It carries out and is rutile type Ti0.₂The thin film was formed. Subsequently, this rutile type Ti0₂a thin film -- vinegar Acid copper solution is applied with spray and a coating method -- it reduction [ optical ] (a light source is 20 BLB lamp, distance 10 cm [ from a light source to a sample ], and irradiation time 10 seconds) carried out after this, and obtained the sample. It is deodorization characteristic R about the obtained sample.₃. It evaluated.

The obtained result is shown in The 56 figure. 900degreeC (10% of rate of an open pore) R which can be set

₃₀A value is better than the case of only the rutile which is not supporting metal. Temperature is gone up. When it carries out and is made 1000 degreeC (3% of rate of an open pore), it is a sample which is not supporting metal. R₃. a value decreases sharply -- some fall was observed also Cu addition sample. Thus, it is two reasons that the deodorization characteristic falls by 1000 degreeC as compared with the time of 900 degreeC. It depends. Rutile of the photocatalyst in which one can contact the cracked gas accompanying decline in the rate of an open pore Type T i 0₂It is the fall of the area of a thin film. The deodorization characteristic by the sample which is not supporting metal It is considered to be based mainly on this reason to have fallen. already -- one reason -- Openness it follows on decline in the rate of a hole -- the area in which the metal particles which deposit by optical reductionism may exist -- low -- Carrying out lower is raised. It was to which the average free path in electronic movement becomes large It loves and is To.

which shows A g in the solution at the time of a coat, and the relation between Cu concentration and color difference in Drawing 57. comparing Cu with A g also in any of color difference and brightness change from this figure -- smallness -- It turns out that Coloring is not conspicuous. the difference in this coloring and the system of Cu -- One if it is -- ESCA (electron beam spectroscopic method for a chemical analysis) etc. -- the analysis to depend -- zerovalency of C u from [ that the univalent thing is detected ] -- this -- it is hard to carry out coloration It seems that the univalent ingredient has influenced.

(Example 48)

TiO of average-particle-diameter 0. 01 m₂the ammonia dispersion liquid of sol -- the evening of 15 cm angle it applies by spray and the Co 1 Tyng method on a A ring board -- it is calcination at various temperature about this carrying out -- Lucinole type Ti0₂The thin film was formed. Subsequently, this rutile type Ti0₂a thin film -- Nitrogen acid Ginsui solution is applied with spray and a coating method -- next -- optical reduction (light sources are a 20 ♪ BLB lamp, distance 10 c m from a light source to a sample, and irradiation time 10 seconds) It carried out and obtained the sample. It is rutile type Ti0 about the obtained sample.₂The rate of a stoma and Prevention of a thin film Smell characteristic R₃. And the result of having evaluated The just to abrasion resistance is shown in The 58 figure.

By making the rate of a stoma into 10% or more, they are an example, and less than 40% and To about good deodorization property. By To, abrasion resistance can be made more than O.

sliding wear which used the plastic eraser is performed about abrasion resistance -- appearance change is compared -- it evaluated. An evaluation index is shown below.

O : With no change to a 40 times round trip

O: Crack Enters by Less Than 40 Sliding 10 Times or More -- Titanium Oxide Film Exfoliates

delta: In a crack, entering and a titanium oxide film exfoliate in less than ten sliding 5 times or more.

X : a crack enters by less than five sliding -- a titanium oxide film exfoliates

(Example 49)

It is TiO of average-particle-diameter 0. 01 m on the alumina substrates of 10 cm angle in which the glaze layer was formed beforehand.₂the ammonia dispersion liquid of sol -- Soup-- and a coating method -- Paint cloth is carried out -- calcinating this above 850 degreeC and by less than 1000 degreeO -- rutile type 1^0₂Thin film It formed. Subsequently, this rutile type Ti0₂a thin film -- silver nitrate solution -- Spray and Co -- tee it applies by the Tongue method -- next -- optical reduction (a light source is 20-W BLB lamp, distance 10 cm [ from a light source to a sample ], and irradiation time 10 seconds) It carried out and obtained the sample.

About the obtained sample, antibacterial properties, abrasion resistance, fissility-proof, resistance to contamination, acid resistance , alkali resistance, and A g coloring nature were evaluated.

About antibacterial properties, it is coliform bacillus. (Es c he r i c h i a c o 1 i W31)

It examined using ten shares. the multifunctional material beforehand sterilized by ethanol 70% -- the maximum -- fungus liquid 0.15m l (1~50000CFU) is dropped at the surface -- put on glass board (1 00X 100), and it was made to stick to the substrate outermost surface, and was considered as the sample. the sample which irradiated with white light (35 00 lux) the irradiation back during 30 minutes, and sample maintained under the shading condition fungus liquid is wiped with sterile absorbent gauze, and it collects to 1 10 m of physiological salines -- it asks for the probability of survival of a bacillus -- it was considered as the index of evaluation. Index + of evaluation + About ++10 and +1, it is the above. It is the same.

a fissility-proof examination -- the conditions of an abrasion resistant test -- more -- severe -- it is the done examination -- plus tic -- an eraser -- sand eraser (L I OK TYPEWR I TER ERASER 502) to which big shearing force is added by a substitute is used. Concrete evaluation The sample surface is rubbed 20 times by equivalent power with a method and a sand eraser, and it is a correlation sample. It carries out by comparing visually the state where the crack entered. A valuation basis is shown below. O : completely with no change

O: Optical Degree -- Small -- Change Check

△: A slight change check

-- X : -- eyes -- a change check

A contamination-resistant examination is an examination on the difficulty of attaching of a stain. concrete are . a valuation method makes a stain from 0. 5% methylene blue solution on the sample surface -- it washes after dryness -- it carries out by observing the existence of a stain visually. It is the bottom about a valuation basis.<img file="WO9515816A1_D0018.tif" />

O : a stain disappears completely.

O: although Color of Stain is not Known, Remain Slightly

△ : -- thin -- Color strength of a stain -- &lt; -- it remains

X : clearly -- Remain strong of a stain

About acid resistance, they are the 120-hour immersion back and the substrate surface to 10%H C 1 solution.

A Rutile type T i 0 which supported g₂Viewing observed and estimated the abnormalities of the thin film layer. A valuation basis is shown below.

O : with no change

O: Very -- Small -- Discoloration

delta: Discolor slightly.

X : clearly -- discoloration

About alkali resistance, they are the 120-hour immersion back and a substrate to 5%N a OH solution. Rutile type T i 0 which supported surface A g₂Viewing observes and estimates the abnormalities of a thin film layer. It was. A valuation basis is shown below.

O : with no change

O: Very -- Small -- Discoloration

△: Discolor slightly. X : It discolors clearly.

A Comparison by viewing with the sample which does not add A g about the g-th place chromatic nature It evaluated. A valuation basis is shown below.

O : with no coloring

O: Very -- Only -- Coloring

delta: Color slightly.

X : those brown with a coloring section

Above, the evaluation result of seven items is summarized to (table 2 4), and is shown. It is Exterior to antibacterial properties. The influence of To film thickness and calcination temperature is shown in (table 2 5).

(Table 2 4)

Relation between the thickness of a photocatalyst thin film, and the characteristics

Film thickness (micro etaiota) antibacterial-properties (L) abrasion resistance *-proof Inertia Resistance to contamination Acid resistance Alkali-proof Ag coloring nature

0.1 + + +O C O O O C

0.2 + + +C O C O O C

0.3 + + +O C O O O O

0.4 + + +C O O O O O

0.5 + + +O O O O O O

0.6 + + +O O O O O O

0.7 + + +O O O O O O

0.8 + + +O O O O O O

0.9 + + +O O O O O O

1.0 + + Nothing [ +O X X O Omicron X Glaze ]

(0.4) △ (table 2 5) Influence of the film thickness exerted on the antibacterial properties of a photocatalyst thin film, and calcination temperature

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It will be + if each makes calcination temperature proper in within the limits film thickness 0. 1 / more than z m of the photocatalyst thin film produced in this example about antibacterial properties, and below 1 m. + It is as good as +. The result was shown. however, a table -- 2 Below in 0. 2^m, film thickness becomes thin as shown in 4. 9 8 The tendency for antibacterial properties to fall ++ and a little by the sample calcinated at the high temperature of 0 °C accepts. , -- Was done . This is prodigal and is [ a photocatalyst thin film ] in a glaze layer locally by softening of a --A layer. Since it was buried, it thinks. Power which has antibacterial activity in A g itself -- these antibacterial properties Tendency of sexual calcination temperature dependence, The antibacterial activity of the combined member produced by this application method shows that the characteristic of rutile type T iO 2 thin films other than the antibacterial action of A g is involving. (since Ag is made to support after calcination as mentioned above) which is.

Subduction into the glaze layer of the photocatalyst thin film accompanying softening of a glaze layer, the power considered to have produced to some extent in all the samples -- &lt;&lt; -- if calcination temperature is made proper by this example -- at least 0.1 or more -- a photocatalyst thin film -- gray It was checked that it can maintain at the outermost layer of a A layer.

film thickness of photocatalyst thin film produced in this example about abrasion resistance 0. -- with -- In within the limits below upper 1 m, all indicated the good result to be O. the sample produced without being prodigal with the manufacturing method same for comparison, and passing 1 A this result -- △ -- Buddy as opposed to that of It was -- the result of having excelled extremely is brought. This to which this passes glaze By having carried out, it is prodigal at the time of calcination, and is lower layer 1 of a photocatalyst thin film by *-ization of 1 A. It is thought that it is because a part is laid underground into a glaze layer.

as opposed to it -- a fissility-proof examination -- more than 0. -- below 0. 4 m -- O and 0. -- by O and 1 m, it becomes X above at below 0. 9 / m -- film of a photocatalyst thin film it worsens with the increase in thickness -- tendency power observation was carried out. Glaze [ as opposed to film thickness in this ] It is considered a Noodle sake that it is easy to exfoliate with the decrease of the ratio of burial thickness. To. In an abrasion proof examination, it is based on the difference in the size of shearing force that that it was normal got worse by the friction test-proof.

About resistance to contamination, more than film thickness 0. l m of a photocatalyst thin film is below 0. 4 m. O and more than 0. 4 m are [ X and ] a photocatalyst at O and 1 m in below 0. 9 / m. The tendency which worsens with the increase in the film thickness of a thin film was observed.

In within the limits more than film thickness 0. l/m of the photocatalyst thin film produced in this example about acid resistance, and below 1 m, each showed the good result. however, O and more than 0. l m are O in more than 0. 4^m and 1 or less below at 0. 4 m -- film thickness The thinner one showed the desirable value.

In within the limits more than film thickness 0. 1 mu m of the photocatalyst thin film produced in this example about alkali resistance, and below 1/m, each showed the good result. However, in more than O, and 0. 1 / m, below by 0. 4 m, it is c and the one where and film thickness are thinner showed the desirable value 0.4 or more and 1 or less. Ag coloring nature -- a photocatalyst -- thin -- more than membranous film thickness 0. l/um -- below 0. 4 m -- O and 0.4 111 or more and 0.9 m or less -- O, and 1/111 it becomes -- bad in the increase in the film thickness of a photocatalyst thin film Trend was observed. This tendency is in agreement with resistance to contamination.

It is good Up above that the thickness of the film thickness of a photocatalyst thin film of more than 0. l m is more than 0. 1 m and below 0. from the examination of seven items more preferably than below 0. 9 m. It is by carrying out and is .. By fixing a photocatalyst thin film to a substrate via glaze, it is abrasion-resistant. It was accepted that Abrasion improves.

The characteristic on a design also changes with film thickness. namely, more than 0. 2 m -- less than 0. 4 / im -- the interferential action of visible light and a photocatalyst thin film -- the striped pattern of an iris color -- raw -- Tooth and an exterior -- a unique impression is given. Conversely, below 0. 2^m and more than 0. are 0.

9 the striped pattern of the above-mentioned iris color does not arise below in m -- the color or glaze of a substrate This which harnesses the color constituted, a pattern, or the appearance concerning the combination as it is It can do.

(Example 50)

Ti0 of average-particle-diameter 0. 01 m₂the ammonia dispersion liquid of sol -- the evening of 15 cm angle it applies with spray and a coating method on a A ring board -- calcinating this by 900 degreeC The -- thickness -- rutile type Ti0 of 0. 8;/m₂The thin film was formed. Subsequently, it is copper acetate solution to this tile table side. (0.2 % of the weight of solution concentration) 0. 5 % of the weight and 1% of the weight of Paint Clothes volume is changed and it is spray and Co 1 tee. It applies by the Tongue method and is this crepuscular-rays reduction. (light source a 20 Watt BLB lamp, distance 10 cm from a light source to a sample, irradiation time 3 0 second) It carried out and obtained the sample. Antibacterial properties were evaluated per [ which was obtained ] sample. Cu Responsibility Difference with the copper quantity which the amount of Possession collected remains solution after irradiation, and were collected with the early copper quantity

^ o which tB(ed)

It is to Drawing 59 at the amount of Cu support, and light irradiation time. (L) and the bacillus probability of survival of time of dark (D) A relation is shown. A figure shows the following things.

Antibacterial properties improve by support of Cu in the first place first. Next, Ho of time of light irradiation (L) Antibacterial properties improve in the amount of Cu support with less Cormorant than time of dark (D). This is light irradiation. Rutile type Ti0 which recovered optical activity by Cu support to time (L)₂Photocatalyst of a thin film It is for an operation to work. It is 0. 12 gZcm from a figure.²It is the above addition and they are +10 and 0 .3 gZcm.²It is + by the above addition. + It improves to +.

it is known that the Cu itself has an antibacterial action -- therefore, antibacterial improvement will be accepted if the amount of support of C u is made to increase also at the time of dark. In this case, 0. 7 gZ cm²It is the above support and they are +10 and 1. 2 gZcm.²It is + by the above support. + It is the Kougami To to +. Wanting to carry out, when ++ level estimates, it is 0. 12 gZcm.²It is 0. * gZcm above.²The following and + + When + level estimates, it is 0. S^gZcm.²The good antibacterial properties of time of light irradiation in amount of C u support of 1. 2 mu g / following (L) are C u above. Rutile type Ti0₂It is considered the unique effect by the thin film having been put together, and is rutile type TiO.₂The amount of Cu support can be lessened by existence of a thin film. It is such. When especially a thing that can be decreased in the amount of C u support uses this combined member for a circumference of water It is important character. Use in environment where Cu can be eluted underwater, For example, Washing Also when using it for a field stand, a ball side in sanitary chinaware, etc., it is few in the amount of elution. It stops. Things are made.

In Cu, it is Cu.₂The same effect is acquired also in the form of 0. This and Light reflex Univalent [ of Cu ] is detected on the surface at the time of former by E S C A, and it is Cu.₂+ It is a portion to -&gt;Cu+. It is because the photoactive restorative effect is observed in spite of being-like.

-- They are a way and the amount of support of Cu 0. 7 g/cm²As mentioned above, it is 1. 2 g/c m preferably.²They are good antibacterial properties irrespective of the existence of irradiation of light by carrying out above. A sex can be obtained.

Drawing 60 is the relation between the amount of applications of Cu at the time of Cu concentration lWt % in solution, and the amount of support of Cu -- this figure -- the amount of applications of Cu -- simple -- many -- even if it carries out -- copper the amount of support does not increase -- the copper amount of support -- 0. 7 gZcm²For considering it as the above, it is 0. 2 mgZcm.²It is 2.7 mg/cm above.²Hereinafter, 1. 2 g/c m²the above -- carrying out -- 0. Smg/cm²It is 2. 4 m g/ c m above.²Below may be used.

(Example 51)

Ti0 of average-particle-diameter 0. 01 m₂the ammonia dispersion liquid of sol -- the evening of 15 cm angle it applies with spray and a coating method on a A ring board -- this -- 900. calcinating by C The -- thickness -- Lucinole type Ti0 of 0.8₂The thin film was formed. Subsequently, it is silver nitrate solution to this tile table side. (0.2 % of the weight of solution concentration) 0. 5 % of the weight and 1% of the weight of Paint Clothes volume is changed, and it applies with spray and a coating method, and is this crepuscular-rays reduction. (light source a 20-W B L B lamp, distance 10 c m from a light source to a sample, irradiation time 3 0 second) It carried out and obtained the sample. Antibacterial properties were evaluated per [ which was obtained ] sample. Ag Responsibility the amount of Possession and remains solution after irradiation are collected -- difference of an early silver content and the collected silver content It computed.

It is to Drawing 61 at the amount of Cu support, and light irradiation time. (L) and the bacillus probability of survival of time of dark (D) A relation is shown. A figure shows the following things.

First, curve of the case and difference in Cu, and the bacillus probability of survival of time of light irradiation (L), and time of dark (D) Heavy. a result which is different from the case of C u in Ag produced this not but, the antibacterial activity of A g is far large rather as compared with Cu -- the amount of support it came out in small quantities very much, and the effect arose -- sake, The amount of required support of time of light irradiation (L), and time of dark (D) It seems that a difference To settle to experimental error within the limits, and is pine Result.

It is 0. 05 gZcm about the amount of support of Ag from a figure.²As mentioned above, it is 0 .1 gZcm preferably.²Good [ irrespective of the existence of irradiation of light ] by carrying out above are . Antibacterial properties can be obtained.

By a relation with color difference with the sample which has not carried out silver support with the silver amount of support on the other hand in Drawing 62 There and the silver amount of support are 1 mu gZcm.²Color difference will become large rapidly with Go beyond, and it will surpass 2. When color difference generally becomes two or more, the difference in a color comes to be conspicuous. since it will become black from tea if silver adheres -- an exterior -- desirable, since it becomes unsightly it is -- . therefore, as for color difference, suppressing to two or less is preferred -- for that purpose -- silver Responsibility the amount of Possession -- 1 cm²It turns out that below may be used. Measurement of color difference is a part. It measured with optical type color difference plan (Product made from Tokyo Denshoku ).

by the way, it sets in the above-mentioned example -- active Cyto of a photocatalyst -- finishing agent night train the fall of transformation by being covered by a molecule substance, dust, etc. -- as much as possible -- prevention or activity In order to make it recover, How to cover the active point of the particulates which have photocatalyst activity by metal particulates, such as silver, copper, platinum, palladium, gold, nickel, iron, cobalt, and zinc Although indicated, Power and the metal to cut are substrates when it applies so much, since it is a colored metal. A color peculiar to the surface is attached, and designs, such as the end, a color of a substrate, and a pattern, are spoiled and carried out. Maro.

Then, high photocatalyst It is Impaired about designs, such as a color of a substrate, and a pattern, maintaining a sex. are . L and a decoloring method are described below.

It is To immobilize about metal particulates to the particles which have photocatalyst activity as a fundamental method. Step The above-mentioned metal particles, solution, or gas is made to react, and it is a metal particle at least. By two processes of the process of forming colorless or white salt in the child surface, it is a metal particle. It is because a catalyst including a child is produced.

Here, the turn of performing the two above-mentioned processes is as being in random order and either lines. It does not matter. That is, colored metal particulates are fixed to the particles which have photocatalyst activity. After turning, The above-mentioned metal particulates, solution, or gas is made to react, and it is metal at least. Colorless or white salt may be formed in the particulate surface, Colored metal particulates Solution or gas is made to react and colorlessness or white [ on the metal particulate surface ] at least It may fix to the particles which have the photocatalyst activity after forming salt.

To the substrate after mixing the particles which have photocatalyst activity, and colored metal particulates It may fix. In this case, for example, the particles which have photocatalyst activity and a colored metal Process of mixing particulates, the process of applying the above-mentioned mixed-solution to a substrate -- calcinating -- above-mentioned Mixed making it react to the process and gas which fix Compound to a substrate -- at least -- the metal particulate surface The process of forming colorless or white salt is depended on carrying out one by one.

in addition -- making it react to the process of calcinating and fixing the above-mentioned mixture to a substrate, and gas -- few -- Even if there is nothing, the process of forming colorless or white salt in the metal particulate surface is performed simultaneously. Things are also made.

colored metal particulates have a small ionization tendency of silver, copper, platinum, palladium, gold, nickel, iron, cobalt, zinc, etc. -- metal particle to which self is easy to be returned A child is said.

The case where colorless or white salt is formed by a solution reaction, or metal particulates The colorless or white salt formed a business ^ and To case in a fluid in the catalyst to include is refractory. The insolubility is [ being a sex or ] better.

It is photocatalyst activity when using the catalyst containing metal particulates for a substrate, fixing. Since the particles which it has are beforehand fixed to the substrate, the catalyst containing metal particulates is produced. The is also good and it may fix to the substrate after producing the catalyst containing metal particulates. Since the particles which have photocatalyst activity are beforehand fixed to the substrate, it is Including about metal particulates. When Catalyst is produced, A which forms the particle layer which has photocatalyst activity in a substrate The process of fixing colored metal particulates a degree and on it, and the above-mentioned colored metal particulates The process of forming colorless or white salt so that it may cover is depended on carrying out one by one. The process of forming colorless or white salt so that colored metal particulates may be covered, For example, even if it reacts to the above-mentioned colored metal particulates and there are few metal particulates, it is colorlessness to the surface. Or method of contacting the solution which can form white salt to metal particulates, Or on Even if it reacts to account colored metal particulates and there are few metal particulates, they are colorlessness or white to the surface. The reactant gas which can form the salt of a color is performed by the method of making metal particulates contacting. Poor solubility or insoluble in the thing of the white in the salt of the above-mentioned colored metal particulates, or colorlessness It is preferred that it is sexual salt. a solution reaction -- metal particulates -- at least -- the surface salt can be formed easily -- it is because it can be stably used in the environment which has water again. As the thing of the white in the salt of the above-mentioned colored metal particulates, or colorlessness, For example, silver chloride, silver bromide, silver iodide, oxalic acid silver, and thiosulfuric acid silver, Cyanidation silver and Rodin-izing They are copper, the first copper of cyanidation, the Rodin-ized first copper, and the oxidization first silver, a cuprous chloride, and for a start [ bromination ]. Copper, zinc phosphate, oxalic acid zinc, a zinc cyanide, cyanidation palladium, and sulfuration Zinc, carbonic acid zinc, the first iron of a carbonic acid, and Zinc oxide robbery are mentioned. The above-mentioned salt can be formed. In the case of Solution, for example, silver chloride Chlorination power Rium solution and Sodium chloride solution In the case of liquid, ammonium chloride solution, ferric chloride solution, etc. and silver iodide Yaw although-izing power Rum solution, Jo-ized sodium solution, the Jo-ized second iron solution, hydrogen peroxide solution , ozone water, etc. are mentioned, it is not limited to it -- if it is soluble salt solution containing shade Iron of each salt, it can be used widely.

Kitade Ah in which the reactant gas which can form the above-mentioned salt also contains the shade Iron element of each salt Leave -- it can be used widely. For example, it is if the above-mentioned salt is oxides, such as a zinc oxide and copper I oxide. Heating in The, the atmosphere, oxygen, and vapor, or 0₃Acid of etc By making it react to a-izing agent, the metal particulate surface is oxidized and it is an oxide layer to the surface. It can be made to form.

A concrete example is given to below.

(Example 5 2)

1 the tile substrate surface of 5 cm angle -- titanium oxide sol of average-particle-diameter 0. O l^m After an application and 9 it heat-treats by 00 °C -- the rutile type titanium dioxide thin film was formed. This stage Let the sample stopped on the story be comparison sample 1. Then, silver nitrate solution is applied by spray and the Co 1 Tyng method, the BLB lamp of 20W is made into a light source, and it is on a rutile type titanium dioxide thin film about 10-minute Mitsuteru putting and silver. It fixed. The amount of support of the silver at this time is 1. 2 g/cm.²come out and it is -- brown -- coloration It carried out. Let the sample stopped in this stage be comparison sample 2.

Then, 0. lmo 1 Z Ri It is 0. 1 c cm on comparison sample 2 about potassium iodide solution of Toru.²It was made to apply and react by Percentage. as a result, the sample surface -- yellow it changes to white -- it was white-ized. considered since the silver iodide layer was formed. Let this sample be operation sample 1.

About these samples, color difference, optical activity, the deodorization characteristic, and antibacterial properties were evaluated. Measurement of color difference is a spectrum type color difference meter. (Product made from Tokyo Denshoku ) It measured. In that case, it is a mark. The semi- sample was made into comparison sample 1. A result is shown in The 63 figure. To as a result, the thing processed in potassium iodide solution in comparison sample 2 while it was color difference 3.5 By operation sample 1, it decreased to color difference 1 and the degree of coloration decreased.

About optical activity deltarho H examination estimated. Result of optical activity and the deodorization characteristic It is shown in The 64 figure. having supported silver by comparison with comparison samples 1 and 2 optical activity is recovered by The and comparison sample 2 -- deltarhoeta -- R₃. (L) is Show about a good result. It carried out. deltarhoeta is also R when operation sample 1 is compared with comparison sample 2.₃. (L) -- a basis is also boiled and it becomes an almost comparable value -- not producing change with optical activity by decolorization processing -- a good carrying-out [ characteristic power maintenance ] mosquito -- &lt;&lt; -- it became clear. ,

It examined using coliform bacillus (3110 shares of E s c he r i c h i a c o l i W) about antibacterial properties. It is fungus liquid 0. 15m l (X[ 2 ] 10) to the maximum surface of the sample beforehand sterilized by ethanol 70%.⁴CFU is dropped -- it puts on glass board (100 XI 00), and makes it stick to the substrate outermost surface -- it was considered as the sample. sample (L) which irradiated with white light (3500 lux) for a predetermined period, and the sample (D) number of microorganism maintained under the shading condition are wiped with sterile absorbent gauze, and it collects to 1 10 m of physiological salines -- counting a viable cell count It evaluated.

The result related with antibacterial properties is shown in The 65 figure. Support silver with comparison sample 1. By that which is, the antibacterial effect of (D) is not accepted at the time of dark. as opposed to it -- by operation sample 1, although the silver surface was changing to the compound by decolorization processing, the antibacterial effect of time of dark (D) was accepted. the time of light irradiation -- an antibacterial effect stronger against (L) -- observation -- Re and not only an antibacterial silver effect but photocatalyst activity restorative effect of a rutile type titanium thin film It was observed.

(Example 53)

15 glaze application-on sanitary chinaware fabrication foundation of cm angle-back, and 1100* 1200"C -- glow applying the Formation back and Anatase oxidization Chi evening Sol of average-particle-diameter 0.01 m -- 900 it calcinates by -1000"C -- a sanitary chinaware fabrication foundation substrate top -- rutile type titanium dioxide thin film It fixed.

then, silver nitrate solution is applied on it -- irradiating with ultraviolet rays -- titanium oxide -- thin -- Silver was made to deposit on a film. aqueous ferric chloride is applied on it -- outside of purple it will be decolorized if it irradiates with a line -- color difference decreased from 3 to 0.3. it is contacting the time of dark in a sample for 30 minutes the time of antibacterial properties and light irradiation -- having carried out the raw bacillus less than 10% of the number of microorganism of a basis is checked -- the good result was shown.

(Example 54)

15 glaze application-on sanitary chinaware fabrication foundation of cm angle-back, and 1100* 1200"C -- glow [ ] -- L 00 (it calcinates by TC -- rutile type titanium dioxide thin film was fixed on the sanitary chinaware fabrication foundation substrate.) applying the Anatase titanium oxide sol of the Formation back and average particle diameter 0.01 -- 900 *:

then, silver nitrate solution is applied on it -- irradiating with ultraviolet rays -- titanium oxide -- thin -- Silver was made to deposit on a film. The sample was decolorized by neglecting it for abbreviation 2 hours during [ with Ozonizer / ] one Desike evening (ozone concentration l O p pm). having carried out the raw bacillus less than 10% of the number of microorganism of a basis is checked -- the good result was shown.

(Example 55)

15 The glaze application-on sanitary chinaware fabrication foundation of cm angle-back, and 1100*120 (it is a glow at TC [ It accomplished. ]) A of average-particle-diameter 0. 01 m dispersed on it in nitric acid solution It calcinated, after applying the mixed-solution of Na evening-Ze titanium oxide sol and silver nitrate solution, and the oxidization Chi evening A thin film was fixed on the sanitary chinaware fabrication foundation substrate. At this time, they are less than 700 The. Although coloration was carried out to brown in calcination, it was decolorized when calcinated above 700"C. Silver table Since the field reacted to the ingredient in the atmosphere, it is understood. moreover -- calcinating by 850 degreeC -- Sanitary ware the sample which fixed the Anatase type titanium oxide thin film on the vessel fabrication foundation substrate -- anti- -- If fungosity is measured, will contact the time of dark in a sample for 3 hours the time of light irradiation, 1 of the number of microorganism of a basis having carried out the raw bacillus of less than 0 % is checked -- good result It was shown.

(Example 5 6)

1 One after applying glaze to the sanitary chinaware fabrication foundation of 5 cm angle 1 0 0~1 2 0 It is a glow at 0 °C. It accomplished. an it top -- average particle diameter 0.0 Anatase titanium oxide sol of 1 m applying -- 9 0 0~1 0 it calcinates by 00 °C -- a sanitary chinaware fabrication foundation substrate top -- rutile The type titanium oxide thin film was fixed.

then, silver nitrate solution is applied on it -- irradiating with ultraviolet rays -- titanium oxide -- thin -- Silver was made to deposit on a film. furthermore -- if hydrogen peroxide solution is applied on it -- decolorization -- Was done. what the time of dark contacts antibacterial properties in a sample for for 3 hours the time of light irradiation -- 1 of the number of microorganism of and a basis having carried out the raw bacillus of less than 0 % is checked -- good result It was shown.

Next, rutile type T i0₂Particles and tin oxide are mixed and it is the precise nature of a photocatalyst thin film. While improving adhesion nature, the point of aiming at active improvement is described.

It is based on either the formation method of a photocatalyst thin film or the two following methods.

One is T i 0.₂sol and tin oxide sol are mixed beforehand and it applies to the substrate surface -- calcination It is the method of carrying out.

T i 0₂It carries out in mixture of sol and tin oxide sol, and basic solution. Both are good. It is because good distribution is electrochemically seen shown and it is the Al power Li side. basic aqueous one Water oxidization which contains ammonia, the Al power Li metal, or the Al power Li ground metal as liquid the power in which a thing is raised -- &lt; -- ammonia since a metal contaminant does not generate after heat treatment It is especially desirable. Dispersing agent and the finishing agent of an organic system and a phosphoric acid system, and a surface-active agent may be further added to the dispersion liquid of these.

As a coating method, they are spray and coating, and dip and Co about the above-mentioned mixed-solution. One tee Tongue, mouth 1 Le and Co 1 tee Tongue, spin and Co 1 Tyng, C V D, and electron Power which carries out beam vapor deposition, sputtering, etc. and has the method of carrying out a coat The any may be sufficient. it carries out -- the other method may be used. however, spray and coating, and dip and coatee Tongue and roll' coatee Tongue -- C V D, electron beam vapor deposition, and the Spat evening etc. -- it compares and does not need special equipment -- o with the advantage in which a coat is cheaply possible

The application back, a film may be dried, before calcinating. Dryness is a room temperature * 1 o o °c grade. It is good to carry out.

Calcination temperature is performed at temperature sufficient on this condition for rutile to generate. Temperature 3 (it is more than TC.) Under normal pressure, it is 8 under tin oxide coexistence.

T i O₂It is not necessary to form the solid solution of tin oxide. T i 0₂Solid of tin oxide it is necessary to hold at high temperature for a long time to form a Melting object -- manufacturing efficiency worsens from -- it is .

One method is already rutile type T iO.₂the formation back of a thin film, and tin oxide sol -- it top it adds -- it is the method of calcinating.

By this method, the starting material which contains T i first is applied to a substrate. It is a starting material here. It is Ti O if it carries out.₂sulfate of sol, T i Alkoxide, and T i, and chloride solution of T i etc. -- it uses. T i0₂It is T i0 when using sol.₂Isoelectric points are P H 6. 5 and Ho. It is on business t and The base material about the solution distributed with acid or alkali since it was Neutral. If it applies, it will be easy to apply uniformly. Corrosion-resistant view when a substrate is metal at this time A point to alkali dispersion liquid are preferred. In the cases of pottery, a tile, ceramics, etc. Acid and which dispersion liquid of alkali may be used. As acid, nitric acid, sulfuric acid, chloride , acetic acid, phosphoric acid, organic acid, etc. are raised. As alkaline water solution, it is Ammonium. Since a metal contaminant does not generate after and heat treatment although hydroxide containing 2 Completion, the Al power Li metal, or the Al power Li ground metal is raised, especially ammonia is preferred. The dispersing agent of an organic system and a phosphoric acid system, a finishing agent, and a surface-active agent may be further added to the dispersion liquid of these. Ti 0 of a starting material₂The average particle diameter of sol is 0.0. Below 5 m is 0.0 preferably. Below 1 m is good. If particle diameter is small, it will sinter the first stage. Since it produces at low temperature more, the photocatalyst thin film which was excellent in peel strength at low ^ and temperature is generated. They are salted entrails and roe of the ayu, or sweetfish. They are spray and a coatee about the coating method to a substrate, and these. Tongue, and dip and a coatee Tongue, and roll and a coatee Although there is the method of carrying out and carrying out the coat of Tongue, Soubinh and Co 1 Tyng, C V D, electron beam vapor deposition, the sputtering, etc., the -- it is a gap may be sufficient -- it may carry out and the other method may be used. However, spray and coatee Tongue

Di A . coatee Tongue and roll' coatee Tongue -- C V D and Electron beam evaporation it wears and does not need special equipment as compared with Spack etc. -- a coat is cheaply possible -- Ah There is Benefits. The application back, a film may be dried, before calcinating. Dryness is room temperature * 1. 0 It is good to carry out by a 0 °C grade.

next combined member come out of and applied is calcinated. which performs calcination at the temperature which rutile generates. The temperature is 9 under normal pressure. 0 It is more than 0 °C.

The starting material which serves as a source of S n further is applied on the combined member which carried out cooling solidification after that. It calcinates. S There are tin oxide sol etc. as a starting material used as the source of n. Oxidization A It is good for Zusol to use basic solution. Tin oxide sol is seen electrochemically. It is because it is stable at the alkali side. as basic solution -- ammonia and Al power although hydroxide containing the Li metal or the Al power Li ground metal is raised -- after heat treatment ammonia power since a metal contaminant does not generate -- especially, it is desirable. These It is Attach further to dispersion liquid about the dispersing agent of an organic system and a phosphoric acid system, a finishing agent, and a surface-active agent. Addition may be carried out. They are spray and a coatee about the coating method to a substrate, and these. Tongue and A dave[ Tongue and spin . coatee Tongue, c ] . Coating and roll . Coatee

V D although electron beam vapor deposition, the Spat evening, etc. are carried out and there is the method of carrying out a coat -- the -- it is absent Re may be sufficient -- it carries out -- the other method may be used. however, spray and coating, and Di A 'coating and roll' coatee Tongue does not need special equipment as compared with C V D, electron beam vapor deposition , sputtering, etc. -- a coat is cheaply possible There is an advantage. The application back, a film may be dried, before calcinating. Dryness is room temperature * 1.

0 It is good to carry out by a crc grade. Tin oxide to calcination temperature and an organic additive ingredient are Steam. It may be the temperature to emit. The temperature is 3 under normal pressure. 0 It is more than 0 °C. Again

T It is not necessary to form the solid solution of iO 2 and tin oxide. T dissolution of iO 2 and tin oxide it is necessary to hold at high temperature for a long time to form the body -- does manufacturing efficiency worsen? , -- it is .

It is rutile type T i O to the substrate surface.₂Crystal monster 0.0 Mixed of tin oxide of less than 1/m the thin film which consists of Compound is formed -- further -- an it top -- C u, A g, P t, F e, C o, N i, Pd, and Cu₂At least one sort of metal may be fixed among 0. there are such metal and an electronic capture operation -- thereby -- rutile type T i 0₂crystal Path 0.0 the photocatalyst activity of the thin film which consists of a mixture of tin oxide of less than 1 m -- Kougami To by C u and A g, itself has antibacterial activity especially -- dark activity about antibacterial properties Since it can give, it is possible to give the antibacterial activity of the grade which has not carried out light irradiation, either. It becomes. C u, A g, P t, Fe, C o, N i, Pd, Cu₂the inside of 0 -- few -- Both -- the fixing method of one sort of metal and at least one sort of metal salt solution of these metal are applied -- it fixes with optical reductionism or heat treatment method after this. Metal salt solution and a metal kind should just be dissolving as a positive ion fundamentally. Specifically, copper acetate, silver nitrate, carbonic acid copper, copper sulfate, a cuprous chloride, the second copper of chlorination, platinum chloride acid, a palladium chloride, nickel chloride, a cobalt chloride, ferrous chloride, ferric chloride, etc. are raised.

Although there is a coating method of metal salt solution, spray and a coating method, or dip , a coating method, etc., there is little amount used and it ends -- it can apply uniformly it is possible not to attach to things, that it is easy to control film thickness, and the back -- Ah Spray and a coating method are more preferred by the reasons of To etc.

It irradiates with the light which includes ultraviolet rays after that in the case of optical reductionism, and returns metal Iron. It carries out and is rutile type T i0.₂Diameter 0.0 of a crystal It consists of a mixture of tin oxide of less than 1;. They are C u, A g, P t, Fe, C o, N i, P d, and Cu on a thin film.₂It is few among 0. To fixes one sort of metal.

The light source which irradiates with light including ultraviolet rays may irradiate with light including ultraviolet rays, and is Ah. Leave may be good and any, such as being concrete, an ultraviolet-rays lamp, a B L B lamp, a xenon lamp, a mercury lamp, and a fluorescent light, may be sufficient. To the irradiation method of light including ultraviolet rays, and an irradiation side It is preferred to arrange a sample so that light may hit perpendicularly. Irradiation efficiency is most excellent. It is from To. The distance from the light source of a sample is 1c m*3. 0 c m is preferred. Distance If too short, the whole sample side will not be irradiated with almost uniform illumination, but it is With of the above-mentioned metal kind. The illumination of the light with which it will be irradiated if distance is too long as soon as variation becomes empty in the flesh to wear is Distance. Since it becomes small in inverse proportion to the square of Separation, it is difficult to adhere a metal kind firmly. It becomes. It heats to sufficient temperature for metal to adhere after that in the case of heat treatment method, and is Solid. It law-izes. More than 100 degreeC of the temperature is preferred. however, for example, more than 800 degreeC When -- oxidizing in that case, since metal will oxidize if it processes at the said high temperature Or it does not lose the electronic capture effect, it is limited to the metal which does not lose antibacterial properties. That is, it will be limited to AgC u. the case of Ag and Cu -- high temperature Since the electronic capture effect or antibacterial properties are not lost even if it calcinates, the process shown below is also possible. it is . Namely, TiO₂mixing sol and tin oxide sol beforehand -- it is an application to the substrate surface it carries out -- it is the method of calcinating, after ranking next and applying metal salt solution. getting twisted in this method it becomes possible to be 1 time and to clear up The and a calcination process -- a productivity drive and a manufacturing cost -- low -- A decrease has an effect.

A concrete example is given to below.

(Example 55)

Ti0 of diameter of crystal 0. 01 m₂Ammonia solution solution which adjusted sol to PH 11 It added 4*6% of the weight, and produced suspension A. It is diameter 0.003 of a crystal to another container. It is 10 % of the weight to the ammonia solution solution which adjusted the tin oxide sol of 5 to PH 11. It added and produced suspension B. make it mix at a predetermined rate and carry out suspension A and suspension B -- dryness back 85 (it calcinated by TC for 2 hours, and obtained the sample.) the tile substrate surface of after It was and 15 cm angle -- spray and a coating method -- application T i 0 in the obtained sample₂A Crystals type is a rutile type and is Oh. Powder It is an X diffraction and T iO.₂Of the lattice constant It is TiO when measured.₂Dissolution of tin oxide to the inside of a lattice was not accepted. Optical activity and abrasion resistance were evaluated about the obtained sample.

about optical activity, potassium iodide solution is dropped at the sample surface -- ranking next -- drop the given iodination power Rium solution is irradiated with ultraviolet rays for 30 minutes -- iodination power before irradiation the difference of PH of Rum solution, and PH of iodination power Rum solution after irradiation -- criticism Value was carried out. That is, if the optical activity on the surface of a sample is high according to this method, it is shown below. Since an oxidation-reduction reaction [ like ] advances more, P H after irradiation is quantity from P H before irradiation. Wards intermediary To go.

Oxidation reaction: 2 I -- +2 h⁺= I²

Reduction reaction: O2+2H₂0 + 4 e -- =40H1 Abrasion resistance performs sliding wear which used the plastic eraser, and its appearance is strange again. -izing is compared -- it evaluated. About evaluation index O, O, △, and X, it is the same as that of the above, and is Aho.

It is Show about the wear-resistant change to the weight ratio of tin oxide [ Drawing / 66 ] in a thin film. To. abrasion resistance shows a good result irrespective of the existence of tin oxide -- O -- or it became O. it processed at the high temperature 850degreeC -- a sake -- the particles in sintering Force generation and a film -- said -- Samurai joined together firmly -- it is considered a sake.

It became O when especially tin oxide surpassed 30%. This is TiO of a starting material.₂Sol (diameter of crystal 0. 01 rn), and tin oxide sol (diameter of crystal 0. 0035 / zm) The tin oxide particles of a particle since the particle diameter ratio is two or more are TiO(s).₂gap of particles restoration nature improves by burying -- the film elaborated more -- it is considered a sake. which shows change of the optical activity to the weight ratio of tin oxide in a thin film in Drawing 67. Rutile type Ti0 which shows antibacterial properties good for comparison, and the deodorization characteristic₂It is alike and Responsibility about C u. Sample which it had (R)₃. so 60% of deltarhoeta, very good antibacterial properties, and deodorization Anatase type Ti0 which shows the characteristic₂Sample₃. It comes out, 97% of deltarhoeta is also united, and it is Show. It carried out. Rutile type Ti0 which added tin oxide₂of deltarhoeta and the announcer evening -- Ze type Ti0₂being alike -- although not reached, the addition weight ratio of tin oxide surpasses 10% -- less than 80% good Wait to spread -- 20% or more and 70% or less -- Lucinole type TiO₂It became clear that there were an example and good optical activity about a bigger value than △ P H of the sample which was alike and supported C u.

It is Photocatalytic activity even if it adds this and with an average particle diameter of 0-01 or more tin oxide. A sex does not improve, the upper part of the position of the electric conduction belt by tin oxide microatomizing shift power -- band and gap which is sufficient for generating active oxygen since it is not enough It is because tin oxide particles do not have. It is sufficient light if 10% is not surpassed. It is based on shortage of the quantity ratio of that activity does not arise and tin oxide particles. on the other hand -- 80% or more The probability that tin oxide in a photocatalyst layer adjoins and that an effect becomes weaker exists becomes high. it is that -- It was to which the frequency which carries out grain growth average particle diameter 0.01 / more than m at the time of heat treatment becomes high Because -- it is guessed.

(Comparative example 56)

Ti0 of diameter of crystal 0. 01 m₂Ammonia solution solution which adjusted sol to PH 11 It added 4*6% of the weight, and produced suspension A. It is the tin oxide sol of diameter of crystal 0. 01 / m to another container PH 1 It adds 10% of the weight in the ammonia solution solution adjusted to 1. It carried out and produced suspension B. after mixing suspension A and suspension B at a predetermined rate, it applies to the tile substrate surface of 15 c m angle with spray and a coating method -- it calcinated by after-dryness 850-degreeC for 2 hours, and obtained the sample. Ti0 in the obtained sample₂A Crystals type is a rutile type and is Oh. Powder It is an X diffraction and is T i 0.₂Of the lattice constant is measured. It is Ti0 when carried out.₂Dissolution of tin oxide to the inside of a lattice was not accepted. This trial Optical activity and abrasion resistance were evaluated about the charge.

It is Show about the wear-resistant change to the weight ratio of tin oxide [ Drawing / 68 ] in a thin film. To. Irrespective of the existence of tin oxide, abrasion resistance showed the good result and became O.

it processed at the high temperature 850degreeC -- sintering arises in a sake -- the particles in a film -- firm -- it joined together -- it is considered a sake. However, it is even if it makes the amount of addition of tin oxide Add this time. Abrasion resistance was not able to be raised more. This is T i 0 of a starting material.₂the particle diameter ratio of sol (Crystal monster 0. 01^m) and oxidization Suzsol (diameter of crystal 0. 01 mupiiota) -- almost -- etc -- and fold is thought.

which shows change of the optical activity to the weight ratio of tin oxide in a thin film in Drawing 69. Rutile type T i 0 which shows antibacterial properties good for comparison, and the deodorization characteristic₂It is alike and Responsibility about C u. The announcer evening which shows △ P H of a sample, the very good antibacterial properties, and the deodorization characteristic to which it held -- Ze type T i 0₂△ P H of the sample was also united and shown. Rutile type Ti0 which added tin oxide₂It is the announcer evening of deltarhoeta and this time. -- Ze type Ti0₂Sample It is rutile type T i 0 also to deltarhoeta.₂△ P H of the sample which was alike and supported C u was not attained to far, either.

(Example 57)

Ti0 of diameter of crystal 0. 01 zm₂Ammonia solution solution which adjusted sol to PH 11 It added 4*6% of the weight, and produced suspension A. It is diameter 0.003 of a crystal to another container. It is the tin oxide sol of 5 m PH 1 It is 10 % of the weight to the ammonia solution solution adjusted to 1. It added and produced suspension B. mixing suspension A and suspension B at a predetermined rate the tile substrate surface of after It was and 15 c m angle -- a spray' coating method -- application it carries out -- it calcinated by after-dryness 850 The for 2 hours, and obtained the combined member. To the obtained combined member T i 0 which can be set₂A Crystals type is a rutile type and is Oh. Weight ratio of tin oxide in a thin film It was 60%. Powder It is an X diffraction and TiO.₂TiO when [ ] Of the lattice constant was measured₂Dissolution of tin oxide to the inside of a lattice was not accepted. this combined member , -- drying copper acetate solution after an application with spray and a coating method 5% of the weight -- and this crepuscular-rays reduction (a light source is 20 Watt BLB lamp, distance 10 cm [ from a light source to a sample ], and irradiation time 1 minute) It carried out and obtained the sample. It is deodorization characteristic R about the obtained sample.₃. It evaluated.

It is here and is R.₃₀It asks by Is and the examination shown below. cracked gas -- Methylmel power butane is used -- diameter 2 for which the initial concentration of methyl Merca butane was adjusted to 2 p pm A sample is installed in the cylindrical vessel of 6 cmx height 21 cm. Deodorization characteristic R at the time of light irradiation₃₀(L) carrying out 8 cm Separation of the BLB fluorescent light of Is and 4 W from a sample -- light -- 30-minute irradiation it carries out -- it computes and asks for the concentration pace of decrease of methyl Merca butane. Deodorization characteristic R of dark B₃₀(D) methyl mercaptan when 30 minutes pass without applying Is and light -- dark -- It computes and asks for a degree pace of decrease. A result is shown in (table 26). It carries out for comparison. Sample produced in Example 55 and comparative example 56 (60% of weight ratio of tin oxide) Even if attached, it united and examined. (Table 26) having added Cu -- with -- It became clear that there was an effect taken below.

(Table 26)

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(The Heavy presentation ratio of Sn 02 yes, also a gap 60 %)

It compares with the sample of Example 53 from (Table 26), and is R.₃. the improvement in some sees to (L) , -- Was done . This is considered to be based on the electronic capture effect by Cu. Example 5 It compares with the sample of 3 and comparative example 54, and is R.₃. (D) acted as Kougami remarkably. This dark It is understood as active improvement being based on a copper catalytic effect.

by the above explanation, it sets to the member in which the photocatalyst thin film was formed on the substrate surface -- Light touch Ti 0 of an intermediation thin film₂By processing with the calcination temperature used as a rutile type, an ingredient is enough. are . Precise nature and Ti0₂Film strength can be given. It is rutile type T i0 that time.₂When except has with a diameter of a crystal of less than 0.01 tin oxide, it is Light touch of a photocatalyst thin film. Intermediation activity can be raised.

It is on a photocatalyst thin film among C u, Ag, P t, F e, Co, N i, and Pd. By fixing at least one sort of metal, it is a photocatalyst by electronic capture operation. Activity can further be raised. Industrial applicability

As mentioned above, deleterious material concerning the present invention, such as antibacterial properties, a product made from antifouling, deodorization property, and N Ox Multifunctional material which has a photocatalyst function which decomposes quality, Stone used as pavement of the artificial waterfall of wall material, a tile, glass, a mirror, and a circular filtration apparatus, for example, a water cycle method, or a fountain Or feeling in the hospital of bacteria, such as sanitary chinaware, such as a toilet bowl and a washstand, and MRS A It is business to the equipment in a hospital for stain prevention, housing equipment apparatus, anti-mold equipment, antivirotic equipment, etc. It is suitable for it being.