Coating material for forming photocatalyst/titanium oxide composite film

Specification

Ointment for photocatalyst titanium monoxide composite membrane formation Technical field

It is related with the present invention and the ointment for photocatalyst titanium monoxide composite membrane formation. Background art

if semiconductors, such as titanium oxide, are irradiated with a purple outdoor daylight line and Z, or visible light -- semiconductor an electron hole with the excitation electron which absorbs light and has a reduction operation, and an oxidization operation is generated -- semiconductor An oxidation-reduction reaction decomposes the molecular species which contacted.

such an operation is called a photocatalyst operation -- the field of versatility [ operation / this / recent-years and photocatalyst ] -- Application is carried out. For example, decomposition of N O X in the atmosphere; dirt in habitation space and working clearance Decomposition removal of prevention, a bad smell substance, mold, etc.; rings, such as an underwater organic solvent, agricultural chemicals, and a surface-active agent It is application to decomposition removal of a boundary contaminant, etc.

Contact of the substance which undergos a photocatalyst operation and an oxidation-reduction reaction, and the semiconductor which has photocatalyst activity It is demonstrated in respect of Touch. Therefore, film which applies an ointment, dries on a substrate and contains a photocatalyst It is Ba of an ointment in order to make Match to form demonstrate the photocatalyst operation to the utmost. It is necessary to make a particulate semiconductor contain at high concentration in Inda 1. however, usual -- an owner -- Particulate semiconductor in the tunic which was formed in the case of the ointment using machine binder 1 a binder decomposes by Photocatalyst operation and a film becomes weak -- namely, -- lightfastness is insufficient there is a problem of being -- long-term Therefore * Kumi was not obtained. The indication of an invention

even if the object of the present invention and the particulate semiconductor which has photocatalyst activity are included in high concentration -- 10 it has part lightfastness -- the titanium oxide film moreover firmly united with the particulate can be formed It is in providing the ointment for Photocatalyst titanium monoxide composite membrane formation.

It will become clear by other objects and features of the present invention, and the following statements. This artificer inquired wholeheartedly that the above-mentioned object should be achieved. as a result, photocatalyst activity -- an owner -- as the inorganic binder to the particulate semiconductor to carry out -- peroxotitanic acid solution -- business Beforehand, in peroxotitanic acid solution, the surface treatment of Les and the particulate semiconductor is carried out, and they are used. Match Oxidization Chi firmly united with the particulate with the ointment containing these Photocatalyst which was excellent in that an evening A film can be formed and the formed photocatalyst titanium monoxide composite membrane Demonstrating an operation and the composite membrane obtained are excellent in lightfastness, therefore it has long-term endurance. To etc. were found out. It is completed based on the present invention and this new knowledge. The present invention, the ointment for photocatalyst titanium monoxide composite membrane formation shown below, and this were used. The article obtained by the photocatalyst film formation method and the method is provided.

1 . (A) Hydrolytic Titanium Compound, Low Condensation Thing of Hydrolytic Titanium Compound, Water At Least One Sort Chosen from Group Which Consists of a Low Condensation Thing of Titanium Oxide and Titanium Hydroxide In Peroxotitanic Acid Solution Produced by Mixing Titanium Compound with Hydrogen Peroxide Solution, and Row,

(B) Particulate semiconductor 1 which has photocatalyst activity 0 As opposed to 0 weight section, Peroxoxanthine acid water solution (A) -- conversion solid content -- 0.5*1 it mixes at a 0-weight section rate -- Heat dry Carry out Dry. The particle which covered the titanium oxide film which has a hydroxy titanium base on the surface Ointment for photocatalyst titanium monoxide composite membrane formation containing a child.

2 . peroxotitanic acid solution (A) -- a hydrolytic titanium compound and Z -- or -- Paint given in the above-mentioned paragraph 1 which is what is produced by mixing the low condensation thing with hydrogen peroxide solution Cloth agent.

3 . Hydrolytic Titanium Compound is General Formula.

T i (O R) 4 (1)

(-- the inside of a formula, and R -- it is the same or different -- the Alkyl machine of carbon number 1*5 is shown.) -- a table -- Ointment given in the above-mentioned paragraph 2 which is To be tetra-alkoxy titanium.

4 . Low Condensation Thing of Hydrolytic Titanium Compound is General Formula.

T i (O R) 4 (1)

(-- the inside of a formula, and R -- it is the same or different -- the Alkyl machine of carbon number 1*5 is shown.) -- a table -- The degree 2*3 of condensation which comes to carry out the self condensation reaction of the To be tetra-alkoxy titanium Compound of 0 it is -- ointment given in the above-mentioned paragraph 2.

5 . Peroxotitanic Acid Solution (A) is Hydrolytic Titanium Compound, Hydrolysis It consists of a low condensation thing of the low condensation thing of a sex titanium compound, titanium hydroxide, and titanium hydroxide. At least one sort of titanium compounds chosen from a group, About hydrogen peroxide solution, it is former 10. The latter is mixed at 1*1 and a 000-weight section rate by hydrogen peroxide conversion to 0 weight section. Ointment given in the above-mentioned paragraph 1 which is a Was obtained thing.

6. Particulate Semiconductors Which Have Photocatalyst Activity are Titanium Oxide and Tungstic Oxide, a zinc oxide, oxidization hafnium, a zirconium dioxide, titanic acid strontium, and oxidization Chi an evening A 1 zirconium-dioxide compound oxide and an oxidization silicon titanium monoxide compound oxide -- from It is a statement to the above-mentioned paragraph 1 which are the particulates of at least one sort of metal oxides chosen from the To group. Ointment.

7. In above-mentioned paragraph 6 whose particulate semiconductors which have photocatalyst activity are titanium oxide particulates Ointment of a statement.

8. Titanium Oxide Particulates are C R, Ru, V, Nb, Fe, and N I, at least one or more sorts of metal chosen from the group which consists of Cu, Mg, Ag, Mn, Pd, and P t -- self--- Ointment given in the above-mentioned paragraph 7 which supports or contains the body, its oxide, a halogenation thing, or a complex.

9. as opposed to 100 weight sections of conversion solid content of peroxotitanic acid solution (A) -- half--- Ointment given in the above-mentioned paragraph 1 containing 10*500 weight sections of conductor particulates (B).

10. on a substrate, in the above-mentioned paragraph 1, the ointment of a statement is applied and it dries -- photocatalyst 1 oxidization Chi Formation method of the photocatalyst film forming an evening A composite membrane.

11. The article which forms a photocatalyst film on a substrate by a method given in the above-mentioned paragraph 10. The ointment for photocatalyst titanium monoxide composite membrane formation

The ointment for photocatalyst titanium monoxide composite membrane formation of the present invention, and peroxotitanic acid aqueous Liquid (A) and its surface are covered with the titanium oxide film which has a hydroxy titanium base. The particulate semiconductor (B) which has Photocatalytic activity is contained.

Peroxotitanic acid solution (A)

It is a pair to peroxotitanic acid solution (A) in a present invention ointment, and a particulate semiconductor. It functions as an inorganic system binder to carry out. peroxotitanic acid solution (A) -- Addition the low condensation thing of a water resolvability titanium compound and a hydrolytic titanium compound, and titanium hydroxide -- and -- At least one sort of titanium compounds chosen from the group which consists of a low condensation thing of titanium hydroxide It is obtained by mixing with hydrogen peroxide solution. Especially as the above-mentioned hydrolytic titanium compound, it is a general formula. (1)

T i (O R) 4 (1)

the (inside of a formula and R are the same or different -- the Alkyl machine of carbon number 1*5 is shown.) -- being expressed To tetra-alkoxy titanium is preferred. Alkyl machine of carbon number 1*5 shown by R If it carries out, they are [ -- A butyl group, s e c1 butyl group, t e r t / -- A butyl group etc. / It is mentioned. ] a methyl group, a Ethyl machine, and n. -- A propyl group, i s o -- A propyl group, n_butyl group, i so

moreover -- as the low condensation thing of the above-mentioned hydrolytic titanium compound -- above-mentioned general formula (1) The degree 2*3 of condensation which comes to carry out the self condensation reaction of the compound it is preferred to use the thing of 0 -- the degree 2*1 of condensation It is more preferred to use the thing of 0.

as the low condensation thing of titanium hydroxide -- for example, aqueous [, such as a titanium chloride and titanium sulfate, ] Alt. obtained by the reaction of liquid and alkaline water solution, such as ammonia and caustic alkali of sodium Titanic acid (titanium hydroxide gel) etc. -- it can be used. the low condensation thing of titanium hydroxide -- the degree of condensation to kick -- 2*3 the compound of 0 can be used -- especially -- the degree 2*1 of condensation Also one of 0 within the limits It is preferred to use that.

it sets to manufacture of above-mentioned peroxotitanic acid solution (A) -- titanium compound of materials Hydrogen peroxide solution, former 1 0 as opposed to 0 weight section -- the latter -- hydrogen peroxide conversion -- 1*1 and 0 0 0 weight section -- desirable -- 1 0*2 0 mixing at a 0-weight section rate is appropriate -- is there. When the latter will be less than 1 weight section by hydrogen peroxide conversion, it is formation of peroxotitanic acid. Since it becomes insufficient and a nebula precipitate is formed, it is not desirable. On the other hand, it is 1 and 0. 0 0 weight section Active oxygen dangerous during storage is emitted that unreacted hydrogen peroxide remains easily if it exceeds. It is not desirable.

the hydrogen peroxide concentration of hydrogen peroxide solution -- although not limited in particular -- 3*4 0% of the weight of example It is preferred from a point of the ease of dealing with it that it is in an enclosure.

Mixture with the titanium compound of the above-mentioned materials, and hydrogen peroxide solution, 1*7 [ usually, ] a 0 °C grade -- 1 0 minute *2 it is desirable to carry out under churning for about 0 hour -- accepting necessity in the case of mixture The -- for example Methanol, ethanol, and n -- propanol and i s o -- iso -- proper alcohols solvent [, such as Knoll, ]; -- ethylene glycol monobutyl ether, Pro Water, such as alcoholic ethers solvents, such as pyrene glycol monomethyl ether, is good. The soluble organic solvent can also be used.

Above-mentioned peroxotitanic acid solution (A), the titanium compound of materials -- hydrogen peroxide solution by making it mix, the former is hydrolyzed with water -- hydroxyl group content titanium compound it generates -- rank next and hydrogen peroxide makes at least Arrangement immediately this hydroxyl group content titanium compound -- Pell It is inferred as what is obtained by forming Oxo titanic acid.

The solid content concentration of this peroxotitanic acid solution (A), usual, and 0.1*1 Zero-fold It is a quantity % grade. Stability is quantity in this peroxotitanic acid solution (A) and a room temperature region. It is equal to preservation of Long term.

It is storage stability about at least one sort of compounds chosen from Assetanilide, phenacetin, and Oxy quinoline in above-mentioned peroxotitanic acid solution (A) if needed. It may add a sake [ on a disposition ]. The amount of addition of the compound, Solid content 1 of (A) 0 It is 0.0 to 0 weight section. 1*2 It is Ah especially 0 weight section within the limits of 0.2*2.0 weight section. That of To is preferred.

Particulate semiconductor (B)

Particulate semiconductor 1 which has photocatalyst activity also in a present invention ointment 0 It is a pair to 0 weight section. It carries out, peroxotitanic acid solution (A) -- conversion solid content -- 0.5*1 0 weight section it says -- specific -- it comes out comparatively and mixes -- drying by heating is carried out -- it has a hydroxy titanium base on the surface It is indispensable to use the particulate (B) which covered the titanium oxide film.

it sets on these specifications -- the conversion solid content of peroxotitanic acid solution (A), and aqueous [ the ] The value which multiplied the weight of liquid by solid content concentration is meant.

Present invention ointment and particulate semiconductor [ by which the surface treatment was carried out in this way ] (B) is included. Forming the titanium oxide film firmly united with the particulate semiconductor by things It is because it can do.

As the above-mentioned drying by heating conditions, it is usually 4. 0*2 5 It is 1*2 at a 0 °C grade. About [ 4 hour ] line Twisting is desirable.

absorbing a purple outdoor daylight line and Z, or visible light as a particulate semiconductor used as materials -- light a catalytic action may be revealed -- a publicly known particulate semiconductor -- especially -- restriction -- nothing -- It can be used.

As an example of a particulate semiconductor, they are titanium oxide and tungstic oxide, zinc oxide Oxidization hafnium, a zirconium dioxide, titanic acid strontium, and titanium oxide acid Metal oxides, such as a-izing zirconium compound oxide and an oxidization silicon titanium monoxide compound oxide etc. -- particulates are mentioned. It is vanadium (V) to the surface of the particulate semiconductor of these, chromium (C r) and manganese (Mn) Iron (Fe) Cobalt (Co) , nickel (N i) and copper (Cu) Zinc (Zn) ruthenium (Ru) , rhodium (Rh) rhenium (Re) Osmium (Os) , Palladium (Pd) Platinum (P t), iridium (I r), and niobium (Nb) Metal of molybdenum (Mo) etc. What supported or contained the very thing, its oxide, the halogenation thing, or the complex is mentioned. It is these particulate semiconductors and independent, or two or more sorts can use it, mixing.

It being cheap as a particulate semiconductor and the titanium oxide particulates which are excellent in photocatalyst activity are good Up. It is by carrying out and is .. As titanium oxide particulates, they are Anatase type titanium oxide particulates and Luchi. Both Le type titanium oxide particulates and brookite type titanium oxide particulates can be used. the titanium oxide particulate surface -- the metal itself, such as C r, Ru, V, Nb, Fe, N i, Cu, Mg, Ag, Mn, Pd, and P t, the oxide of those, and a halogenation thing -- or -- The thing which made the complex support or contain can be used preferably.

It is the titanium oxide particulates which have a stable oxygen defect, and is a wave more than 420 nm. In electron spin resonance spectrum (ESR) measured under the light irradiation of a long region, g value The titanium oxide particulates by which the main signal which is 2.004*2.007, and two subsignals whose g values are 1.985*1.986 and 2.024 are observed are also use. It cuts.

As a primary mean particle size of a particulate semiconductor, it is 1 nm* : 1, a 000 nm grade, and good Up It is suitable that it is a range about [ to spread ] 5 nm of Is *100 nm. 1 of a particulate semiconductor That what has the following mean particle size smaller than 1 nm is difficult to manufacture, one side, and particulate semiconductor When a primary mean particle size becomes larger than 1 and O O Onm, it is intermediary light with small surface area. Since catalyst activity becomes is hard to be demonstrated, it is not desirable.

The primary mean particle size of a particulate semiconductor, for example, a transmission electron microscope, (TEM) Business Can be and it can measure.

Ingredient combination of the ointment for photocatalyst titanium monoxide composite membrane formation

Pell who is an essential ingredient in the ointment for photocatalyst titanium monoxide composite membrane formation of the present invention Semiconductor particles (B) by which the surface treatment was carried out to Oxo titanic acid solution (A) as above-mentioned Content rate, usually, conversion solid content 1 of peroxotitanic acid solution (A) 0 0 weight section it receives -- a particulate semiconductor (B) -- 1 0*5 0 It is preferred that it is about 0 weight section. Since the double-ed layer on the surface of a particulate semiconductor will check a thick intermediary and a photocatalytic reaction if (B) ingredient is less than a mentioned range, it is not desirable. On the other hand, it is a mentioned range. (B) ingredient Since a particulate semiconductor (B) will become easy to deviate if large, it is not desirable.

The above-mentioned content rate and conversion solid content 1 of peroxotitanic acid solution (A) 0 0 weight section It receives and a particulate semiconductor (B) is 5. 0*3 0 From it being about 0 weight section, it is good Up. It is by carrying out and is ..

Mixture with above-mentioned peroxotitanic acid solution (A) and a particulate semiconductor (B), this -- fine -- the distributed particle diameter of particles (B) -- 1 0 nm* 1 0 m, preferably 1 0 nm* 1 z m grade From the point that performing distributed processing so that it may become enlarges photocatalyst activity surface area It is desirable.

When dispersing a particulate semiconductor, distributed particle diameter exists like one particle, after primary particles have condensed, but it means the diameter of a particle in the state where it condensed. this -- Distributed particle diameter is measurement in the state of dispersion liquid by a submicron particle analysis device, for example. It cuts. As a commercial item of a submicron particle analysis device, for example, "C0ULTER MODEL N4SDJ (a brand name, COULTER ELECTRONICS, product made from IN) can be used.

necessity other than the ointment for photocatalyst titanium monoxide composite membrane formation of the present invention, the above-mentioned (A) ingredient, and the (B) ingredient is accepted -- various additive agents can be contained.

The organic acid from the point which raises the storage stability of an ointment as such an additive agent and Z, or its salt can be mentioned.

As organic acid, they are acetic acid, oxalic acid, and Glico 1 Le acid, Organic carboxylic acid, such as lactic acid, malic acid, citrate, tartaric acid, and dull contest acid; Metasunsuru phone acid, Etah Thun phone acid and p -- Organic Sour Von acid, such as benzene Sulfone acid; 2 -- Amino 1 ethane sulfinic acid, p -- organic sulfinic acid [, such as toluene sulfinic acid, ]; -- Nito Lome Than, Nitrothane, nitroglycerine propionic acid, nitroglycerine catechol, and 2 -- Nitroglycerine Resorcinol, Organic nitro compounds, such as nitrobenzoic acid; phenol and power Toko 1 Le, Resorcinol, hydroquinone, pyrogallol, and salicylic acid, Gallic acid, benzoic acid, Thiopheenol, and 2 -- Friend Nochio phenol, 4-Chi Le tilchio Fenno Phenol, such as Le; 1 -- Hydroxy methane 1 and 1-Diphosone acid, 1 -- Hyd 1 and 1 -- mouth Xishtan 1 -- Diphosone acid, 1-hydroxy propane 1, and 1-Jiho Suchon acid, Two Tori mouths (Amino) Trimethylene phosphonic acid, 2 Tori mouth (Amino) Triethylene phosphonic acid, and 2 Tori mouths (Amino) Tripropylene phosphonic acid, Echile Phospho [ Ndiamine tetramethylen phosphonic acid and / ethylene diamine tetra-ethylene ] A acid, Ethylene diamine tetra-propylene phosphonic acid, N, N -- Screw (2 -- Hoss Wöchl) Hydronalium Xiamin, N, N -- Screw (2 -- phospho methyl) Hydronalium Xiamin and 2 -- Hydroxyethyl phosphonic acid Dimethyone 1 Tell's hydrolysis thing, 2 -- Hydroxy phosphono acetic acid and 2 [ An organic phosphorus acid compound is mentioned. ] -- Phosphono butane 1, 2, 4 -- Tricarboxylic acid etc.

What an alkali compound is added to the above-mentioned organic acid for as salt of organic acid The salt of the organic acid formed can be used. Organicity or nothing that contains lithium, sodium, potassium, ammonium, etc. as the alkali compound, for example A machine Al power Li compound is mentioned.

using what has solubility in water as organic acid or organic acid salt -- good -- better To, In particular, they are glycolic acid, lactic acid, malic acid, citrate, and tartaric acid, dull contest acid etc. Hydroxycarboxylic acid; 1 and 1 -- 1-hydroxy methane 1 -- Diphosone acid, 1 _ Hydronalium Xishtan-- 1, 1-Diphosone Acid, and 1 -- Hydroxy Propane 1 and 1 -- Di Hydroxyl Machine Content Organicity Phosphorous Acid, Such as Phosphonic Acid; 2 -- Hydroxy Phosphono Acetic Acid, 2 -- Power report Xyl machine content organicity, such as phosphono butane 1, 2, and 4 1 tricarboxylic acid At least one sort of compounds chosen from the group which consists of phosphorous acid and these salt are used. Carrying out is preferred from demonstrating the effect excellent in the storage stability of an ointment, etc. The amount of addition in the case of making a present invention ointment contain the above-mentioned organic acid and/, or organic acid salt, and usual, Solid content 1 of the (A) ingredient 0 It is 1*4 to 0 weight section. The range of about 00 weight sections, especially 1 0*2 0 It is preferred that it is the range of about 0 weight section.

a present invention ointment -- necessity is accepted further -- as an additive agent -- a basic neutralizer, a thickener, the organic solvent, a surface-active agent, an antimicrobic agent, a Prevention * agent, lubricant, an antifoaming agent, a chelating agent, and Lepel A Tongue agent, a color pigment, constitution paints, Prevention * paints, etc. can be contained. As a basic neutralizer, they are ammonia, an organic base compound, and an alkaline metal. Hydroxide, alkaline-earth-metals hydroxide, etc. can be mentioned. organic base combination 2 -- as a thing -- For example, Dimethyl etano 1 Ramen and 2 -- Amino 1 -- methyl 1 1 Propano 1 Le, Triethylamine, morpholine, etc. can be mentioned. As alkali metal hydroxide, lithium hydroxide, sodium hydroxide, water oxidization power Rum, etc. can be mentioned.

For example, Acetyl acetone etc. can be used as a chelating agent.

As a color pigment, red ocher, colored glass frit powder, etc. are mentioned. It can do. As constitution paints, for example, my power, talc, silica, fine powder silica, Baryta, clay, etc. can be mentioned.

Solid content concentration of an ointment for photocatalyst titanium monoxide composite membrane formation of the present invention, It is usually about 0 .1*6 0 % of the weight. It has the outstanding storage stability.

A formation method of a photocatalyst film

a formation method [ of the photocatalyst film of the present invention ], and substrate top -- photocatalyst titanium monoxide composite of the present invention the ointment for film formation is applied and it dries -- the method of forming the photocatalyst film which is the composite membrane -- is there. It is that with the substrate which wants to demonstrate a photocatalyst operation as a substrate which can apply the present invention method. It is not The(ed) and restricted.

the quality of the material of a substrate is not restricted, either -- for example, the substrate of all the quality of the materials of metal, pottery, plastics, textiles, glass, concrete, etc. can be used. As opposed to a photocatalyst operation As opposed to substrates, such as plastics of resolvability, and textiles, for example, Silica, such as Silike 1 A the coating liquid containing acid chloride, peroxotitanic acid, etc. -- a substrate side -- beforehand -- an application or impregnating place Reason is given -- the tunic for insulating from a photocatalyst operation can be formed. They are which forms, such as tabular, a globular shape, the shape of a rectangular parallelepiped, and the shape of a cylindrical shape, also as shape of a substrate. A state may be sufficient. a porous object, a granular material, etc. are used as a substrate -- internal processing of a porous object It is also possible to perform a surface treatment and the surface treatment of a granular material. As a porous object, for example, a foaming object, a honeycomb structural body, a corrugated structure, etc. can be mentioned. As a granular material, it is a constitution of for example, my power, talc, silica, barium sulfate, clay, etc. Mentioning color pigments, such as paints, red ocher, cobalt blue, and colored glass fritto It can do.

as a concrete substrate -- the exterior of a construction building, interior, a windowpane, and power 1 -- ten; way Protective barrier of a way; inner wall; of a tunnel -- the interior of vehicles, and windowpane; -- a mirror etc. are mentioned To. A present invention ointment is painted to the field which needs a photocatalyst operation of these substrates. It can do. It may paint beforehand to the member which constitutes these substrates.

Paint of an ointment

The ointment of the present invention is applied on a substrate and it dries, (A) What in an ingredient Luoxo titanic acid forms a titanium oxide film, and it is some peroxotitanic acid. At least one pair on the surface of a particulate semiconductor which has the photocatalyst activity carried out in the specific surface treatment It reacts, Photocatalyst titanium monoxide composite membrane which the particulates and titanium oxide film unified A certain photocatalyst film is formed.

It may be based on the coating method to a substrate top, and a publicly known coating method. For example, printing paint, A knife coater paint, doctor blade paint, dip coating, shower paint, and a spray Various coating methods, such as paint, roll paint, and electrodeposition coating, are employable. you make it impregnated to a substrate side -- it may paint. It is usually 1. It is hard to exfoliate in the application of 0. With an excellent in adhesion thickness of one or more photocatalyst -- A titanium oxide composite membrane can be formed. of course, necessity is accepted -- it may apply two or more times.

Although dryness and normal temperature dryness are also possible, a particulate semiconductor and a titanium oxide film are fully 1. Heating and drying is desirable in order to carry out embodying. As heating temperature, it is usually 4. 0 °C*2 5 It is 8 preferably about 0 °C. 0*2 0 Zero It is suitable that it is a grade. Cooking time is usually 1, although changed with temperature. It is Suitable which is considered as about 0 minute * 3 hour. It is [ this ]. As a heating method, an electric furnace, a gas heating furnace, heat by microwave, Miku Mouth Wave induction heating, etc. are desirable.

the dry film thickness of a photocatalyst titanium monoxide composite membrane -- it is not limited in particular. This film thickness, usual, and 0.0 0 1*2 It is preferred that it is 0 m grade, and it is 0. : !. * 1 It is 5 m grade. It is more desirable.

In this way, it is photocatalyst 1 oxidization Chita uniform on a substrate by the formation method of the above-mentioned photocatalyst film. The article in which it comes to form a A composite membrane can be prepared. The best form for inventing

hereinafter, the example of manufacture, an example, and a comparative example are given -- the present invention is explained more concretely_t "part" in each example and "%" are all weight standards.

Peroxotitanic acid solution -- (A) -- Manufacture Tetra [ Mixture of zero copy Thing, ] i s o -- A propoxytitanium 1 * part and i so -- Propanol 1 3 0 % hydrogen peroxide solution 1 Zero copy and deionized water 1 0 It is 2 in the mixture of zero copy. It was dropped while carrying out ultrasonic churning over 1 hour by 0 °C. after that 2 it ripes by 5 °C for 2 hours -- Yellow transparent a small portion of Ming -- viscous peroxotitanic acid solution was obtained. This is diluted with water and it is a solid. It was considered as peroxotitanic acid solution (i) of part concentration 3 %.

Example 2 of manufacture

Tetra_n -- butoxytitanium 1 Zero copy and i s o -- propanol 1 the mixture of zero copy -- 3 0 % hydrogen peroxide solution 2 Zero copy and deionized water 1 0 the inside of the mixture of zero copy -- two 0 °C -- 1 hour It was dropped while carrying out Keep it. ultrasonic wave churning. after that 2 it ripes by 5 °C for 2 hours -- yellow -- transparent -- few -- Peroxotitanic acid solution which carries out and is viscous was obtained. This was diluted with water to make peroxotitanic acid solution (i i) of solid content concentration 1 %.

Example 3 of manufacture

Tetra-ethoxy titanium 1 Zero copy and methoxy ethanol 1 It is a mixture of five copies 3 0 % hydrogen peroxide solution 2 Zero copy and deionized water 1 0 It is 2 in the mixture of zero copy. It applies by 0 °C for 1 hour, and is Super. It was dropped while carrying out sound wave churning. after that 2 it ripes by 5 °C for 2 hours -- yellow -- transparent -- a few -- viscosity The existing peroxotitanic acid solution was obtained. This is diluted with water and it is solid content concentration 2 %. It was considered as peroxotitanic acid solution (i i i).

Manufacture and evaluation of the ointment for photocatalyst titanium monoxide composite membrane formation

Example 1

Peroxotitanic acid solution (i) 2 of solid content concentration 3 % obtained in example 1 of manufacture To zero copy, Good Visibility light response type photocatalytic oxidation titanium (brand name "mu rho tau -- 6 2 1") Ishihara Sangyo Co., Ltd. -- Seven copies of make and mean particle size 7 n m, and alumina bead 5 zero copy is added -- 2-hour shaking distribution carrying out separation removal of the bead from dispersion liquid after carrying out -- 1 5 0 °C -- 3 Carry out drying by heating on the conditions for 0 minute. The surface treatment of The and titanium oxide particles was carried out.

subsequently, 100 copies of alumina beads are added into this -- Pelo of 3% of solid content concentration 80 copies of Xo titanium acid water solution (i)s are added -- after carrying out shaking distribution for 15 minutes -- from dispersion liquid separation removal of the bead is carried out -- ointment (I) for photocatalyst titanium monoxide composite membrane formation was obtained. the above-mentioned ointment (I) is applied with an air spray method so that dry film thickness may be set to 2 m to aluminum substrate (49. 5mmX 10 OmmX 3. Om m) -- drying by heating is carried out by 170"C for 30 minutes -- the photocatalyst titanium monoxide composite membrane was formed. Lead of this composite membrane Brush hardness was 5 H.

the aluminum substrate in which the above-mentioned composite membrane was formed is used -- decomposition rate of NOx gas It measured. Namely, nitrogen oxide measurement machine (brand name "nitrogen oxide meter C LAD for environmental air measurement -- 1000") Shimadzu Co., Ltd. -- make is used -- standard with a NO concentration of 2 ppm Pass NO X gas (NO gas concentration l ppm) proofread by gas 2 L/mi n. A which formed the above-mentioned composite membrane while irradiating with halogen 100W quartz lamp of AM 1. 5 The decomposition rate of the NOx gas of a Luminum substrate was evaluated. As a result, NOx decomposition rate 81 % was obtained.

the above-mentioned ointment (I) is used for a foaming aluminum substrate (49. 5mmX 10 OmmX 3. size of zero mm coming porous board of To) -- it is made the same except carrying out dip coating -- the photocatalyst titanium monoxide composite membrane was formed. It is a scanning electron microscope about the section of this composite membrane.

(SEM) having computed the real surface area from the average film thickness and coat weight which were observed and obtained by time -- the abbreviation of substrate surface area (49. 5mmX 100mm) -- they were 3 times. This composite membrane The decomposition rate of the N O X gas of the formed foaming aluminum substrate was evaluated similarly. As a result, more than NO X decomposition rate 98 % has been attained.

Example 2

To 25 copies of peroxotitanic acid solution (ii)s of solid content concentration 1 % obtained in example 2 of manufacture, Brookite type photocatalytic oxidation titanium (brand name "NTB -- 200") Showa Denko Co., Ltd. -- the mean particle size before make, 2. 5% water distribution sol, and solation adds 100 copies of 10 nm -- Vibration it obtains and carries out drying by heating on the conditions of 4 hours by 80"C after distributing -- surface place of titanium oxide particles Reason was carried out. subsequently, 75 copies of peroxotitanic acid solution (i i) of solid content concentration 1 % and 0.001 copies of Assetanilide are added into this, and shaking distribution is carried out for 30 minutes -- Light touch The ointment for intermediation titanium monoxide composite membrane formation (I I) was obtained.

This ointment (II) was applied with the air spray method so that dry film thickness might be set to 0. 1 m to I TO transparent conductive glass substrate (5 OmmX 10 OmmX 2m m), drying by heating was carried out by 150 °C for 30 minutes, and the photocatalyst titanium monoxide composite membrane was formed. This composite membrane Pencil hardness was 2 H.

the glass board material in which the above-mentioned composite membrane was formed -- 1% methylene blue solution -- 10 -- it is immersed between parts -- methylene blue was made to stick to the film surface the solution on the film surface -- Filtration paper is made to suck up and it removes -- the substrate for evaluation which made the film surface pollute blue was obtained. this it uses -- the bottom of irradiation of 27W fluorescent light stand (distance 3 O cm) -- methylene blue It evaluated photodegradable. As a result, methylene blue 1 decomposed in 30 hours.

Example 3

To 20 copies of peroxotitanic acid solution (iii)s of 2% of the solid content concentration obtained in example 3 of manufacture, Nanoparticle platinum support rutile type titanium dioxide photocatalyst (brand name "nano pure DR35PT 30") DAIKEN CHEMICAL Industry Three copies of make and mean particle size 10 nm, five copies of talc, 0.1 copy of red red ocher and 50 copies of alumina beads are added -- separation removal of the bead is carried out from dispersion liquid after carrying out shaking distribution for 2 hours -- drying by heating is carried out on the conditions of 6 hours by 90"C -- oxidization Chi The surface treatment of evening A particles was carried out.

subsequently, 100 copies of alumina beads are added into this -- Pelo of 2% of solid content concentration 80 copies of Xo titanium acid water solution (iii)s, and ten copies of 10 % hydrogen peroxide solution, Puccilse mouth 0.2 copies of Sorb are added -- after carrying out shaking distribution for 15 minutes -- dispersion liquid to a bead -- Separate and remove is carried out -- ointment (III) for photocatalyst titanium monoxide composite membrane formation was obtained.

On the surface of PET film (5 OmmX * 5 OmmX 0. lmm) which performed surface hydrophilicity-ized processing by plasma treatment beforehand, Peroxotitanic acid solution (ii) of solid content concentration 1 % is applied by one Rolco evening 1 method so that dry film thickness may be set to 0. 2 xm, 120 on [ after carrying out drying by heating for 10 minutes by °C ] it, the above-mentioned ointment (piiota) is applied by Rolco 1 Tha 1 method so that dry film thickness may be set to 1 m, and drying by heating is carried out by 180 degreeC for 1 minute -- porosity The nature photocatalyst titanium monoxide composite membrane was formed on the PET film. Pencil of this composite membrane Hardness was 4 H.

The PET film in which this composite membrane was formed is put into the glass container of 50 Om 1, 2 under irradiation of 7 W fluorescent light stand (distance 30 cm), the air containing Asset aldehyde 300 p p m is circulated -- gas is extracted every 10 minutes -- gas chromatography -- aldehyde concentration was measured by --. as a result, 12 hours -- Asset aldehyde -- dark -- a degree becomes below 1 ppm -- the photodegradation ability of Asset aldehyde was able to be checked. Example 4

To 20 copies of peroxotitanic acid solution (i)s of 3% of the solid content concentration obtained in example 1 of manufacture, Anatase type titanium oxide (Product made from brand name "AMT_600" and Thika ) average particles seven copies and 50 copies of alumina beads are added the diameter of 30 nm -- separation removal of the bead is carried out from dispersion liquid after carrying out shaking distribution for 2 hours -- drying by heating is carried out on the conditions for 30 minutes by 150"C -- oxidization The surface treatment of titanium particles was carried out.

subsequently, 100 copies of alumina beads are added into this -- Pelo of 3% of solid content concentration 80 copies of Xo titanium acid water solution (i)s are added -- after carrying out shaking distribution for 15 minutes -- from dispersion liquid separation removal of the bead is carried out -- ointment (IV) for photocatalyst titanium monoxide composite membrane formation was obtained. the above-mentioned ointment (IV) is applied with an air spray method so that dry film thickness may be set to 2 m to aluminum substrate (49. 5mmX 10 OmmX 3. Om m) -- drying by heating is carried out by 170"C for 30 minutes -- A photocatalyst -- the titanium oxide composite membrane was formed. Lead of this composite membrane Brush hardness was 5H. It winds by load 200 g with a Mad cow disease type abrasion testing machine, and is Return. It checked that carried out and abnormalities did not have 20 times in a deed and a composite membrane in an attrition test.

the aluminum substrate in which the above-mentioned composite membrane was formed is used -- decomposition rate of NOx gas It measured. Namely, nitrogen oxide measurement machine (brand name "nitrogen oxide meter C LAD for environmental air measurement -- 1000") Shimadzu Co., Ltd. -- make is used -- standard of NO concentration 2 ppm NOx gas (NO gas concentration 1 ppm) proofread by gas is passed 2 L/mi n -- * intensity outside purple: 0. 8 mW / cm²while irradiating with ultraviolet rays with a of black light -- the above -- double -- The decomposition rate of the NOx gas of the aluminum substrate in which the Synthesis film was formed was evaluated. As a result, NO decomposition rate 87 % was obtained.

Comparative example 1

In 20 copies of Anatase type titanium oxide sol solution of 3% of solid content concentration, Visible light response type photocatalytic oxidation titanium (brand name "MPT -- 621") Ishihara Sangyo Co., Ltd. -- Add seven copies of make and mean particle size 7 nm, and 40 copies of alumina beads. Solid after carrying out shaking distribution for 2 hours Anatase type titanium oxide sol solution 8 of type part concentration 3 % adding zero copy -- 1 5-minute shake after distributing, separation removal of the Bi 1 A is carried out from dispersion liquid -- photocatalyst titanium monoxide for comparison Ointment (V) for composite membrane formation was obtained.

The above-mentioned ointment (V) is applied with an air spray method so that dry film thickness may be set to 2 m to aluminum substrate (4 9 .5 mmX 1 0 O mmX 3 .O m m), and it is 1. 7 It is 3 at 0 °C. Although drying by heating was carried out for 0 minute, the formed film is weak -- it vibrates -- or if a substrate is leaned, a film will separate and fall -- evaluation could not be presented.

Comparative example 2

Peroxotitanic acid solution (i) 1 of solid content concentration 3 % obtained in example 1 of manufacture 0 To zero copy, Anatase type titanium oxide (brand name "alphamutau -- 6 0 0") Thika Co., Ltd. -- Make and average grain Child diameter 3 Seven copies of 0 nm, and alumina bead 2 5 zero copy is added -- a shaken part scatters for 2 hours separation removal of the bead is carried out from the It was back and dispersion liquid -- photocatalyst titanium monoxide composite membrane type for comparison Ointment (VI) for Formation was obtained.

About the above-mentioned ointment (VI), it is an aluminum substrate. (4 9 .5 mmX 1 0 O mm X 3 .O m m) applying with an air spray method so that dry film thickness may be set to 2 m -- 1 7 0 °C -- 3 drying by heating is carried out for 0 minute -- the photocatalyst titanium monoxide composite membrane was formed. Lead of this composite membrane Brush hardness was 2 B. It is load 2 with a Mad cow disease type abrasion testing machine. 0 It winds by 0 g and is Return. It carries out and is 2. When the attrition test was done 0 times, the film separated and the aluminum side was exposed. EFFECT OF THE INVENTION

According to the present invention ointment, the following prominent effects are acquired.

(1) Apply the ointment of the present invention on a substrate and it dries, (A) ingredient While inner peroxotitanic acid forms a titanium oxide film, peroxotitanic acid The particulate semiconductor (B) surface which has the photocatalyst activity made into the part in the specific surface treatment at least one copy reacts -- firm Light touch which the particulates and titanium oxide film unified The photocatalyst film which is an intermediation titanium monoxide composite membrane can be formed.

The reason, Oxidization Chi by the self condensation reaction of the peroxotitanic acid in the (A) ingredient The Than formation operation, It is formed in the particulate semiconductor (B) surface of the above-mentioned specific surface treatment. Condensation reaction of a It was hydroxy titanium base and the peroxotitanic acid, What is depended on the (A) ingredient and (B) ingredient carrying out a chemical bond is presumed.

(2) The photocatalyst titanium monoxide composite membrane obtained with a present invention ointment, and outstanding Light touch An intermediation operation is demonstrated. it is a strong inorganic tunic -- it generates by a photocatalytic reaction since degradation of photodegradation etc. is not received more radically but it excels in lightfastness -- long-term endurance It is obtained.

Therefore, decomposition of N O X in the atmosphere; dirt prevention in habitation space and working clearance, and bad smell thing Decomposition removal of quality, mold, etc.; environmental pollutants, such as an underwater organic solvent, agricultural chemicals, and a surface-active agent Decomposition removal; it is preferably applicable to the use of the electrode of a photoelectric cell, etc.

(3) A present invention ointment and storage stability are improving by leaps and bounds. Half the reason The hydroxy titanium base of the conductor particulate (B) surface, Perukoshita in the (A) ingredient It is protected by the hydrophilicity of the Peroxo machine of A acid by the sterically-hindered functional group. What is depended is presumed.

(4) The ointment of the present invention and the particulate semiconductor which has photocatalyst activity are included in high concentration. Photocatalyst 1 oxidization Chita which can form the titanium oxide film firmly united with the particulate even if it was A A composite membrane can be formed. Porous by including a particulate semiconductor in high concentration A composite membrane can be formed.