Untitled record

Field of the Invention

the present invention relates to a photocatalyst-supporting Structure for Antifouling, cleaning water, deodorization, pasteurization, treatment of wastewater, water degradation, control of algae growth and various chemical reactions is suitable.

Background of the Invention

titanium dioxide, an n-type semiconductor is known as a photocatalyst, the by ultraviolet radiation energy of various chemical Activated reactions, such as. For example, during a process of water degradation, Deodorization, pasteurization, water purification, treatment of waste water or the like occurring chemical reactions. It is said that the catalytic activity of a Photocatalyst may be generally high when either Powder form or in the form of a suspension in a solvent is used. However, in many cases has such a photocatalyst used in a layer applied to a particular substrate form be. In order to efficiently ultraviolet radiation energy from light use, it is advantageous to use a substrate in the form of a paper or bring sheet, the larger of the Light irradiated area can ensure. also it is further advantageous, the surface of the substrate a porous structure to give, so that the contact surface of the substrate with a reactant with which the progression an actual chemical reaction is desirable in the presence of a photocatalyst, is increased.

Various a photocatalyst-containing substrates were in the past proposed. For example: (A) a light transmissive material such as cellulose nitrate, Glass, polyvinyl chloride, plastics, nylon, methacrylic resin and polypropylene is in the <patcit><text>Japanese Patent Publication No. Sho 62-66861</text></patcit>Disclosed; (B) polypropylene fibers and ceramics are in <patcit><text>Japanese Patent Publication No. Hei 2-68190</text></patcit>Disclosed; and (C) glass, ceramics, nylon, acrylic and polyester resins are <patcit><text>Japanese Patent Publication No. Hei 5-309267</text></patcit>Disclosed.

however is reported by the above disclosed materials that an organic material as its main component comprising Material has the disadvantage that the organic material due to a caused by the photocatalyst contained in said material can be decomposed and destroyed catalytic reaction, and consequently Its durability has been problematic (s. Fumiaki Ootanio .. Kobunsi Kako No. 42, vol 5, p 18 (1993); "Titanium dioxide", by Manabu Kiyono, Ed. Gihodo, p 165).

Further have to, although the substrate made of an inorganic material such as glass and Ceramics, some of the durability characteristic of the substrate solved problems concerning be such. B., if an organic polymer resin as an adhesive used to attach a photocatalyst on the substrate is, the photocatalytic activity may be reduced because the surface is covered by photocatalyst particles with such a resin, and the photocatalyst of the substrate due to the corrosive and destructive Action of said organic polymer resin due to its photocatalytic can flake type.

Around such problems as described above, to avoid were a Spatterverfahren described process wherein no organic materials remain (<patcit><text>Japanese Patent, Publication No. Sho 60-044053</text></patcit>), A method of coating and firing a organic titanate (<patcit><text>Japanese Patent Publication No. Sho 60-118236</text></patcit>), A method of spraying and firing a titanium sol (<patcit><text>Japanese Patent Publication No. Hei 5-253544</text></patcit>), And other used when the substrate used is consisted of an inorganic, heat-resistant material.

however these methods have a problem in that it has a burn need of the substrate at a high temperature to manufacture and crystallisation the photocatalyst particles on the substrate and adhesive property to achieve with the substrate. Consequently, it is difficult to obtain a photocatalyst be applied in a wide range, and the production according to these The method entails very high costs.

To the Applying a photocatalyst on a fiberglass plate a method using a metal oxide sol as an adhesive proposed (s. <patcit><text>Japanese Patent Publication No. Hei 5-309267</text></patcit>).

&lt;?page 3?&gt;

the Adhesive property of a metal oxide sol, such as a Silica sol, however, is very weak because it is due to van der Waals forces (s. Fine Ceramics, Vol. 1, pp 216-223, 1980), so that the bonding strength and durability of the adhesive were insufficient. Furthermore, requires a method additionally Firing at a high temperature and thus was not available for all types of substrates applicable, including usually used types of resins that are easily decomposed by heating.

From an example in which as a metal oxide, such. silica gel and clay mineral, in a sol state with a photocatalyst powder it was used, it was reported that the photocatalytic decomposition reaction of propionaldehyde gas as due to the effect of a substrate Adsorbent is accelerated (s. Symposium "Recent development in Photocatalytic Reaction ", preceding Manuscripts, published by the Society for the Study of Functional Photo Material, no. 2-11, P 39, 1994).

however is so far no report, is described in that Substrate is obtained, the excellent adhesive property and durability while maintaining the high photocatalytic activity of the photocatalyst, of, as described above, uniformly in a metal oxide sol is distributed, has.

On A method for attaching a photocatalyst using a fluorescein has also been proposed (s. <patcit><text>Japanese Patent Publication No. Hei 6-315614</text></patcit>). However, the price of a fluorescein high and it is necessary that the majority of the surface the photocatalyst particles is covered with the fluorescein to the photocatalyst particles to stick permanently. Accordingly, catalytic activity a photocatalyst lowers relative to the activity of the same Photocatalyst in powder form. Although an example is known (S. <patcit><text>EP 633 064 A1</text></patcit>) which suggests to apply a photocatalyst onto a substrate, by the photocatalyst with a binder such as fluororesins and poly-organosiloxane is mixed, the resistant to decomposition is, this is not sufficient to these problems with respect to adhesive property and durability practically solve.

<patcit><text>EP A 633 064</text></patcit> disclosed a substrate exhibiting a photocatalyst mixture with is a first layer provided having an adhesive the no photocatalyst particles contains, said first layer with a second layer is that a less easily degradable adhesive and photocatalyst particles having. The second layer contains 5-98 vol.% Photocatalyst particles based on the total amount of photocatalyst particles and less easily degradable adhesive. Example 8 from<patcit><text>EP A 633 064</text></patcit> discloses a Photocatalyst mixture consisting of a first layer with a less easily degradable adhesive without photocatalyst particles equipped substrate (transparent acrylic plate) and a second Layer of less readily biodegradable adhesive and 90 vol.% Photocatalytic Function comprising titanium oxides is.

<patcit><text>EP A 684 075</text></patcit> disclosed a multi-functional, a photocatalytic function exhibiting Material (a) a carrier / base layer, (B) a bonding layer and (c) a photocatalytic layer, wherein the photocatalytic layer on the surface of Base layer is arranged by means of the bonding layer, and wherein the photocatalyst layer an outwardly directed surface layer and includes an embedded in the bonding layer lower layer, the surface layer from photocatalyst particles consists. The lower layer of the photocatalytic layer is partially embedded in the binder layer after the layers aggregate to a temperature was heated to above the melting temperature the bonding layer, but below the melting temperature of the base layer lies.

<patcit><text>EP A 792 687</text></patcit> disclosed a photocatalyst structure comprising (a) a substrate, (b) a a Binder containing intermediate layer and (c) a photocatalyst layer includes. According to example 2 from <patcit><text>EP A 792 687</text></patcit> can the intermediate layer by coating with a liquid, a silica sol and trimethoxy-methylsilane in a weight ratio of 3: 1 exhibiting Material can be produced on an aluminum substrate, followed by Drying at 150 ° C, after which the titanium oxide-containing photocatalyst layer applied is.

As described above, the following three points as when applying a photocatalyst onto to be solved, a substrate Problems are specified: (1) the adhesion between the photocatalyst and the substrate should be good, (2) the photocatalytic activity of the photocatalyst must not diminish when it is applied to a substrate, and (3) both the substrate and the adhesive should not due to the presence of the photocatalyst applied thereon destroyed be and the substrate has its binding ability, durability and catalytic activity can preserve.

Moreover, when a photocatalyst-carrying structure under conditions of high temperatures &lt;?page 4?&gt;and high humidity is employed, for example a property of the structure necessary excellent adhesion to to keep the immersion in boiling water.

It is for a used for applying a photocatalyst onto a substrate Photocatalyst coating material required a property exhibit that the photocatalyst coating material neither to increase its viscosity still results in its particle sedimentation even after its storage for at least one month and preferably more than three months. As well is a property required, which allows a photocatalyst to a substrate without destroying its photocatalytic activity when applied the photocatalyst on a product for practical use is.

the The present inventors have found a process, a photocatalyst firmly to adhere to a substrate by a specific adhesion provided between a photocatalyst layer and a substrate is, thus, the adhesion of the intended substrate before its degradation due to the photocatalytic activity to protect the photocatalyst and the photocatalyst layer firmly adhere to the substrate, and a solution of the above-described provide problems in that the adhesion layer resistant to deterioration due photocatalytic activity is made.

Disclosure of the Invention

the The present inventors have found that with silicon modified resin, such as. for example, acrylic-silicon resin or epoxy-silicon resin, the 2-60% containing by weight of silicon, a 5-40% Mass fraction of colloidal silica containing resin, and 3-60% Mass fraction of polysiloxane-containing resin which is a polycondensation reaction product a means of formula (1) compound represented represents: <st32:che xmlns:st32="http://lighthouseip.com/">SiCln₁(OH) n₂R¹n₃(OR²) n₄ (1),</st32:che>in the R¹ a 1-8 carbon atoms which Alkyl group is unsubstituted or substituted with an amino group, is substituted a carboxyl group or a chlorine atom, R² a 1-8 carbon atoms which alkyl group or a 1-8 carbon atoms containing alkoxy-substituted Alkyl group, n₁ 0, 1 or 2, n₂ and n₃ each independently 0 or one of integers from 1 to 3, n₄ a Integer from 2 to 4, wherein the sum of n₁. n₂, n₃ and n₄ 4, glue a photocatalyst fixed and can protect the substrate from photocatalytic activity of the photocatalyst.

Also have the inventors of the present invention for solving the problem with respect to the photocatalyst coating material found that a photocatalyst coating material 0.001-5 wt% one or more alkoxysilanes containing the general by means of a Formula (2) are shown: <st32:che xmlns:st32="http://lighthouseip.com/">SiR³n₅(OR⁴)₄-n₅ (2)</st32:che>where R³ a 1-8 carbon atoms which alkyl group is unsubstituted or substituted by an amino group, a chlorine atom is substituted or a carboxyl group, R⁴ a 1-8 carbon atoms having alkyl group or an alkoxy-substituted, 1-8 carbon atoms which alkyl group is n₅ 0, 1 or 2, or the hydrolysis products thereof, 1-30 wt% a metal oxide sol and / or a metal hydroxide sol on the basis of of solid particles and 0.1-30 wt% of a photocatalyst as a powder and / or sol, for a long time can be stable, and not to an increase viscosity and particle sedimentation leads, and accordingly, they have completed the present invention.

Also have also found the inventors of the present invention that The photocatalyst-carrying structure and the above-described Photocatalyst coating material on various substrates, such as glass, plastics, metals, fabrics and wooden Materials, can be applied and, on a lens, adhesive films Window darkening, nonwoven textiles, wooden doors, etc., by utilizing the photocatalyst coating material according to the present invention can be applied.

the present invention is described in detail below in more detail.

&lt;?page 5?&gt;

in of the present invention is a resin for forming the adhesive layer to be used in the photocatalyst-carrying structure, . From a group of modified silicon resin, such as Acrylic-silicon resin or epoxy-silicon resin, the 2- 60 wt% containing silicon, a 5-40% by weight colloidal silica containing resin and a 3-60% Mass fraction of polysiloxane having resin selected.

If a silicon-modified resin containing silicon in an amount contains less than 2% by weight, such as an acrylic-silicon resin, a resin containing polysiloxane in an amount of less than 3% by weight contains, and a resin containing colloidal silica in an amount of less contains 5% by weight, is used, the connection strength between reduced the adhesion layer and the photocatalyst layer and the adhesive layer is due to the action of the photocatalyst destroyed, wherein the photocatalyst layer tends to flake easily. In contrast, when using silicon-modified resin, such as in an amount containing greater than 60% by weight of acryl-silicon resin is used, deteriorate the connection between the adhesive layer and the substrate and the abrasion resistance of the structure is by the lowering of the Hard of adhesion reduced.

Meanwhile, when a polysiloxane in an amount of more than 60% by weight -containing resin or a colloidal silica in an amount of more than 40% by weight containing resin is used, the adhesion porous, under the adhesion layer intended substrate is due to the action of a photocatalyst destroyed and the connection state between the substrate and the adhesive layer deteriorates, and the photocatalyst layer tends case to easily peel off from the substrate.

At the Use of a silicon-modified resin, such as an acrylic-silicon resin and an epoxy-silicon resin, as an adhesion layer material can any silicon-modified resin according to any of methods for introducing Silicon into the resin, such. As an ester-exchange method, transfer reaction method using silicon macromers and reactive silicon monomers, Hydrosilylierungsreaktions method and block copolymerization was prepared, be used in the present invention.

As Resin, to be introduced into the silicon, are acrylic resins, and Epoxy resins, the most suitable for their properties of Film formation, their resilience and their adhesion properties on Substrate. However, other resins, such as alkyd resins, urethane resins and polyester resins, as well as be used. additionally can these resins whether in the form of solutions or emulsions be used. Likewise, there is no problem if such a Resin an additive such. B. contains a crosslinking agent.

A Photocatalyst-carrying structure with improved adhesive property and durability can be achieved if one for forming an adhesive layer Resin used is a polysiloxane, wherein the polysiloxane is a Hydrolysis of 1-5 carbon atoms and having a silicon-alkoxide or a derivative of such a hydrolysis product is. If the alkoxy group of silicon alkoxide 6 or more carbon atoms contains, is one such resin expensive and the adhesive property and durability the resin will be destroyed, since it is difficult, the alkoxide in the resin due to its low cure rate of hydrolysis.

It is also possible, to use a polysiloxane which is obtained by partially Chlorine-containing silicon alkoxide is subjected to hydrolysis. However, a substrate may be due to the presence of chloride ions corrode as impurity, when a high level of a chlorine ion-containing Polysiloxane is used, which as well as the adhesive property of the adhesive layer reduced.

As a method for introducing a polysiloxane in a resin are the same method of mixing in the form of a silicon alkoxide monomer with a resin solution and followed Hydrolyzing with moisture in the air at the time of formation an adhesion layer and method for mixing of a product by means of partial Hydrolysis of the silicon alkoxide with a resin and then hydrolyzing the mixture with moisture in the air at the time of formation a protective film, etc., is known. Any method which uniform mixing with a resin allowed, can be used. A small amount an acidic or basic catalyst may be for changing the Rate of hydrolysis of the silicon can be added.

As examples for one for the insertion a polysiloxane suitable resin may include acrylic resins, acrylic silicon resins, Epoxy-silicon resins, silicon-modified resins, urethane resins, Epoxy resins, poly&lt;?page 6?&gt;ester resins, alkyd resins etc. can be used. however are silicon-modified resins including acryl-silicon resins and epoxy-silicon resins the most preferable in terms of their durability characteristic.

If the adhesion layer of a colloidal silica containing resin is composed, it is preferable that the diameter of the colloidal silica particles is 10 nm or less. If the diameter exceeds 10 nm, the resin in the adhesion layer further destroyed due to the influence of a photocatalyst and Binding condition between the photocatalyst layer and the adhesive layer also deteriorates. As a method for introducing such colloidal silica in the resin is known that a method to mix a resin solution with a solution colloidal silica, the then applied and then to form an adhesive layer is dried, this is easiest. However, a method for Forming an adhesive layer, by a resin is allowed to polymerize while colloidal silica in the Resin is dispersed, and then the synthesized resin applying and drying, as well as acceptable. It is also possible, colloidal silica to use after to a silane coupler Improve the adhesive property and the dispersibility of colloidal silica, and a resin was treated.

As examples for a resin is introduced into the colloidal silica, are acrylic resins, Acryl-silicon resins, epoxy-silicon resins, silicon-modified Resins, urethane resins, epoxy resins, polyester resins, alkyd resins etc. to disposal. However, silicon-modified resins including acryl-silicon resins and Epoxy-silicon resins in terms of durability best appropriate.

As colloidal silica , any silica sol, either by performing cation exchange of a sodium silicate solution, or by performing a are hydrolysis of a silicon alkoxide is produced, used.

For an object, the destruction one for an adhesion layer prevent resin used by the influence of a photocatalyst and to improve its durability, a mixing of the resin with a photo-stabilizing agent and / or ultraviolet absorbent or similar a good effect supply. As usable photo stabilizing Agent impaired amine compounds are preferably used. However, all other connections are used. triazole have the ultraviolet absorption agents may be used. The amount of the resin to be added to the ultraviolet absorber is a range of 0.005 wt% to 10 wt% based on of the weight of the resin, and preferably from 0.01% by weight to 5% by weight. By treating the surface of the adhesion with a silane-containing or titanium-containing coupler can connect conditions between the adhesive layer and the photocatalyst layer can be improved.

As a method of applying an adhesive to a substrate can a method of coating the substrate with a resin solution according to all Printing method, sheet-pressing method, sputtering, dipping and Coating method, spin coating method, etc. and then Drying the coated substrate may be used. The temperature drying the coated substrate is preferably 150 ° C or less, although depending the type of solvent and the resins varies. When a thickness of an adhesive layer 0.1 microns or more, it is possible to provide a prepare photocatalyst-carrying structure which is fixed with can connect a photocatalyst layer and a substrate and having high durability. In the case of a coating process, such as. for example, a gravure printing process, the process for drying a and curing the adhesion layer requires a short time, it is also permitted, the adhesion layer material from 0.1% to 10% by weight based on the mass of the solid component of the adhesion layer material, dependent on the required cure speed, a curing agent add, such. as a silicon compound or the like.

On present in the photocatalyst layer or the metal oxide gel Metal hydroxide gel provides an effect, the photocatalyst powder to fix and firmly connect it with an adhesive layer, and hence shows a such a metal oxide gel and / or metal hydroxide gel having photocatalyst-carrying structure excellent adhesion, Durability and weather resistance, such as in the examples of embodiment of the present invention. In addition, such metal oxide gel and metal hydroxide gel, a porous Structure and acts adsorbing, and they also have a reinforcing Effect on the photocatalytic activity. The content of a such metal oxide gel or metal hydroxide gel in the photocatalyst layer is between 25% and 95% by weight. If this content is less than 25% mass&lt;?page 7?&gt;share is, the compound can be with an adhesive layer be insufficient, the photocatalytic activity may be insufficient if the content exceeds 95% by weight.

Further can the compound described above and the photocatalytic activity improved , when the specific surface of the metal oxide gel or the metal hydroxide gel after drying at 150 ° C at 50 m²/ G or higher, preferably at 100 m²/ G or higher.

As examples for a metal stand in the metal oxide gel and the metal hydroxide gel described above Silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, Tungsten, tin, etc. are available.

the Adhesive property of a photocatalyst layer after dipping can be improved in boiling water, by using a metal oxide gel or a metal hydroxide gel is used, the two or more metals selected from a group of silicon, aluminum, titanium, zirconium and niobium, contains. As examples of a combination of metal compounds, the insensitivity to boiling have water, are silicon-aluminum, silicon-titanium, silicon zirconium, Silicon-niobium, aluminum-titanium, aluminum-zirconium, Aluminum niobium, tantalum aluminum, titanium-zirconium, titanium-niobium, Titanium-tantalum, silicon-aluminum-zirconium and silicon-aluminum-titanium as preferable available and metal oxide gels and metal hydroxide gels comprising metals such. As silicon-aluminum, silicon-titanium, silicon-zirconium, silicon-titanium-aluminum and silicon-aluminum-zirconium stand out as being more preferable available.

If a specific surface area this metal oxide or metal hydroxide gels gels at 50 m²/ G or higher, they provide a Photocatalyst layer good adhesive property and improved photocatalytic Activity, wherein the photocatalyst-carrying structure after the immersion in boiling water still retains very good adhesion property. In practical use can produced both by mixing a sol to form a gel Gels and by co-precipitation method complex oxide gels or the like can be used produced. For mixing with a photocatalyst, it is desirable, either a metal oxide or metal hydroxide in a sol state before forming of the gel to mix evenly or in a raw material state before the production of a sol to mix.

As a method for manufacturing of gels, a method to hydrolyze a metal salt, a method to decompose a metal salt by means of neutralization, a method to exchange ions, a method for hydrolyzing a metal alkoxide and the like be used. However, all methods by which gel is present in the one state, in the dispersed photocatalyst uniformly in the gel be is used. Since the adhesive property and photocatalytic activity of a impaired photocatalyst could be, when many impurities are contained in the gel, it is preferable to use a less impurities containing gel.

Further Is it possible, by either adding a silicon-modified resin or Silankopplers between 10 and 50% by weight of a Photocatalyst layer, to obtain a photocatalyst layer, the immersion, even after the in boiling water for 15 minutes high photocatalytic activity reserves and excellent bonding property with more than 6 points according to the evaluation test of adhesion property, the cross-cut Scotch tape test accordance with JIS K5400 having.

The Silicon-modified resin or silane coupler, which in a Photocatalyst layer inflict are, exhibit an improving effect on the adhesive property of the Photocatalyst layer on a substrate in boiling water on. As the silicon-modified resin can generally available resins such as Silicon-acrylic resin and silicon-epoxy resin, either in a dissolved State in a solvent be used or as a suspension in water. On the other hand can as silane coupler a means of general formulas RSi (Y)₃ and (R)₂Si (Y)₂ compound represented, wherein R is a organic functional group and Y is a chlorine atom or an alkoxy group represents, and similar be used. In the general formulas described above methyl, ethyl, vinyl, gamma-glycidoxypropyl, gamma-methacryloxypropyl, Gamma- (2-aminoethyl) aminopropyl, Gamma-chloropropyl, gamma-Mercapopropyl, gamma-aminopropyl and gamma-Acryloxpropyl etc. as examples of a reproduced from R substituents available. In addition to a chlorine atom are all C₁-C₅Alkoxy groups, such as. B. Methoxy, ethoxy, beta-methoxyethoxy, and beta-ethoxyethoxy, as well usable as a reproduced Y substituent.

the a photocatalyst layer to be added amount of silicon modified resin and a silane coupler is preferably between 10% and 50% by weight based on solids. If This amount is less than 10% by mass, the connection property of the layer after performing the test may be reduced with boiling water. If the added Volume 50% mass&lt;?page 8?&gt;exceeds share, can significantly Decrease in the photocatalytic activity caused. As either the modified method of adding the silicon Resin or Silankopplers to a photocatalyst layer is a method of adding such resin into a photocatalyst either in powder form or in sol form and a process for their Addition to either a metal oxide sol or a metal hydroxide sol, used for forming a metal oxide gel and with a photocatalyst be added, available. The addition of modified silicon resin described above in emulsion to the sol is particularly preferable since it the connection property a photocatalyst layer can be improved in boiling water, in almost no decrease in the photocatalytic activity.

As well , an additive such as a crosslinking agent with the with Silicon-modified resin or the silane coupler can be combined.

Of the Photocatalyst of the present invention is in powder form, sol or solution before and can be used if it is with an adhesive layer can show connect and photocatalytic activity after at a drying temperature for the photocatalyst layer was dried. When a photocatalyst is used in a sol state, preferably with the particle diameter of 20 nm or less, more preferably of 10 nm or less, used because the transparency of a photocatalyst layer improves can be and its linear transmittance increases, so it is particularly preferable to such a photocatalyst for coating use of glass substrates and plastic molds, most transparent must be. Further, a surface coated with such a photocatalyst transparent Photocatalyst layer advantageous if color and / or pattern be applied to an underlying substrate because this no adverse influence to colors and / or patterns of the underlying have substrates.

As of the according to the present invention the photocatalyst layer to be used can photocatalyst TiO₂, ZnO, SrTiO₃, CdS, GaP, InP, GaAs, BaTiO₃, KNbO₃. Fe₂O₃, Ta₂O_s, WHERE₃. SnO₂, Bi₂O₃, NiO Cu,₂O, SiC, SiO₂, MoS₂, InPb, RuO₂, CeO₂ and similar and mixtures of these photocatalysts with a metal or a Metal oxide such. As Pt, Rh, RuO₂, Nb, Cu, Sn, Ni and Fe are used. In addition, all by adding a metal such as Pt, Rh, RuO₂, Nb, Cu, Sn, Ni and Fe, to the photocatalyst by using a reduction reaction the mixtures photocatalyst prepared as in the present Invention is applicable. The photocatalytic activity increases with the increase of the photocatalyst content in the photocatalyst layer to. However, it is preferable to set the content at 75% by weight or less in view of maintaining enough good connection property to leave.

The Photocatalyst coating material according to the present invention is characterized in that the solution of a silicon compound in an amount of 0.001-5% comprising by weight, a metal oxide sol and / or a metal hydroxide sol in an amount of 0.1-30% Wt, based on solid components, and a photocatalyst powder and / or sol solid in an amount of 0.1-30% by weight, based on Components.

As examples for the photocatalyst coating material of the present Invention added silicon compound may be an alkoxysilane is represented by the general formula (2): <st32:che xmlns:st32="http://lighthouseip.com/">SiR³n₅(OR⁴)₄-n₅ (2)</st32:che>where R³ a 1-8 carbon atoms which alkyl group is unsubstituted or substituted by an amino group, a chlorine atom is substituted or a carboxyl group, R⁴ a 1-8 carbon atoms containing alkyl group with a 1-8 Carbon atoms having alkyl group or an alkoxy is substituted, and n₅ 0, 1, 2 or 3 is, and the mixtures with one or more of the respective hydrolysis products thereof can be used. In the general formula (2) are methyl, Ethyl, vinyl, gamma-glycidoxypropyl, Gamma-methacryloxypropyl, gamma- (2-aminoethyl) aminopropyl, gamma-chloropropyl, Gamma-mercaptopropyl, gamma-aminopropyl, gamma Acryloxpropyl and the like as examples of means R³ reproduced substituents available. C₁-C_8thAlkoxy, such as z., methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, beta-ethoxyethoxy and 2-ethylhexyloxy are examples of the means -OR⁴ reproduced preferred substituents.

As examples for the means of the general formula (2) reproduced silicon compounds can Tetramethoxy silane, tetraethoxy silane, Methyltrimethoxy-silane, silane-Methyltriethoxy and mixtures of one or more hydrolysis products of these above mentioned compounds preferably available.

&lt;?page 9?&gt;

by means of Adding a small amount of the silicon compound described above to a coating solution for forming a photocatalyst layer, a stable coating material be obtained for forming a photocatalyst layer, leading to a smaller increase in viscosity and particle sedimentation leads, even when stored for a long period. In terms of of the coating material for forming a photocatalyst layer amount to be added to silicon compound is preferably between 0.001 and 5% by weight added to the solid component basis. If such amount is less than 0.001% by weight, is the stability of the coating material for forming a photocatalyst layer when stored for reduced for a long time, while a significant decrease The photocatalytic activity is caused when such an amount to be added about 5% by weight lies. As a method for adding a silicon compound to a coating material for forming a photocatalyst layer a method of adding to a photocatalyst solution either in Powder or sol form, a method of adding to a sol of either a metal oxide or a metal hydroxide, which together are added with a photocatalyst, and the like be used. Alternatively, the coating material partially hydrolyzed silicon compounds are added. There which the coating material for forming a photocatalyst layer be added silicon compound an increasing effect on the connection property has a photocatalyst in boiling water, it is possible that to reduce amount of addition of the silicon compound when the Silane coupler as described above or the like to the coating material was added.

It is preferable to use a metal oxide sol and / or a metal hydroxide sol in an amount of 0.1-30 wt% and photocatalyst powder and / or sol in an amount of 0.1-30 wt% based on solid components, each in proportion to the mass of the coating material for forming the photocatalyst layer, to admit called coating solution.

If a ratio an amount to be added of the metal oxide sol and / or metal hydroxide sol low than 0.1% by weight is, is the ability to to connect a photocatalyst to a substrate, insufficient his while, if the ratio more than 30% by weight is, the amount of added photocatalyst powder and / or sol simultaneously reduced must be, thereby decreasing the photocatalytic activity becomes. The photocatalytic activity will be too low if a ratio of Amount of to be added photocatalyst powder and / or sol low than 0.1% by weight is, and a photocatalyst layer is easily peeled off, because the amount of a metal oxide sol and / or metal hydroxide sol to Connecting the layer must be reduced to a substrate, when a ratio an addition amount of photocatalyst powder and / or sol is 30 wt% or more.

The Coating material for forming a photocatalyst layer according to the present Invention is the same with a coating material for Forming an adhesive layer used, with an adhesive layer formed between a photocatalyst layer and a substrate can be. As the coating material for forming an adhesive layer a composition from 1 to 50% by weight based on solid Components, a 2 to 60% by weight of silicon-containing with Silicon-modified resin, a 3-60% by weight of polysiloxane containing resin and a 5 to 40% by weight of colloidal silica containing Resin.

As one for the use in a coating composition for forming an adhesion layer suitable resin, it is preferable that as described above for an adhesion layer to use resins usable either singly or in a mixture with each other of these resins. Such a coating composition then must preferably either in solution of an organic solvent or in aqueous Emulsion are prepared and the content of the resin as a solid Ingredient should preferably between 1 and 50% by weight chosen will. When in a coating composition, the concentration the solid content of such resin is 1% or less, the adhesion layer too thin formed and joining the photocatalyst layer is difficult produce. On the other hand, when in a coating composition the concentration of the solid content of such a resin 50% or more, the adhesion layer too thick formed and it will be difficult to form a coating film right to produce and with a coating composition properly deal because it is too viscous.

If a photocatalyst layer is formed on an adhesive layer, can be a suspension wherein a photocatalyst in a sol of either a metal oxide or a metal hydroxide is dispersed, by coating according to a Procedures are applied, the the to form an adhesive layer is equal to. Alternatively, a photocatalyst in a solution of precursor of either egg&lt;?page 10?&gt;nem metal oxide sol or a metal hydroxide sol are dispersed and then by a hydrolysis process or neutralizing decomposition during Coating process to either a sol form or a gel form produced. If the used sol prepared as described above is a dispersant, such as. for example, an acid or a base may be added to improve the stability of the sol. As well Is it possible, to improve the adhesive property and simplicity in handling further, by the sol to 5% by weight or less of a surfactant Substance, a silane coupler, or the like is added, based on the mass of the photocatalyst. The Drying temperature at the time when a photocatalyst layer is formed, preferably between 50 and 200 ° C, although They resin materials used by the different substrates and for the adhesion depends.

Although a thicker photocatalyst layer provides higher photocatalytic activity, there is no great difference type, if the thickness exceeds 5 microns. The photocatalyst layer having a thickness of 5 microns or less, preferable because they have high photocatalytic activity and light transmittance provides that the adhesion layer less noticeable power. However, it is not to be expected, even though the light transmittance in the case of a thickness of the photocatalyst layer is less than improved 0.1 microns is that high photocatalytic activity is achieved, since the photocatalyst usable ultraviolet rays as the photocatalyst layer penetrate. The entire light passage of a photocatalyst layer and an adhesion layer at a wavelength of 550 nm is 70% or more, respectively, when a thickness of the photocatalyst layer in a range from 0.1 .mu.m to 5 microns is set, and a photocatalyst of which particles have a Diameter of 40 nm or less and either a metal oxide gel or a metal hydroxide gel, whose specific surface content 100 m²are / g or more, is used. In the case a photocatalyst-carrying structure, the entire light passage at a wavelength of 550 nm is 70% or more, can be obtained by the structure of light passing visible light for Illumination are used while such a structure from the decorative point of view is useful since it does not waste design to a substrate when the substrate is of such a structure opaque.

The Substrate may be formed in all complex forms such. B. as a film, a plate, tubular, as Fiber and as a network, and the adhesion layer and the photocatalyst layer can are provided on each such substrate, so that a desired photocatalyst-carrying Structure. In terms of the size of the substrate can both the adhesion layer wear and the photocatalyst layer, if there is a size of 10 microns or more having. Even an organic polymer at the time of coating must not be heated, and a metal that is easily oxidized and by means of heat or with water is corrosive, can be used as the materials for the Substrate is used, so that it is possible, make a structure to which an adhesive layer and a photocatalyst layer are provided, which both high photocatalytic activity and high exhibit durability. To the close adhesion between a substrate and an adhesive layer to improve, a substrate may also be used, the surface a discharge process, a primer process and the like is subjected.

As indicated in the below-described examples of this patent, is the photocatalyst-carrying structure according to the present invention useful for colors for architectural Using, Wall Murals, window glass, blinds, curtains, carpets, Lighting applications, lighting, black lights, colors for a Hull and fishing nets, fillings for water treatment, vinylchloride films for use in agriculture, Films for preventing the growth of weeds, packing materials etc .. In addition, , the photocatalyst-carrying structure can be made to a structure the high under conditions of high humidity and temperatures is usable.

According to the present Invention, it is possible a an adhesion layer and carrying a photocatalyst layer structure with high durability characteristic provide, in accordance with a Test the adhesive property, the so-called cross-cut Scotch tape test accordance with JIS K5400, even after the irradiation with an ultraviolet radiation intensity of 3 mW / cm² -terminated black light for 500 hours at 40 ° C and 90% relative humidity with an evaluation point of 6 or expressed higher. additionally was in an accelerated weathering test using a Sunshine-weathering meter a obtained photocatalyst-carrying structure, such an excellent, in a test of the adhesive property for 500 hours in accordance with this Crosscut Scotch tape test accordance with JIS K5400 with an evaluation point of 6 or more reproduced weathering resistance. In addition, a scored structure, high resistance opposite to boiling water shows, so that the means of cross-cut Scotch tape test accordance with JIS K5400 after immersion in boiling, an electrical conductivity of 200 ĩS / cm at 20 ° C exhibiting water for 15 min rated adhesive property of the structure with an evaluation point is represented by 6 or more. Since high photocatalytic activity in all Samples of these structures is observed is assumed that the structure according to the present inventions&lt;?page 11?&gt;tion as described above satisfactory properties in respect has various applications.

If a substrate made of glass is produced, the glass may in all complex Forms such as a plate, tubular, spherical, and be as fibers formed, and is connected to said adhesive layer and said photocatalyst layer is provided. Regarding the size thickness can contribute a thickness of 10 microns or more stable this glass. It should also it is also possible, dependent of its application, such as. for example, in window glass, display cabinets and Glasses, apply such layers on the treated glass, such that a photocatalyst-carrying glass according to the present invention will be produced.

The Photocatalyst-carrying glass according to the present invention can for different objects are used, the antibacterial, deodorizing and dirt require repellent effects, but such. as cameras and lenses, even window glass, cover glass for Instruments, lighting applications, lighting, blue fluorescent lamps with black light and fillers for water treatment.

A according to the present Invention a photocatalyst-supporting plastic mold can be used for different Applications are used, the antibacterial, a deodorizing and a dirt-repelling action require such. as for cameras and lenses, but also for Wall Murals, shelves for interior decoration, furnishings, electrical applications and vehicle parts.

Regarding the Shape of the above-described plastic mold can all complex shapes, such as. for example, as film, plate-shaped, tubular, spherical and as a fiber, for the manufacture of a structure of a plastic mold with said adhesive layer and said photocatalyst layer can be used. Regarding the thickness can Such plastic molds such layers with a thickness of 10 microns or more stable carry. also it is also possible, dependent by applications such. as for building materials, home electrical applications and spectacles, such layers to the plastic mold apply, so that a photocatalyst-carrying plastic mold according to the present Invention is manufactured and, consequently, is to be understood that the Structure of the present invention is essentially a wide has scope.

Lots Fabric types can for the Substrate of the present invention are used; as examples called: fabric, knitted fabric and nonwoven textiles, including single or mixed fibers consisting of natural fibers such as wool, silk, Cotton and hemp yarn, regenerated fibers such as rayon and acetate, synthetic fibers such as nylon, acrylic, polyamide, polyester, polyacrylonitrile and polyvinyl chloride, and heat-resistant fibers such as aramid fibers. Also, as the structure of the present invention with a water-repellent material coated fabric such. B. a silicon-containing water repellent, a fluorine containing water repellent including perfluoroalkyl, zirconium containing containing water repellent material and ethylene urea Water-repellent material, a repellent with both water Material and with a crosslinking agent such. as ethyleneimine coated fabric, epoxy and melamine compounds improving the resistance, if necessary, an imitation leather made ​​of formed fibrils com plex Polyamide and polyester fibers, and a synthetic leather, wherein a polyurethane resin layer on a substrate such as a woven fabric, Nonwoven textiles and knitwear by a polyurethane are formed adhesive is formed, used. Likewise, by means Application of such a water-repellent material and the like on substances etc. processed into umbrellas, tents, bags are, the photocatalyst-carrying substances according to the present Invention are achieved.

Of the described in the present invention photocatalyst-carrying Fabric is for various applications used, the antibacterial, deodorizing and a dirt repellent effect requires, z. B. Interiors like curtains and wallpapers, tents, umbrellas, everyday items such as tablecloths, Packaging materials for Foods and the like and for agricultural use such. as films for seedling beds.

For the present, according to the Invention photocatalyst-carrying metal, an alloy such as stainless Steel, brass, aluminum alloy and titanium alloy, as well as single-element metals such as aluminum, iron and copper are used as a substrate. In addition, if so forth of the design and from the viewpoint of quality as a metal to be used is concerned, it is also possible, both an adhesion layer and a photocatalyst layer according to the present invention on the substrate, such, for example, a painted with colors normal metal foil and plate and a colored steel plate &lt;?page 12?&gt;or aluminum plate apply. In this case, it is further preferable that when the light transmittance both the adhesion layer and the photocatalyst layer of sufficiently good and transparent is, these layers are no bad influence on the color of the comprising the underlying substrate.

Regarding the Shaping of the metal, there is no difficulty in the metal any complex shape, such. as plate-shaped, tubular, spherical, as Fiber and film-like to design so that it this adhesion and this photocatalyst layer can be applied. also the metal can wear these layers stable if its thickness 10 microns or more. Further, depending z of their use. B. for Windows, showcases and spectacle lenses, all of which are further processed, the photocatalyst-carrying Metal according to the present Invention by depositing these layers on the further processed Metals are produced.

The Photocatalyst-carrying metal according to the present invention can for different applications are used, the antibacterial, require deodorizing and dirt repellency, z. B. sieves Filters and the like also for Windows, furniture, accessories and decoration, paneling for indoor and outdoor decoration, fillers for water treatment etc ..

Regarding the Design of timber and wooden Materials on which the adhesion layer and the photocatalyst layer according to the present invention is provided, any complex configuration, such as, for. example, can plate-shaped, tubular, spherical, and are film-like, used. These timbers or wooden materials in a thickness of 10 microns or more sufficiently wear these layers thereon, and it is possible, a photocatalyst-carrying lumber or wood material according to the present prepare invention by these layers to this timber and these wooden Materials, such as walls, wood paneling, columns, Furniture and timbers that were processed previously applied, be.

The a photocatalyst-supporting timber and wood Materials according to the present invention can for different applications are used, the antibacterial, require deodorizing and dirt repellency, z. B. for building materials, Furniture, timbers and materials for interior decoration.

by means of the advantageous properties as a dirt-repellent, a antibacterial and deodorizing function, a with the photocatalyst-carrying structure according to the present invention equipped plastic film can be produced as a film whose Area, not carrying the photocatalyst is coated with an adhesive is, and these films can on the inner surface window glass of an entity such as cars and various means of transport, buildings, applied freezer and refrigerator-showcases and greenhouses , whereby it is made possible with this glass, highly transparent glass provide that the decomposition of the interior existing traces of harmful Substances and accelerated on a glass surface dirt repellency and its destruction has a preventive effect on the shattering of the glass. When the photocatalyst-carrying structure according to the present invention using a thin Plastic film is prepared as a substrate, this can be used as a Einpackfolie for use used as food packaging will. As a for Such plastic films suitable resin may be a resin such. B. Polyethylene telephthalate resin, Polycarbonate resin, polyacrylate resin, polymethyl methacrylate resin, Polyethylene resin, Polypropylene resin, polyamide resin, polyimide resin, polystyrene resin, Polyvinyl chloride resin, Polyvinylidene fluoride resin, ethylene fluoride-propylene copolymer resin and ethylene fluoride-ethylene copolymer resin to form a highly light-transmissive synthetic Resin film or sheet can be pressed, the linear light transmittance at a wavelength of 550 nm is 50% or more, be used. In addition, the photocatalyst-carrying exercises Structure according to the present Invention, as it is transparent, no negative effect on on the surface the underlying wallpaper and decorative sheets printed Design and pattern, so that the photocatalyst layer advantageously on the surface an opaque material such. as wallpaper and decorative films, with an adhesive layer and a removable film have on its back, applied can be.

in these synthetic films or sheets of resin described above Is it possible, the adhesive property of the adhesive layer in the photocatalyst-carrying structure by treating the surface of these films and sheets, on the surface thereof an adhesive layer is applied, while physically a trace amount oxidation subjected to corona discharge treatment and UV-ozone treatment are, and those whose contact with an adhesive layer by lighter application of a surface treatment agent such as silicon-containing Compounds is improved, can preferably &lt;?page 13?&gt;be used. Additionally, it is also possible, as in the examples for embodiment of the present invention illustrated, a thin film on the surface, or the back such materials for providing reflective and shading Functions over Heat Radiation and ultraviolet radiation to fix, whereby heat-ray reflection films and ultraviolet ray interruption films same dirt-repellent, antibacterial and deodorant act, are achievable. It is understood that the photocatalyst-carrying Structure according to the present Invention has both high durability and photocatalytic activity, and consequently could it an extremely useful his and valuable product.

As a method for providing the above-described heat-ray reflection function can Various methods, such as. for example, a method of forming a Film on a film surface of an electrically conductive Metal, eg. As Al, Ag, Cu, Cr, Ni, Ti, stainless steel and aluminum alloys, or an electrically conductive Metal, z. B. indium oxide, tin oxide and tin-indium compound, according to physical Methods such. As sputtering and vacuum evaporation, a process for forming a film on a film surface by means of applying and subsequent Drying an electrically conductive Metal oxide solution or sol on the film surface or using either electroplating or CVD method and a method for admixing a material having Heat ray-reflecting property and / or heat ray-interrupting property are added to the substrate used. Nevertheless, can be used as a method of Providing the interrupt function for ultraviolet rays different Methods are used, such as. For example, a method of forming a Film on a film surface absorbing means applying an ultraviolet ray Agent as impaired Amine-containing compounds and titanium oxide, and an ultraviolet Ray reflecting agent and a method for preliminary Admixing an ultraviolet ray absorbing agent in a Film substrate, and are dependent on their purpose and their chemical structures auswahlbar. When titanium dioxide blocking ultraviolet rays as agent or used as ultraviolet ray reflecting agent is, the one is preferably used, that its photocatalytic activity due to thin Coating the titanium dioxide surface with soluble glass or the like lost because surrounding organic materials due to the photocatalytic activity are decomposed when titanium dioxide is present alone, as described in detail is explained in the present invention.

Materials, a heat ray-reflecting have function and an ultraviolet ray blocking function, can be integrated into an adhesive layer on the back side a film for providing these functions is formed. To the Example is a material such as a clear coating agent to Blocking ultraviolet rays, as in "Convertec" March 1996, page 95 describes a dispersible in the solvent Variety and is for the above purpose applicable. Adhesives such as acrylic type and Silicon-containing compounds are normally used. However, it is also possible different types of absorbing ultraviolet rays agents and heat ray blocking Agents should admit. In view of the remaining with the adhesive caused contamination at the time of renewal the photocatalyst carrying Film, it is recommended that the use of an adhesive with strong connection property to avoid. As a method for Providing an adhesive and a releasable film again on a photocatalyst-carrying film, a method in which First, an adhesive in solution by gravure printing on the back side the film is applied and then the coated film together peelable again with a dry polypropylene film and to roll, thereby to laminate it, simple and can be preferably used.

Brief Description of Drawings

<figref idrefs="S70">1</figref> shows a representation of a cross section of the photocatalyst-carrying Structure according to the present Invention.

Best Mode for carrying out the invention

the present invention is finally explained with reference to the described in the following examples, but should not, the present invention referred to in these examples Application described are limited.

&lt;?page 14?&gt;

evaluation procedures

1) Evaluation of the photocatalytic activity

A carrying a photocatalyst sample having a size of 70 mm × 70 mm is placed in a 4 L Pyrex beaker. A gas mixture of Air and acetaldehyde was introduced into this beaker and the concentration of the acetaldehyde was set to 500 ppm. The sample was for 2 hours by black light irradiated (Type: FL 15BL-B; manufactured of Matsushita Electric Industry Co., Ltd.) with an ultraviolet ray intensity of 2 mW / cm², Then, the concentration of the Azetaldehydgases in the vessel under Using gas chromatography determined and the photocatalytic activity was calculated based on the reduced concentration. criteria for the Evaluation was provided as follows. <tables><table frame="all"><tgroup cols="2" colsep="1" rowsep="1"><colspec colname="1" colwidth="2.00*" /><colspec colname="2" colwidth="1*" /><tbody><row><entry colname="1">Azetaldehydgas concentration after 2 hours</entry><entry colname="2">evaluation ranking</entry></row><row><entry colname="1">&lt;50 ppm</entry><entry colname="2">A</entry></row><row><entry colname="1">50-200 ppm</entry><entry colname="2">B</entry></row><row><entry colname="1">200-300 ppm</entry><entry colname="2">C</entry></row><row><entry colname="1">300-450 ppm</entry><entry colname="2">D</entry></row><row><entry colname="1">450 ppm &lt;</entry><entry colname="2">e</entry></row></tbody></tgroup></table></tables>

2) Evaluation of adhesive property

the Evaluation of adhesive property was in accordance with the cross-cut Scotch tape test accordance with JIS K5400 performed. A distance between cross-cut lines was set to 2 mm, and the number of squares is determined on 25th

the Evaluation points were on a method described in JIS K5400 criterion ajar.

3) immersion test in boiling water

tap water having an electrical conductivity in the range 170-230 ĩS / cm was added together with a small amount of boiling stones into a 1000 mL Pyrex beaker filled, to a size of 70 mm × 70 mm tailored sample was measured using a normal clip hung in boiling water, so that all of the sample after heating and boiling the water it plunged. After 15 minutes immersion in boiling water was the sample for cool at room temperature for 4 hours and allowed to dry, then was described in Section 2) performed test of adhesion property, so that evaluation points according to the in JIS K5400 criterion described were obtained.

4) Total light transmittance

the total light transmittance at a wavelength of 550 nm of an adhesive layer and a photocatalyst layer-bearing sample was measured using an automatic recording spectrophotometer (Model: U-4000 manufactured, by Hitachi Seisakusho) in comparison to a substrate to which no adhesion and photocatalyst layer was applied is performed.

5) Evaluation of Durability

the coated sample was for 500 hours a black light irradiation with ultraviolet radiation intensity of 3 mW / cm² in a chamber at 40 ° C and 90% exposed to relative humidity, then was the Section performed 2 described test of adhesion property, so that evaluation points according to the in JIS K5400 criterion described were obtained.

6) Accelerated weathering test Using the Sunshine Carbon Arc weathering meter

Expedited Weathering test using the provided in JIS K5400 Sunshine Carbon Arc Weathering Meter was prepared using the same meter (Type: WEL-SUN-HCH; manufactured by Suga Shikenki Co., Ltd.) Conditions, namely Test duration of 500 hours, black panel temperature of 63 ° C, 120 min Cycle and 18 min rain event performed. 3 pieces of samples were accelerated subjected to weathering test, then the samples were visually evaluated with regard &lt;?page 15?&gt;Swelling, cracking, peeling, fading and surface change in comparison with the original test pieces before they subjected to conditions of accelerated weathering tests were, according to the following Criteria. <tables><table frame="all"><tgroup cols="2" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="4.00*" /><tbody><row><entry colname="1">evaluation ranking</entry><entry colname="2">criteria for evaluation</entry></row><row><entry colname="1">A</entry><entry colname="2">all 3 samples showed no change.</entry></row><row><entry colname="1">B</entry><entry colname="2">1 or 2 samples showed slight changes.</entry></row><row><entry colname="1">C</entry><entry colname="2">all 3 samples showed slight changes, or 1 or 2 samples showed significant changes obviously.</entry></row></tbody></tgroup></table></tables>

After performing this test was the test described in Section 2) of the adhesive property for Obtaining evaluation points according to the method described in JIS K5400 Criterion performed.

7) Test method for antibacterial property

the a piece of size 5 cm × 5 cm tailored Sample is disinfected with 80% ethanol and then dried at 150 ° C, and 0.2 mL of a bacterial suspension of intestinal bacteria, previously and cultured to a concentration of 10⁵/ mL dilute was, was added dropwise onto the surface of the sample and this placed in an incubator. For all irradiation conditions were 4 per sample for the test provided, namely 4 samples for Black light irradiation (15 W × 2 Lamps, distance between a light source and the sample is 10 cm), 4 samples for Irradiation with fluorescent lamp (15 W x 2 lamps, distance between a light source and the sample is 10 cm) and again 4 samples were for the test provided without irradiation. After the predetermined Time had elapsed (after 1, 2, 3 and 4 hours), the samples were taken out and adhering to the sample bacteria solution was using disinfected, with sterilized physiological (Cooking) salt solution soaked Gauze wiped. The sterilized gauze used was in 10 mL sterilized saline given and carefully shaken. The supernatant the bacterial solution thus obtained was one in a sterilized using an autoclave petri dish made of 95 mm diameter agar medium inoculated. Then, the number of at 36 ° C 24 Hours cultured colonies of intestinal bacteria counted. A other, according to the same procedure from Huftropfen the bacteria solution to for bodies recovered in an incubator sample was in accordance with the above treated methods described and the number of intestinal bacteria colonies was counted. Based on the determined number, the survival rate of the bacteria was after respective predetermined time for each group, namely without Irradiation, irradiation with black light or irradiation with a Fluorescent lamp, is calculated. The evaluation criterion corresponded the following table. <tables><table frame="all"><tgroup cols="2" colsep="1" rowsep="1"><colspec colname="1" colwidth="1.5*" /><colspec colname="2" colwidth="1*" /><tbody><row><entry colname="1">Survival (%) Of the intestinal bacteria after 4 hours</entry><entry colname="2">evaluation ranking</entry></row><row><entry colname="1">&lt;20%</entry><entry colname="2">A</entry></row><row><entry colname="1">20-40%</entry><entry colname="2">B</entry></row><row><entry colname="1">40-60%</entry><entry colname="2">C</entry></row><row><entry colname="1">60-80%</entry><entry colname="2">D</entry></row><row><entry colname="1">80% &lt;</entry><entry colname="2">e</entry></row></tbody></tgroup></table></tables>

As an index for evaluating the dirt-repelling function of the sample A decomposed amount of ordinary, mostly from linoleic existing salad oil quantified on a photocatalyst-carrying structure, to see how quickly decompose on the surface fat and oil can be. On the surface one in pieces a size of 5 cm × 5 cm cut photocatalyst-carrying structure was salad oil slightly at a dose of 0.1-0.15 mg / cm² applied using a paper. The coated amount was calculated from the difference in the weight of Structure before and after application of the oil using an accurate Libra measured. As an index of the stain-proofing property were decomposed amounts of salad oil specified by previously Times by adjusting the distance between the sample and black light determined, where a point was sought to which an ultraviolet radiation intensity on a surface Sample 3 mW / cm² was, and calculating the ratio between elapsed time and weight loss after exposure with black light. &lt;?page 16?&gt;<tables><table frame="all"><tgroup cols="2" colsep="1" rowsep="1"><colspec colname="1" colwidth="1.50*" /><colspec colname="2" colwidth="1*" /><tbody><row><entry colname="1">Remaining Amount (%) of salad oil after 24 hours of light irradiation</entry><entry colname="2">evaluation ranking</entry></row><row><entry colname="1">&lt;10%</entry><entry colname="2">A</entry></row><row><entry colname="1">30-10%</entry><entry colname="2">B</entry></row><row><entry colname="1">50-30%</entry><entry colname="2">C</entry></row><row><entry colname="1">80-50%</entry><entry colname="2">D</entry></row><row><entry colname="1">80% &lt;</entry><entry colname="2">e</entry></row></tbody></tgroup></table></tables>

Examples

Following Materials were used as substrate. <dl><dt>(TA)</dt><dd>Primer-treated polyester film</dd><dt>(TB)</dt><dd>Vinyl chloride film</dd><dt>(TC)</dt><dd>Soda-lime glass plate</dd><dt>(TD)</dt><dd>Metal aluminum plate</dd><dt>(TE)</dt><dd>High density polyethylene mesh (Fiber thickness: 0.2 mm, mesh width: 0.6 mm)</dd><dt>(TF)</dt><dd>Polypropylene tube (inner diameter: 30 mm, outside diameter: 36 mm)</dd></dl>

As in an adhesive layer contained polysiloxane following materials were used. <dl><dt>(PS-1)</dt><dd>Silicon Tetramethoxid monomer (Manufactured by Shinetsu Chemical Industry Co., Ltd.)</dd><dt>(PS-2)</dt><dd>Polymethoxy silane (Manufactured by Colcoat Co., Ltd., trade name: Methyl Silicate 51)</dd><dt>(PS-3)</dt><dd>Polyethoxy siloxane (Manufactured by Colcoat Co., Ltd., trade name: Ethyl Silicate 40)</dd></dl>

As in an adhesive layer contained colloidal silica The following materials were used. <dl><dt>(KS-1)</dt><dd>Trade name: Cataloid SI-350 (Manufactured by Shokubai Kagaku Co., Ltd., Particle diameter: 7-9 nm)</dd><dt>(KS-2)</dt><dd>Trade name: Snowtex ST-XS (produced by Nissan Chemical Industries Co., Ltd., particle diameter: 4-6 nm)</dd></dl>

As Resin solution, is introduced into the polysiloxane or colloidal silica, were The following materials used. <dl><dt>(J-1)</dt><dd>3% by weight of silicon containing acrylic-silicon resin solution in xylene</dd><dt>(J-2)</dt><dd>10% by weight of silicon containing acrylic-silicon resin solution in xylene</dd><dt>(J-3)</dt><dd>20% by weight of silicon containing acrylic-silicon resin emulsion in water</dd><dt>(J-4)</dt><dd>50% by weight of silicon containing acrylic-silicon resin emulsion in water</dd><dt>(J-5)</dt><dd>10% by weight of silicon containing polyester-silicon resin solution in xylene</dd><dt>(J-6)</dt><dd>Acrylic resin solution in xylene</dd><dt>(J-7)</dt><dd>Polyester resin solution in xylene</dd><dt>(J-8)</dt><dd>3% by weight of silicon containing epoxy-silicon resin solution in Methylehtylketon</dd></dl>

Either Polysiloxane or colloidal silica were mixed with a resin solution, and the mixture obtained was applied to a certain concentration diluted, so that a solution for the Use to form an adhesive layer was produced. The adhesion layer was formed using the dipping method when a thickness of the layer of 2 microns or less is their design and different from a plate, while using the Baker applicator was formed when the thickness of 2 microns or more is and plate-shaped design is. In particular, the adhesive layer was to dip-coating formed when designing tubular or reticulated is. The drying process for the adhesion layer found at 80 ° C instead, when the material for the substrate is (TE) or (TF), was at 60 ° C, when the material was (TB), and at 120 ° C in all other cases.

For the photocatalyst The following materials were used. &lt;?page 17?&gt;<dl><dt>(C-1)</dt><dd>Fine powder of Titanium dioxide (manufactured by Nihon aerozil Co., Ltd., trade name: P-25, diameter of the crystallite size: 27 nm)</dd><dt>(C-2)</dt><dd>Titania sol (Sol acidified with nitric acid, Diameter of crystallite size: 10 nm)</dd><dt>(C-3)</dt><dd>Titania sol (weak alkaline sol with pH 9.0, diameter of crystallite size: 20 nm)</dd></dl>

On Metal oxide sol or a metal hydroxide sol which together with a Photocatalyst was coated, was prepared by drying a won the following materials in sol form. <dl><dt>(Z-1)</dt><dd>Silica sol: manufactured by Shokubai Kasei Co., Ltd., trade name Cataloid SI-30, specific surface area after drying at 150 ° C: 180m²/G</dd><dt>(Z-2)</dt><dd>Alumina sol: manufactured by Nissan Chemical Industries Co., Ltd., trade name: Alumina sol-200, specific surface area after drying at 150 ° C: 400 m²/G</dd><dt>(Z-3)</dt><dd>Zirconia sol: This can by hydrolyzing zirconium tetrabutoxide (TBZR; manufactured by Nippon Soda Co., Ltd.) in ethanol, drying at 150 ° C, then heating to 300-500 ° C, followed by dispersing with a dilute aqueous recovered nitric acid solution be. The specific surface area the then at 150 ° C dried product of the sol dispersed in the range of 50 to 80 m²/G.</dd><dt>(Z-4)</dt><dd>Niobium oxide sol: This can by neutralizing an aqueous solution of niobium oxalate, prepared aqueous by CBMM Co., Ltd., with 10% Ammonia, drying at 150 ° C and subsequent Dispersing with a dilute aqueous recovered nitric acid solution be. The specific surface area the then at 150 ° C dried product of the dispersed sol is 60 m²/G.</dd><dt>(Z-5)</dt><dd>20% by weight of silicon containing acrylic-silicon resin emulsion in water.</dd><dt>(Z-6)</dt><dd>Silane coupler, tri (beta-methoxyethoxy) vinyl-silane (Trade name: A-1 72), manufactured by Nippon Uniker Co., Ltd ..</dd></dl>

A solution for forming a photocatalyst layer was prepared by dispersing of titanium dioxide in a solution obtained as described above and adding a predetermined amount of a surfactant manufactured. The photocatalyst layer was formed by the dipping method when the layer 2 to or less and / or the design of a substrate is other than plate-shaped, while formed the photocatalyst layer using a bar coater was when the substrate is a plate and its thickness is 2 microns or more is. The drying process for the photocatalyst layer was performed at the same temperature as drying the adhesive layer.

in the Below are shown in Table 1-4 the compositions in the examples for the embodiment the present invention and disclosed in comparative examples, wherein type, quantity and / or thickness of the materials and / or methods for forming the films are different, and performances the photocatalyst-carrying structure are described.

&lt;?page 18?&gt;

<img img-content="tb" img-format="tif" he="232" wi="146" file="00330001.tif" />

&lt;?page 19?&gt;

<img img-content="tb" img-format="tif" he="235" wi="155" file="00340001.tif" />

in Examples 1 to 18 and Comparative Examples 1 to 4 was Titanium dioxide (P-25) manufactured by Nihon Acrozil Co., Ltd., the is shown in (C-1) used as a photocatalyst. The Result is shown in Table 1 below.

&lt;?page 20?&gt;

in the Comparative Example 1 is supporting a photocatalyst layer given structure without providing an adhesive layer. In this Case, the photocatalyst layer no adhesive property to and is easily peeled. Further, after the durability test, the surface of the polyester film is due to damaged a photocatalytic effect, and holes and cracks were observed on the film.

in Examples 1 and 2 is used a structure in which either Acrylic-silicon resin or polyester-silicon resin as an adhesion layer is used. In this case, the adhesive property of a photocatalyst layer was and durability of the structure found to be excellent.

in Examples 3 to 12, a structure was used in a was used polysiloxane-containing resin as an adhesion layer. In this case, the adhesive property and durability were improved. As the polysiloxane-containing resin obtained and the acrylic-silicon resin (s. Examples 3, 4 and 5) and polyester-silicon resin (see. Example 9) good durability. It was also found that the polysiloxane containing resin either by acrylic resin (s. Example 7) or by Polyester resin (Example 12) could be replaced, both the Structure with excellent characteristics ausstatteten.

in the Contrast, lost, as shown in Example 2, a photocatalyst layer despite the use of polysiloxane-containing acryl-silicon resin for the adhesion, adhesive properties and has been released from the adhesive layer when the content of polysiloxane in the adhesive layer up to a proportion increased from 70% by weight is.

in Examples 13 to 18 is a structure used in a colloidal silica containing resin as an adhesion layer has been used. In these cases were all, the photocatalytic activity, adhesive property and durability, found to be excellent. In particular, when acryl-silicon resin and colloidal silica in fine particle size (KS-2) was used (Examples 15 and 16), the resulting adhesion layer has been found to be very good.

in the Contrast, when the content of colloidal silica in the adhesion increased to 50% by weight was, both the adhesive property and the durability considerably deteriorated.

in Examples 1 to 18 was titanium dioxide (P-25) manufactured by Nihon Aerozil Co., Ltd. represented in (C-1), as a photocatalyst, used and silica sol was in most cases as a metal oxide sol or metal hydroxide sol as part of the photocatalyst layer used, and the structures were in all examples with excellent Properties equipped. In Examples 8 and 9 were the Structures disclosed in which both layers on a substrate of polyethylene or polypropylene mesh tube are applied, and it it is shown that these structures excellent photocatalytic Activity, having adhesive property and durability. It was also found, that this excellent property by lowering the content of silica sol in the photocatalyst layer to 30% by weight of still were noticeable (s. Example 6), however, both adhesive property and the durability were greatly deteriorated when the content was lowered to 20% by weight (s. Example 4).

in Example 11 was a structure used in the alumina sol used in place of silica sol was, and this structure was in its capacity as the same Excellent as found in the use of silica sol.

in Example 17, a structure was used in which a thickness of a adhesion and a photocatalyst layer onto 0.5 .mu.m and 1 .mu.m was set. In this Case, both the adhesive property and the durability excellent, and the photocatalytic activity was found to be very high out, although the thickness of the photocatalyst layer was very thin.

the Data obtained in Examples 19 to 23 are shown in Table 2 below.

&lt;?page 21?&gt;

<img img-content="tb" img-format="tif" he="233" wi="95" file="00370001.tif" />

Example 19 Use of titanium oxide sol

On Coating material for the use for forming a photocatalyst layer was prepared by Adding and dispersing 12% by weight of titanium dioxide containing and with nitric acid at&lt;?page 22?&gt;leavened Titanium oxide sol, and titanium (IV) oxide sol or titania sol, called the a substituent of the fine-grained Titanium dioxide (P-25) manufactured by Nihon Aerozil Co., Ltd., is, to silica gel (Trade name: Cataloid SI-30, manufactured by Shokubai Kasei Co., Ltd.), adjusting the pH to 1.5 and further adding a surfactant Substance produced. a solution was however to be used for an adhesive layer by means of adding polymethoxy silane (PS-2) to an in Example 10 resin solution used in a relationship so that the content of silicon oxide in a dried adhesive layer 35% mass fraction is, produced.

the solution for forming an adhesive layer was performed using a Baker applicator to a soda lime glass substrate applied with a thickness of 1 mm and a size of 7 cm × 7 cm, and the coating material for forming a photocatalyst layer was also using a bar coater on the same substrate applied. The drying temperature was as in the above-described Examples set.

the scored photocatalyst-carrying structure had very high total light transmittance on.

Example 20 Use of silica-alumina sol

A Photocatalyst-carrying structure was prepared using the same Materials and manufactured by the same method as in Example 19, with the exception that the silica sol in Example 19 by a mixed sol solution of alumina sol manufactured by Nissan Chemical Industries Co., Ltd. and silica sol was produced.

For the obtained Photocatalyst-carrying structure have high adhesive property and photocatalytic activity detected.

Example 21 Coating according to the gravure printing process

at Using the gravure printing process were the solution for forming an adhesive layer and the solution for forming a photocatalyst layer on a polyester film (Trade name: Cosmo Shine A4100) manufactured by Toyobo Co., Ltd., at a rate of 10 m / min and at a drying temperature range of 130 ° C applied so that the thickness of the layers was 3 microns. For the Printing method, a micro-gravure coating apparatus having a Width of 70 cm manufactured by Yasui Seiki Co., Ltd. was used.

For the scoring Photocatalyst-carrying structure was very high total light transmittance determined by 95%.

Example 22 coating according to the spray method

the Example 9 used solution for forming an adhesive layer and the solution for forming a photocatalyst layer were carried out using a spray gun (type: RESIST 88, manufactured by Iwata Tosoki Kogyo KK) was sprayed onto a substrate of soda lime glass. Both solutions for forming the adhesion layer and the photocatalyst layer were dried at 120 ° C for 30 minutes.

For the scoring Photocatalyst-carrying structure were good adhesion property and photocatalytic activity detected.

Example 23 Use of Epoxy-silicon resin

A Photocatalyst-carrying structure was prepared using the same Materials and the same method as prepared in Example 12, except that the polyester resin solution in xylene by methyl ethyl ketone solution of 3% by weight of epoxy resin containing silicon has been replaced.

For the scoring Photocatalyst-carrying structure were good adhesion property and photocatalytic activity detected.

the Compositions and the results of performance tests feature the photocatalyst-carrying structures are shown in Table 3 below.

&lt;?page 23?&gt;

<img img-content="tb" img-format="tif" he="249" wi="142" file="00400001.tif" />

&lt;?page 24?&gt;

Examples 24-25

in Examples 24 and 25, a structure disclosed in the acrylic-silicon resin for forming an adhesive layer is used, and a mixture prepared and composed is fine-grained from 50 wt% Titanium dioxide P-25 (C-1), 25% by weight in (Z-1) being played Silica sol and 25% by weight in (Z-2) being played alumina sol to Forming a photocatalyst layer is used. For in These examples disclosed structures were good adhesion property and good durability and resistance determined under accelerated weathering conditions.

Examples 26-31

in Examples 26 to 31, a structure is disclosed in which a Polysiloxane-containing resin to form an adhesive layer was used, and for forming a photocatalyst layer fine-grained titanium dioxide (C-1) in Examples 26 to 28 and titania sol (C-2) in Examples 29-31 was used, and the type and amount of a sol for forming changed a miscible gel has been. For the structures prepared in these examples were good photocatalytic activity and good adhesion property, durability and resistance at on testing boiling water found the following accelerated weathering tests. For the with polysiloxane blended resins such as acrylic-silicon resin (examples 26, 27 and 28) and epoxy-silicon resin (Examples 29 and 30) were good adhesion property, Durability and resistance towards accelerated Weathering observed. Likewise were for mixed with polysiloxane Acrylic resin (Example 31) found good properties.

Examples 32-35

in Examples 32 and 33, a structure shown in the either a polyethylene net or polypropylene tube was used as the substrate, the photocatalyst-carrying structure exhibited good photocatalytic activity, adhesive property and Durability, however, were not obtained.

in Examples 32 to 35 are structures disclosed in which a colloidal silica exhibiting resin was used for forming an adhesive layer, and the photocatalytic activity, adhesive property, durability and resistance opposite to accelerated weathering of these structures were for outstanding found. In particular, when the structure with colloidal silica in small Particles (KS-2) is produced and the colloidal silica in the acryl-silicon resin emulsion (S. Examples 34 and 35) is introduced, have been for this Structure type very determined good properties.

in Example 29 is a structure disclosed in which a photocatalyst layer is formed of a coating material by 12% by weight Titanium dioxide containing titanium oxide sol, silica gel (trade name: Cataloid SI-30, manufactured by Shokubai Hasei Co., Ltd.) and alumina sol-200, manufactured by Nissan Chemical Industries Co., Ltd., dispersed is the pH of the resulting mixture to 1.5 is adjusted and the mixture a predetermined amount of a surfactant Substance is added, and the thickness of an adhesive layer and a photocatalyst layer is adjusted by means of the dipping method, respectively to 0.5 microns and 0.3 microns. For those with the layers equipped structure described above were good found adhesive property and durability as well as high photocatalytic activity, despite the thin Thickness of the photocatalyst layer.

A Structure with excellent physical property was well obtained when the total content of silica gel and alumina sol was lowered into a photocatalyst to 30 wt% (s. Example 30).

the photocatalytic activity of the samples prepared in Examples 24 to 35 was determined again, after a durability test under black light at high Temperature and high humidity, an immersion test in boiling Water and accelerated weathering test using the Sunshine Carbon Arc weathering meter according to the above The method described, in particular, based on the means of Light decomposed amount of acetaldehyde, were subjected. As a Result was found that all samples same decomposition activity with respect to initially decomposed amount of acetaldehyde demonstrated and it has been found that samples their initial photocatalytic activity completely retained. &lt;?page 25?&gt; Table 4 <tables><table frame="all"><tgroup cols="14" colsep="1" rowsep="1"><colspec colname="1" colwidth="1.20*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><colspec colname="8" colwidth="1*" /><colspec colname="9" colwidth="1*" /><colspec colname="10" colwidth="1*" /><colspec colname="11" colwidth="1*" /><colspec colname="12" colwidth="1*" /><colspec colname="13" colwidth="1.20*" /><colspec colname="14" colwidth="1.20*" /><tbody><row><entry morerows="2" /><entry colname="2">carrier</entry><entry namest="3" nameend="5">adhesion</entry><entry namest="6" nameend="12">Photocatalyst layer</entry><entry morerows="2" colname="13">adhesion Thickness (microns)</entry><entry morerows="2" colname="14">Photocatalyst layer thickness (microns)</entry></row><row><entry morerows="1" colname="2" /><entry morerows="1" colname="3">Type</entry><entry morerows="1" colname="4">Contents * 1</entry><entry morerows="1" colname="5">Resin soln.</entry><entry namest="6" nameend="7">titania</entry><entry colname="8">Z-1</entry><entry colname="9">Z-2</entry><entry colname="10">Z-3</entry><entry colname="11">Z-5</entry><entry colname="12">Z-6</entry></row><row><entry colname="6">Type</entry><entry colname="7">Contents * 2</entry><entry colname="8">Contents * 2</entry><entry colname="9">Contents * 2</entry><entry colname="10">Contents * 2</entry><entry colname="11">Contents * 2</entry><entry colname="12">Contents * 2</entry></row><row><entry colname="1">Bsp.-36</entry><entry colname="2">TA</entry><entry colname="3">-</entry><entry colname="4">-</entry><entry colname="5">J-1</entry><entry colname="6">C-1</entry><entry colname="7">50</entry><entry colname="8">40</entry><entry colname="9">-</entry><entry colname="10">-</entry><entry colname="11">10</entry><entry colname="12">-</entry><entry colname="13">10</entry><entry colname="14">6</entry></row><row><entry colname="1">Bsp.-37</entry><entry colname="2">TB</entry><entry colname="3">-</entry><entry colname="4">-</entry><entry colname="5">J-1</entry><entry colname="6">C-1</entry><entry colname="7">40</entry><entry colname="8">40</entry><entry colname="9">-</entry><entry colname="10">-</entry><entry colname="11">20</entry><entry colname="12">-</entry><entry colname="13">10</entry><entry colname="14">6</entry></row><row><entry colname="1">Bsp.-38</entry><entry colname="2">TA</entry><entry colname="3">PS-1</entry><entry colname="4">15</entry><entry colname="5">J-1</entry><entry colname="6">C-1</entry><entry colname="7">40</entry><entry colname="8">10</entry><entry colname="9">-</entry><entry colname="10">-</entry><entry colname="11">10</entry><entry colname="12">-</entry><entry colname="13">7</entry><entry colname="14">7</entry></row><row><entry colname="1">Bsp.-39</entry><entry colname="2">TB</entry><entry colname="3">PS-1</entry><entry colname="4">30</entry><entry colname="5">J-1</entry><entry colname="6">C-1</entry><entry colname="7">25</entry><entry colname="8">-</entry><entry colname="9">-</entry><entry colname="10">-</entry><entry colname="11">50</entry><entry colname="12">-</entry><entry colname="13">7</entry><entry colname="14">3</entry></row><row><entry colname="1">Bsp.-40</entry><entry colname="2">TC</entry><entry colname="3">PS-1</entry><entry colname="4">45</entry><entry colname="5">J-2</entry><entry colname="6">C-1</entry><entry colname="7">20</entry><entry colname="8">30</entry><entry colname="9">10</entry><entry colname="10">10</entry><entry colname="11">30</entry><entry colname="12">-</entry><entry colname="13">3</entry><entry colname="14">3</entry></row><row><entry colname="1">Bsp.-41</entry><entry colname="2">TB</entry><entry colname="3">PS-1</entry><entry colname="4">10</entry><entry colname="5">J-2</entry><entry colname="6">C-1</entry><entry colname="7">25</entry><entry colname="8">50</entry><entry colname="9">-</entry><entry colname="10">10</entry><entry colname="11">15</entry><entry colname="12">-</entry><entry colname="13">5</entry><entry colname="14">3</entry></row><row><entry colname="1">Bsp.-42</entry><entry colname="2">TA</entry><entry colname="3">PS-2</entry><entry colname="4">20</entry><entry colname="5">J-2</entry><entry colname="6">C-1</entry><entry colname="7">40</entry><entry colname="8">30</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">10</entry><entry colname="12">10</entry><entry colname="13">3</entry><entry colname="14">1</entry></row><row><entry colname="1">Bsp.-43</entry><entry colname="2">TB</entry><entry colname="3">PS-2</entry><entry colname="4">30</entry><entry colname="5">J-8</entry><entry colname="6">C-1</entry><entry colname="7">40</entry><entry colname="8">20</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">20</entry><entry colname="12">10</entry><entry colname="13">0.6</entry><entry colname="14">0.2</entry></row><row><entry colname="1">Bsp.-44</entry><entry colname="2">TD</entry><entry colname="3">PS-2</entry><entry colname="4">45</entry><entry colname="5">J-7</entry><entry colname="6">C-2</entry><entry colname="7">50</entry><entry colname="8">20</entry><entry colname="9">-</entry><entry colname="10">10</entry><entry colname="11">20</entry><entry colname="12">-</entry><entry colname="13">5</entry><entry colname="14">3</entry></row><row><entry colname="1">Bsp.-45</entry><entry colname="2">TE</entry><entry colname="3">PS-2</entry><entry colname="4">10</entry><entry colname="5">J-1</entry><entry colname="6">C-2</entry><entry colname="7">50</entry><entry colname="8">20</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">-</entry><entry colname="12">20</entry><entry colname="13">6</entry><entry colname="14">6</entry></row><row><entry colname="1">Bsp.-46</entry><entry colname="2">TB</entry><entry colname="3">PS-2</entry><entry colname="4">20</entry><entry colname="5">J-8</entry><entry colname="6">C-2</entry><entry colname="7">25</entry><entry colname="8">30</entry><entry colname="9">25</entry><entry colname="10">-</entry><entry colname="11">-</entry><entry colname="12">20</entry><entry colname="13">5</entry><entry colname="14">3</entry></row><row><entry colname="1">Bsp.-47</entry><entry colname="2">TB</entry><entry colname="3">PS-3</entry><entry colname="4">30</entry><entry colname="5">J-6</entry><entry colname="6">C-2</entry><entry colname="7">60</entry><entry colname="8">10</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">15</entry><entry colname="12">5</entry><entry colname="13">3</entry><entry colname="14">3</entry></row><row><entry colname="1">Bsp.-48</entry><entry colname="2">TA</entry><entry colname="3">KS-1</entry><entry colname="4">10</entry><entry colname="5">J-3</entry><entry colname="6">C-1</entry><entry colname="7">30</entry><entry colname="8">20</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">35</entry><entry colname="12">5</entry><entry colname="13">10</entry><entry colname="14">6</entry></row><row><entry colname="1">Bsp.-49</entry><entry colname="2">TB</entry><entry colname="3">KS-1</entry><entry colname="4">20</entry><entry colname="5">J-4</entry><entry colname="6">C-1</entry><entry colname="7">50</entry><entry colname="8">30</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">5</entry><entry colname="12">5</entry><entry colname="13">5</entry><entry colname="14">3</entry></row><row><entry colname="1">Bsp.-50</entry><entry colname="2">TC</entry><entry colname="3">KS-2</entry><entry colname="4">30</entry><entry colname="5">J-3</entry><entry colname="6">C-1</entry><entry colname="7">20</entry><entry colname="8">30</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">30</entry><entry colname="12">10</entry><entry colname="13">5</entry><entry colname="14">3</entry></row><row><entry colname="1">Bsp.-51</entry><entry colname="2">TB</entry><entry colname="3">KS-2</entry><entry colname="4">40</entry><entry colname="5">J-4</entry><entry colname="6">C-2</entry><entry colname="7">30</entry><entry colname="8">40</entry><entry colname="9">20</entry><entry colname="10">-</entry><entry colname="11">10</entry><entry colname="12">-</entry><entry colname="13">3</entry><entry colname="14">3</entry></row><row><entry colname="1">Bsp.-52</entry><entry colname="2">TD</entry><entry colname="3">KS-2</entry><entry colname="4">20</entry><entry colname="5">J-3</entry><entry colname="6">C-2</entry><entry colname="7">60</entry><entry colname="8">20</entry><entry colname="9">-</entry><entry colname="10">-</entry><entry colname="11">20</entry><entry colname="12">-</entry><entry colname="13">5</entry><entry colname="14">3</entry></row>&lt;?page 26?&gt;<row><entry colname="1">Bsp.-53</entry><entry colname="2">TE</entry><entry colname="3">KS-2</entry><entry colname="4">30</entry><entry colname="5">J-3</entry><entry colname="6">C-2</entry><entry colname="7">20</entry><entry colname="8">40</entry><entry colname="9">-</entry><entry colname="10">10</entry><entry colname="11">30</entry><entry colname="12">-</entry><entry colname="13">5</entry><entry colname="14">2</entry></row><row><entry colname="1">Comp. Bsp.-5</entry><entry colname="2">TA</entry><entry colname="3">-</entry><entry colname="4">-</entry><entry colname="5">-</entry><entry colname="6">C-1</entry><entry colname="7">40</entry><entry colname="8">30</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">20</entry><entry colname="12">-</entry><entry colname="13">10</entry><entry colname="14">10</entry></row><row><entry colname="1">Comp. Bsp.-6</entry><entry colname="2">TB</entry><entry colname="3">PS-1</entry><entry colname="4">70</entry><entry colname="5">1-1</entry><entry colname="6">C-1</entry><entry colname="7">40</entry><entry colname="8">30</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">20</entry><entry colname="12">-</entry><entry colname="13">10</entry><entry colname="14">6</entry></row><row><entry colname="1">Comp. Bsp.-7</entry><entry colname="2">TA</entry><entry colname="3">KS-1</entry><entry colname="4">50</entry><entry colname="5">J-3</entry><entry colname="6">C-1</entry><entry colname="7">40</entry><entry colname="8">30</entry><entry colname="9">10</entry><entry colname="10">-</entry><entry colname="11">20</entry><entry colname="12">-</entry><entry colname="13">10</entry><entry colname="14">6</entry></row><row><entry colname="1">Comp. Bsp.-8</entry><entry colname="2">TB</entry><entry colname="3">PS-1</entry><entry colname="4">30</entry><entry colname="5">J-1</entry><entry colname="6">C-1</entry><entry colname="7">45</entry><entry colname="8">30</entry><entry colname="9">20</entry><entry colname="10">-</entry><entry colname="11">5</entry><entry colname="12">-</entry><entry colname="13">7</entry><entry colname="14">3</entry></row></tbody></tgroup></table></tables><ul><li>* 1:% by weight as SiO₂ in a dried adhesive layer.</li><li>* 2:% by weight of titanium dioxide and either a metal oxide gel or a metal hydroxide gel in total in a dried photocatalyst layer.</li></ul> Table 5 <tables><table frame="all"><tgroup cols="8" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><colspec colname="8" colwidth="1*" /><tbody><row><entry colname="2">Photocatalytic activity</entry><entry namest="3" nameend="4">adhesion</entry><entry colname="5">Adhäsionseigensch.</entry><entry namest="6" nameend="7">Sunshine Weathering Tester</entry><entry colname="8">Total light transmittance (%)</entry></row><row><entry colname="3">in front durability test</entry><entry colname="4">after durability test</entry><entry colname="5">after Boiling water test</entry><entry colname="6">state of surface test</entry><entry colname="7">Adhäsionseigensch. after test</entry></row><row><entry colname="1">Example-36</entry><entry colname="2">A</entry><entry colname="3">10 Pts.</entry><entry colname="4">8th Pts.</entry><entry colname="5">10 Pts.</entry><entry colname="6">A</entry><entry colname="7">8th Pts.</entry><entry colname="8">68</entry></row><row><entry colname="1">Example-37</entry><entry colname="2">A</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">10</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">65</entry></row><row><entry colname="1">Example-38</entry><entry colname="2">A</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">8th</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">63</entry></row><row><entry colname="1">Example-39</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">8th</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">75</entry></row><row><entry colname="1">Example-40</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">10</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">- * 5</entry></row><row><entry colname="1">Example-41</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">8th</entry><entry colname="6">A</entry><entry colname="7">6</entry><entry colname="8">71</entry></row><row><entry colname="1">Example-42</entry><entry colname="2">C</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">10</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">82</entry></row><row><entry colname="1">Example-43</entry><entry colname="2">C</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">8th</entry><entry colname="6">A</entry><entry colname="7">6</entry><entry colname="8">87</entry></row><row><entry colname="1">Example-44</entry><entry colname="2">B</entry><entry colname="3">- * 3</entry><entry colname="4">- * 3</entry><entry colname="5">- * 3</entry><entry colname="6">A</entry><entry colname="7">- * 3</entry><entry colname="8">- * 4</entry></row>&lt;?page 27?&gt;<row><entry colname="1">Example-45</entry><entry colname="2">A</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">8th</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">- * 4</entry></row><row><entry colname="1">Example-46</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">10</entry><entry colname="6">A</entry><entry colname="7">6</entry><entry colname="8">75</entry></row><row><entry colname="1">Example-47</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">8th</entry><entry colname="6">A</entry><entry colname="7">6</entry><entry colname="8">70</entry></row><row><entry colname="1">Example-48</entry><entry colname="2">A</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">8th</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">66</entry></row><row><entry colname="1">Example-49</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">8th</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">77</entry></row><row><entry colname="1">Example-50</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">10</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">- * 5</entry></row><row><entry colname="1">Example-51</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">10</entry><entry colname="6">A</entry><entry colname="7">8th</entry><entry colname="8">83</entry></row><row><entry colname="1">Example-52</entry><entry colname="2">B</entry><entry colname="3">- * 3</entry><entry colname="4">- * 3</entry><entry colname="5">- * 3</entry><entry colname="6">A</entry><entry colname="7">- * 3</entry><entry colname="8">- * 4</entry></row><row><entry colname="1">Example-53</entry><entry colname="2">C</entry><entry colname="3">10</entry><entry colname="4">8th</entry><entry colname="5">10</entry><entry colname="6">A</entry><entry colname="7">6</entry><entry colname="8">- * 4</entry></row><row><entry colname="1">Comparative Example-5</entry><entry colname="2">A</entry><entry colname="3">2</entry><entry colname="4">2</entry><entry colname="5">0</entry><entry colname="6">C</entry><entry colname="7">0</entry><entry colname="8">54</entry></row><row><entry colname="1">Comparative Example 6</entry><entry colname="2">A</entry><entry colname="3">4</entry><entry colname="4">2</entry><entry colname="5">2</entry><entry colname="6">C</entry><entry colname="7">2</entry><entry colname="8">52</entry></row><row><entry colname="1">Comparative Example 7</entry><entry colname="2">A</entry><entry colname="3">4</entry><entry colname="4">2</entry><entry colname="5">2</entry><entry colname="6">C</entry><entry colname="7">2</entry><entry colname="8">48</entry></row><row><entry colname="1">Comparative Example 8</entry><entry colname="2">B</entry><entry colname="3">4</entry><entry colname="4">4</entry><entry colname="5">2</entry><entry colname="6">C</entry><entry colname="7">4</entry><entry colname="8">51</entry></row></tbody></tgroup></table></tables><ul><li>* 3: Since cross-cut Scotch tape test can not be used, the observation on the surface was the adhesive tape side using a binocular performed. As a result could no photocatalyst layer are bonded.</li><li>* 4: The determination of the light transmission was due to its will not be carried out abnormal design.</li><li>* 5: The determination of the light transmission was due to a opaque carrier not done be.</li></ul>

the Compositions and test results for the performance of the in Examples 36-53 disclosed photocatalyst carrying Structures are shown in Tables 4 and 5. FIG.

in Comparative Example 5 is a structure disclosed in which a photocatalyst layer, but no adhesion is applied. In this case, the photocatalyst layer no adhesive property and is easily peeled off from the substrate, and it is observed, that the surface of the polyester film after performing a durability test was damaged due to the photocatalytic activity, and the presence of holes and fractures on the film was observed by a binocular microscope.

in Examples 36 and 37, a structure disclosed in the acrylic-silicon resin for forming an adhesive layer was used, and a complex prepared and composed from 40-50% by weight fine-grained Titanium dioxide P-25 manufactured by Nihon Aerozil Co., Ltd., 40% Mass fraction in Z-1 reproduced silica sol and 10 to 20 wt% Acryl-silicon resin emulsion and used to form a photocatalyst layer. For the in these examples disclosed structures have been following to the implementation the cooking tests good adhesive property and good durability and resistance opposite to accelerated weathering observed.

&lt;?page 28?&gt;

in Examples 38 to 42 is disclosed a structure in which polysiloxane -containing acryl-silicon resin for forming an adhesive layer was used and the same photocatalyst powder as in Example 36 was used for forming a photocatalyst layer, and Type and content of a sol to form a gel were miscible changed. For the Structures produced in these examples were good photocatalytic activity and good adhesion property, durability and resistance to accelerated Weathering after performing the test detected with boiling water. In both cases, in which the resin was introduced into the polysiloxane, from 3% by weight Silicon containing acryl-silicon resin (Examples 38 and 39) or 10% by weight of silicon-containing acrylic-silicon resin (Examples 40, 41 and 42) was, the adhesive property, durability proven and resistance towards accelerated Weathering of structures as excellent.

in Examples 44 and 45, a structure disclosed in a adhesion and a photocatalyst layer on either polyethylene mesh applied or a polypropylene tube is, and for the structures prepared in these examples were good photocatalytic Activity, Adhesive property and durability found.

These good physical properties were also for the structures observed, in which the resin was introduced into the polysiloxane, an epoxy-silicon resin (Examples 43 and 46), polyester resin (example 44) and acrylic resin (Example 47).

however lost, as shown in Comparative example 6, a photocatalyst layer adhesive properties and was replaced when the polysiloxane content in an adhesive layer 70% mass fraction reached, although polysiloxane-containing acrylic-silicon resin for the adhesion has been used.

in Examples 48 to 53, a structure is disclosed in which a colloidal silica containing resin was used for forming an adhesive layer, and for the structures prepared in these examples were good photocatalytic Activity, Adhesive property after performing the test with boiling water, durability and resistance opposite to accelerated weathering observed. In particular, the structures, in which colloidal silica with small particle diameter (KS-2) and acryl-silicon resin emulsion in that these colloidal silica were launched, used (Examples 50 to 53), reported excellent physical properties.

however proved the adhesive property and durability of the structure, in which the content of colloidal silica in the adhesive layer increased to 50% by weight was deteriorated as strong (Comparative Example 7).

in Examples 44 to 47, a structure disclosed in a adhesion and a photocatalyst layer by the doctor blade coating method were provided, and a coating material for forming the photocatalyst layer by dispersing the titanium oxide sol, the nitric acid acidified was and 12% by weight of titanium dioxide, said by fine-grained Titanium dioxide (P-25) manufactured by Nihon Aerozil Co., Ltd., silica gel (Trade name: Cataloid SI-30), manufactured by Shokubai Kasei Co., Ltd. and either alumina sol-200 manufactured by Nissan Chemical Industries Co., Ltd. or zirconia sol manufactured, was replaced by Nippon Soda Co., Ltd., adjusting the pH the resulting mixture to 1.5 and adding a predetermined Amount of surfactant Substance was prepared to this mixture. For in these examples prepared structures were good adhesive property and durability and high photocatalytic activity in spite of the thickness of relatively thin the photocatalyst layer found.

in Example 47 is a good physical properties was having structure achieved, despite the lowering of the total content of acrylic-silicon resin emulsion and silane coupler in a photocatalyst layer to 20% by weight, However, in Comparative Example 8 were the adhesive property and the Durability is greatly reduced when the total content of 5% by weight was decreased even with adding acryl-silicon resin emulsion to the photocatalyst layer.

the Samples obtained in Examples 36 to 53, all of a durability test under irradiation of black light at a high temperature and high Moisture, an immersion test in boiling water and an accelerated subjected to weathering test using the Sunshine Carbon Arc weathering meter were, and then again as to their photocatalytic activity in accordance with the same procedure at the beginning of the test, based on the decomposition amount of acetaldehyde were examined by light, and it was found that all Sample the same amount of acetaldehyde decomposition &lt;?page 29?&gt;how to start the test showed, yet the initial photocatalytic activity retained with full capacity.

example 54

According to the in Example 42 The method used was a sample of a titanium dioxide photocatalyst layer -bearing structure produced and the antibacterial activity of the sample evaluated.

As a result, it was found that the survival rate by intestinal bacteria on the left in the dark sample 92%, 91% and 91% after 1, 2 and 3 hours was while this rate on the other, the black light-exposed sample 52%, 22% and 11% after 1, 2 and 3 hours, respectively. The antibacterial activity was even found on the under a fluorescent lamp sample and the survival rate the intestinal bacteria here was 76%, 54% and 22% after 1, 2 or 3 Hours, these rates were higher than that of the untreated samples in the dark.

As for a Coating material of a photocatalyst used silicon compound The following materials were used: <dl><dt>(S-1)</dt><dd>5% by weight ethanol solution of tetraethoxy silane (Super Reagent Grade, manufactured by Wako Pure Chemical Co. Ltd.).</dd><dt>(S-2)</dt><dd>5% by weight ethanol solution of tetramethoxy silane (manufactured by Shinetsu Chemical Industry Co. Ltd.).</dd><dt>(S-3)</dt><dd>5% by weight ethanol solution of Methyltriethoxy silane (Super Reagent Grade, manufactured by Wako Pure Chemical Co. Ltd.).</dd><dt>(S-4)</dt><dd>5% by weight ethanol solution of tri (beta-methoxyethoxy) vinyl-silane (Manufactured by Nihon Unikar Co. Ltd., trade name: A-172).</dd></dl>

To a sol solution and in (Z-1) to (Z-3) represented silicon compound solution was either titanium dioxide powder or sol as a photocatalyst together with either water or a solvent mixture dispersed in water and ethanol, while the pH of the mixture in dependence of the type of raw materials and additives to an appropriate value 1.5 to 9 has been set, and also has a pre- fixed amount of surfactant added substance, so that a coating material for forming a photocatalyst layer was obtained. The content of the in this coating material contained components and viscosity and sedimentation of the particles immediately after the preparation of the coating material and 90 days after sealing / melting are shown in Table 6 below. &lt;?page 30?&gt; Table 6 <tables><table frame="all"><tgroup cols="11" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1.00*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1.00*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1.00*" /><colspec colname="7" colwidth="1*" /><colspec colname="8" colwidth="1.00*" /><colspec colname="9" colwidth="1*" /><colspec colname="10" colwidth="1.00*" /><colspec colname="11" colwidth="1*" /><tbody><row><entry namest="2" nameend="3">photocatalyst</entry><entry namest="4" nameend="5">metal dioxide</entry><entry namest="6" nameend="7">silicon component</entry><entry namest="8" nameend="9">at the start</entry><entry namest="10" nameend="11">by 90 meet</entry></row><row><entry colname="2">Type</entry><entry colname="3">Contents * 1</entry><entry colname="4">Type</entry><entry colname="5">Contents * 1</entry><entry colname="6">Type</entry><entry colname="7">Contents * 1</entry><entry colname="8">viscosity</entry><entry colname="9">sedimentation</entry><entry colname="10">viscosity</entry><entry colname="11">sedimentation</entry></row><row><entry colname="1">example</entry><entry colname="3">% by weight</entry><entry colname="4" /><entry colname="5">% by weight</entry><entry colname="7">% by weight</entry><entry colname="8">cP</entry><entry colname="9">%</entry><entry colname="10">cP</entry><entry colname="11">%</entry></row><row><entry colname="1">55</entry><entry colname="2">C-1</entry><entry colname="3">20</entry><entry colname="4">Z-1</entry><entry colname="5">20</entry><entry colname="6">S-1</entry><entry colname="7">1</entry><entry colname="8">31</entry><entry colname="9">100</entry><entry colname="10">43</entry><entry colname="11">90</entry></row><row><entry colname="1">56</entry><entry colname="2">C-1</entry><entry colname="3">10</entry><entry colname="4">Z-1</entry><entry colname="5">20</entry><entry colname="6">S-1</entry><entry colname="7">1</entry><entry colname="8">14</entry><entry>''</entry><entry colname="10">16</entry><entry colname="11">85</entry></row><row><entry colname="1">57</entry><entry colname="2">C-1</entry><entry colname="3">5</entry><entry colname="4">Z-1</entry><entry colname="5">5</entry><entry colname="6">S-1</entry><entry colname="7">0.2</entry><entry colname="8">3</entry><entry>''</entry><entry colname="10">4</entry><entry colname="11">95</entry></row><row><entry colname="1">58</entry><entry colname="2">C-2</entry><entry colname="3">30</entry><entry colname="4">Z-1</entry><entry colname="5">10</entry><entry colname="6">S-1</entry><entry colname="7">2</entry><entry colname="8">33</entry><entry>''</entry><entry colname="10">37</entry><entry colname="11">100</entry></row><row><entry colname="1">59</entry><entry colname="2">C-2</entry><entry colname="3">10</entry><entry colname="4">Z-1</entry><entry colname="5">10</entry><entry colname="6">S-3</entry><entry colname="7">0.1</entry><entry colname="8">7</entry><entry>''</entry><entry colname="10">9</entry><entry colname="11">100</entry></row><row><entry colname="4">Z-2</entry><entry colname="5">0.3</entry></row><row><entry colname="1">60</entry><entry colname="2">C-2</entry><entry colname="3">2</entry><entry colname="4">Z-1</entry><entry colname="5">2</entry><entry colname="6">S-3</entry><entry colname="7">0.01</entry><entry colname="8">1</entry><entry colname="9">''</entry><entry colname="10">1</entry><entry colname="11">100</entry></row><row><entry colname="4">Z-2</entry><entry colname="5">0.05</entry></row><row><entry colname="1">61</entry><entry colname="2">C-1</entry><entry colname="3">0.5</entry><entry colname="4">Z-1</entry><entry colname="5">0.5</entry><entry colname="6">S-2</entry><entry colname="7">0.02</entry><entry colname="8">1</entry><entry colname="9">''</entry><entry colname="10">1</entry><entry colname="11">95</entry></row><row><entry colname="1">62</entry><entry colname="2">C-1</entry><entry colname="3">0.1</entry><entry colname="4">Z-1</entry><entry colname="5">0.1</entry><entry colname="6">S-2</entry><entry colname="7">0,002</entry><entry colname="8">1</entry><entry>''</entry><entry colname="10">1</entry><entry colname="11">95</entry></row><row><entry colname="1">63</entry><entry colname="2">C-1</entry><entry colname="3">3</entry><entry colname="4">Z-1</entry><entry colname="5">6</entry><entry colname="6">S-1</entry><entry colname="7">0.2</entry><entry colname="8">2</entry><entry colname="9">''</entry><entry colname="10">2</entry><entry colname="11">90</entry></row><row><entry colname="2">C-2</entry><entry colname="3">3</entry><entry colname="4">Z-3</entry><entry colname="5">0.2</entry></row><row><entry colname="1">64</entry><entry colname="2">C-3</entry><entry colname="3">5</entry><entry colname="4">Z-1</entry><entry colname="5">7</entry><entry colname="6">S-4</entry><entry colname="7">0.2</entry><entry colname="8">3</entry><entry colname="9">''</entry><entry colname="10">5</entry><entry colname="11">95</entry></row><row><entry colname="1">65</entry><entry colname="2">C-3</entry><entry colname="3">1</entry><entry colname="4">Z-1</entry><entry colname="5">2</entry><entry colname="6">S-3</entry><entry colname="7">0.04</entry><entry colname="8">2</entry><entry>''</entry><entry colname="10">2</entry><entry colname="11">100</entry></row><row><entry colname="1">66</entry><entry colname="2">C-3</entry><entry colname="3">0.2</entry><entry colname="4">Z-1</entry><entry colname="5">0.2</entry><entry colname="6">S-1</entry><entry colname="7">0.01</entry><entry colname="8">1</entry><entry colname="9">''</entry><entry colname="10">1</entry><entry colname="11">100</entry></row><row><entry colname="1">Comparative Ex.</entry></row><row><entry colname="1">9</entry><entry colname="2">C-1</entry><entry colname="3">5</entry><entry colname="4">Z-1</entry><entry colname="5">5</entry><entry colname="6">-</entry><entry colname="8">3</entry><entry colname="9">100</entry><entry colname="10">12</entry><entry colname="11">45</entry></row><row><entry colname="1">10</entry><entry colname="2">C-2</entry><entry colname="3">30</entry><entry colname="4">Z-1</entry><entry colname="5">10</entry><entry colname="6">-</entry><entry colname="8">33</entry><entry colname="9">''</entry><entry colname="10">430</entry><entry colname="11">55</entry></row><row><entry colname="1">11</entry><entry colname="2">C-2</entry><entry colname="3">10</entry><entry colname="4">Z-1</entry><entry colname="5">10</entry><entry colname="6">-</entry><entry colname="8">7</entry><entry>''</entry><entry colname="10">23</entry><entry colname="11">65</entry></row><row><entry colname="4">Z-2</entry><entry colname="5">0.3</entry><entry colname="6">-</entry></row><row><entry colname="1">12</entry><entry colname="2">C-3</entry><entry colname="3">5</entry><entry colname="4">Z-1</entry><entry colname="5">7</entry><entry colname="6">-</entry><entry colname="8">3</entry><entry colname="9">''</entry><entry colname="10">9</entry><entry colname="11">50</entry></row><row><entry colname="1">13</entry><entry colname="2">C-3</entry><entry colname="3">1</entry><entry colname="4">Z-1</entry><entry colname="5">2</entry><entry colname="6">-</entry><entry colname="8">2</entry><entry colname="9">''</entry><entry colname="10">8th</entry><entry colname="11">60</entry></row><row><entry namest="1" nameend="11">NB: was Parikelsedimentation by a ratio of Sedimentationsvolumes in relation to indicated to the total volume of the coating solution.</entry></row></tbody></tgroup></table></tables><ul><li>* 1: The content is% by weight (wt%) reported, relative to the mass of the dried coating solution.</li></ul>

in Examples 55 to 57 are each a photocatalyst-carrying Structure disclosed in the titanium dioxide powder (P-25) as a photocatalyst has been used. Means of adding a small amount of a silicon compound was the stability the coating material of a photocatalyst after 90 days very improved.

in Examples 58 to 60 was acidified with nitric acid titania sol used as a photocatalyst, Silica gel and alumina sol were combined as the miscible metal oxide sol used and Methyltriethoxy-silane was used as a silicon compound in examples 59 and 60 is used. By means of the use of this method was a remarkable improvement of the resistance of the means of applying this coating material with a film formed thereon structure opposite to boiling water, in particular the resistance to boiling Water in tap water obtained.

&lt;?page 31?&gt;

in Examples 61 and 62, a photocatalyst-carrying structure disclosed in the tetramethoxy silane as a silicon component was used, and it is noted that this structure a Advantage showed stability to be able to retain the coating material, although the amount of added Tetramethoxy silane was so low.

in Example 63 A photocatalyst-carrying structure is provided, in the titanium dioxide powder (P-25) and titania sol as a photocatalyst together and silica sol and zirconia sol together as a connectable / miscible Metal oxide sol were used, by adding Tetramth eoxy-silane to the solution a coating material was obtained, the good stability and Sedimentationseigenschaft exhibited.

in Examples 64 to 66, a photocatalyst-carrying structure disclosed in a coating material for forming a photocatalyst layer by changing the type of the silicon compound was prepared, and each in Coating material was produced in these examples all pre-determined amounts to be added as deemed stable.

in the Contrast, in the examples 9 to 13, since the coating material no silicon compound was added, the viscosity of the coating material increases dramatically after 90 days, and the particle sedimentation resulted certainly from, and Consequently, it was difficult to control the conditions for forming films to control when using these coating materials, and it has not been possible to provide a stable quality having photocatalyst-carrying structure to achieve.

Examples 67 to 71

Among Use of the coating materials prepared in Examples 55 to 59 were prepared using the following substrates mentioned in the photocatalyst-carrying Structures produced. The following materials were used as substrates used: <dl><dt>(SA)</dt><dd>Primer-treated polyester film</dd><dt>(SB)</dt><dd>Glass plate of soda</dd><dt>(SC)</dt><dd>Metal aluminum plate</dd><dt>(SD)</dt><dd>High density Polytheylen network (Fiber thickness: 0.2 mm, mesh width: 0.6 mm)</dd><dt>(SE)</dt><dd>Polypropylene mesh (Inner diameter: 30 mm, outer diameter: 36 mm)</dd></dl>

the adhesion was formed by the dipping method, when its thickness 2 .mu.m or less or the design of the substrate was different from a plate, or by a method using a Baker applicator, when the substrate plate-shaped was and its thickness 2 .mu.m or more. The temperature used for drying the adhesive layer was 80 ° C, when the material of the substrate (SD) or (SE) was, and for all other cases was it 120 ° C. The photocatalyst layer was formed by the dipping method, if its thickness 2 .mu.m or less, or the design of the substrate other than plate-shaped was, or by a method using a bar coater when the substrate plate-shaped was and its thickness 2 .mu.m or more. Drying of the photocatalyst layer was at the same temperature carried out as the drying of the adhesive layer. in the Below are the physical properties in Examples and the comparative examples produced photocatalyst-carrying Structures shown in Tables 7 and 8, wherein the type and content of the materials described above, the thickness of a coated film, the method for forming the film, etc. were changed respectively. &lt;?page 32?&gt; Table 7 <tables><table frame="all"><tgroup cols="11" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><colspec colname="8" colwidth="1*" /><colspec colname="9" colwidth="1*" /><colspec colname="10" colwidth="1*" /><colspec colname="11" colwidth="1*" /><tbody><row><entry colname="1">example</entry><entry colname="2">carrier</entry><entry namest="3" nameend="5">Coating solution for adhesive layer</entry><entry namest="6" nameend="9">Coating solution for photocatalyst layer</entry><entry colname="10">Thickness of the adhesive layer (microns)</entry><entry colname="11">Thickness of the photocatalyst layer (Microns)</entry></row><row><entry namest="6" nameend="7">TiO₂</entry><entry colname="8">Z-1</entry><entry colname="9">Z-2</entry></row><row><entry colname="3">Type</entry><entry colname="4">Contents * 1</entry><entry colname="5">Resin soln.</entry><entry colname="6">Type</entry><entry colname="7">Contents * 2</entry><entry colname="8">Contents * 2</entry><entry colname="9">Contents * 2</entry></row><row><entry colname="1">Example-67</entry><entry colname="2">SA</entry><entry colname="3">PS-1</entry><entry colname="4">10</entry><entry colname="5">J-1</entry><entry colname="6">C-1</entry><entry colname="7">20</entry><entry colname="8">20</entry><entry colname="9">-</entry><entry colname="10">3</entry><entry colname="11">3</entry></row><row><entry colname="1">Example-68</entry><entry colname="2">SA</entry><entry colname="3">PS-1</entry><entry colname="4">5</entry><entry colname="5">J-1</entry><entry colname="6">C-1</entry><entry colname="7">2</entry><entry colname="8">0</entry><entry colname="9">-</entry><entry colname="10">1</entry><entry colname="11">3</entry></row><row><entry colname="1">Example-69</entry><entry colname="2">SC</entry><entry colname="3">PS-1</entry><entry colname="4">20</entry><entry colname="5">J-2</entry><entry colname="6">C-1</entry><entry colname="7">5</entry><entry colname="8">5</entry><entry colname="9">-</entry><entry colname="10">4</entry><entry colname="11">2</entry></row><row><entry colname="1">Example-70</entry><entry colname="2">SD</entry><entry colname="3">PS-2</entry><entry colname="4">20</entry><entry colname="5">J-2</entry><entry colname="6">C-2</entry><entry colname="7">30</entry><entry colname="8">10</entry><entry colname="9">-</entry><entry colname="10">5</entry><entry colname="11">3</entry></row><row><entry colname="1">Example-71</entry><entry colname="2">SE</entry><entry colname="3">PS-2</entry><entry colname="4">30</entry><entry colname="5">J-2</entry><entry colname="6">C-2</entry><entry colname="7">10</entry><entry colname="8">10</entry><entry colname="9">0.3</entry><entry colname="10">4</entry><entry colname="11">2</entry></row></tbody></tgroup></table></tables><ul><li>* 1: concentration of solid components of the Resin in the coating solution.</li><li>* 2: concentration of solid components in the coating solution.</li></ul> Table 8 <tables><table frame="all"><tgroup cols="8" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><colspec colname="8" colwidth="1*" /><tbody><row><entry colname="1">example</entry><entry colname="2">Photocatalytic activity</entry><entry namest="3" nameend="5">adhesion</entry><entry namest="6" nameend="7">Sunshine Weathering Tester</entry><entry colname="8">Total light transmittance (%)</entry></row><row><entry colname="1" /><entry colname="2" /><entry colname="3">in front Durable-keits test</entry><entry colname="4">after Durability Test</entry><entry colname="5">after Boiling water test</entry><entry colname="6">Surface Condition to test</entry><entry colname="7">Adhäsionseigensch. after test</entry></row><row><entry colname="1">Example-67</entry><entry colname="2">A</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">- * 6</entry><entry colname="6">A</entry><entry colname="7">10</entry><entry colname="8">63</entry></row><row><entry colname="1">Example-68</entry><entry colname="2">A</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">- * 6</entry><entry colname="6">A</entry><entry colname="7">10</entry><entry colname="8">75</entry></row><row><entry colname="1">Example-69</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">- * 6</entry><entry colname="6">A</entry><entry colname="7">10</entry><entry colname="8">- * 5</entry></row><row><entry colname="1">Example-70</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">- * 6</entry><entry colname="6">A</entry><entry colname="7">- * 3</entry><entry colname="8">- * 4</entry></row><row><entry colname="1">Example-71</entry><entry colname="2">B</entry><entry colname="3">10</entry><entry colname="4">10</entry><entry colname="5">10</entry><entry colname="6">A</entry><entry colname="7">10</entry><entry colname="8">82</entry></row></tbody></tgroup></table></tables>&lt;?page 33?&gt;<ul><li>* 3: Since cross-cut Scotch tape test could not be used, the surface of the adhesive tape was measured by using a binocular considered, however, was no adhesion of Photocatalyst layer observed.</li><li>* 4: The determination could due to the different configurations not done be.</li><li>* 5: The determination could not because of an opaque carrier accomplished be.</li><li>* 6: It was not carried out evaluation.</li></ul>

the in Examples 67 to 71 samples prepared a durability test were under irradiation of black light at a high temperature and high Moisture, an immersion test in boiling water and an accelerated subjected to weathering test using the Sunshine Carbon Arc weathering meter, the photocatalytic activity In each case based on the decomposition amount of acetaldehyde by light according to the same A method as the above-described tests examined. From the result, that the same level of decomposition amount of acetaldehyde as implementation the tests described above for the sample was achieved, it is shown that the original photocatalytic activity in the structures completely has been preserved.

example 72

A Containing titanium dioxide photocatalyst-carrying structure was according to the in Example prepared methods described 67 and an antibacterial Test for the structure according to the above Described methods performed. The survival rate the intestinal bacteria on the structure without irradiation with light was 92%, 91% and 91% after 1, 2 and 3 hours, whereas the survival rate on the irradiation with black light-exposed structure 52%, 29% and 11% after 1, 2 and 3 hours, respectively. also was the survival rate of intestinal bacteria on which the irradiation with a fluorescent lamp exposed structure 76%, 54% and 22% after 1, 2 and 3 hours, what higher antibacterial activity showed as the left in its dark structure.

Example 73 treated with adhesive Movies

A solution for forming an adhesive layer was prepared by mixing 30% by weight of polysiloxane ( by Colcoat Co. Ltd., trade name: Methyl Silicate 51) based on the mass of acrylic-silicon resin, and 5% by weight of a curing agent (silane coupler) based on the weight of acryl-silicon resin to a mixed solution of xylene and isopropanol (mixing ratio 50:50), the 25% mass fraction 3% by weight of silicon-containing acrylic-silicon resin having, prepared and with methyl Ehtylketon diluted, so that the concentration of 10% by weight based on the solid Matter was.

the diluted solution was gravure printing on a polyester film (trade name: Cosmo Shine 50 microns) A4100, manufactured by Toyobo Co. Ltd., is applied so that after drying using a micro gravure coater (width: 70 cm) manufactured by Yasui Seiki Co. Ltd., at a rate of 15 m / s and a dry zone temperature of 13, a 1 micron thick Film.

Of the Polyester film on which an adhesive layer was formed, then was treated with a coating material for forming a photocatalyst layer, which by means of dispersing with nitric acid acidified, 20% by weight of titanium dioxide containing a photocatalyst titanium oxide sol in nitric acid acidified, 20% silica containing silica sol in the presence of a surfactant Substance, and subsequent thinning the dispersion with a mixture of ion-exchange water, and Ethanol (mixing ratio 50:50) fixed to a concentration of 10% by weight based on Components was prepared by gravure printing as for the adhesion coated, so that a polyester film having a after drying thick 1 .mu.m Photocatalyst layer was achieved.

After that was applied to the surface the photocatalyst-supporting, the polyester film having structure to which no photocatalyst was applied, a solution by adding 5% by weight on the solid component basis a coating agent for blocking heat radiation, STS-500 produced, Sumitomo Osaka Cement Co. Ltd., to an adhesive commercially available was prepared, applied by means of using the low pressure procedure. The film provided with the adhesive was during lamination of the film with a polyethylene film (Pyrene film-OT 20 microns) P-2161 manufactured by Toyobo Co. Ltd., in a process for drying and winding up in the dryer section the gravure printing device wound, so that an adhesive layer is provided.

&lt;?page 34?&gt;

These Kind of films can be used as adhesive film for window glass for vehicles, House window glass and window glass for medical facilities be used, and they are expediently by their properties characterized as such. as antibacterial activity, dirt repellency and deodorizing property as well as splinter protection films the breaking of glass.

Example 74 glass plate

On a glass plate made of soda lime glass plate also, which had a thickness of 1 mm and in one piece with an extension of 5 cm × 5 cm was cut, a solution prepared by mixing of 30% by weight of polysiloxane (Methyl Silicate 51 manufactured, by Colcoat Co., Ltd.), based on the weight of acryl-silicon resin, in a mixed solution of xylene and isopropanol (mixing ratio 50:50), the 25% mass fraction 3% by weight of silicon-containing acrylic-silicon resin includes, for Forming an adhesive layer applied using the no. 7 bar coater and at 100 ° C for 60 min dried. After the glass plate was cooled at ambient temperature, was a coating material for forming a photocatalyst layer by dispersing with nitric acid acidified, 20% by weight of titanium dioxide containing titanium oxide sol in with nitric acid acidified, 20% by weight of silicon oxide containing silica sol in the presence of a surfactant Substance produced. The resulting solution was then applied to the above Adhesion described, also using the no. 7 bar coater, and then applied for 60 min at 100 ° C dried so that a photocatalyst-carrying glass plate (Sample No. 1) was obtained.

Example 75 glass fiber paper

the Example 74 used solution for forming an adhesive layer was a xylene-propanol solution (Mixing ratio 50:50) fixed to a concentration of 5% by weight based on Components diluted. A fiberglass paper SAS-030 (Mass: 30 g / m²) manufactured by Oribest Co., Ltd., was in the above described produced, diluted solution dipped and then pulled up, and allowed to stand at 100 ° C for 120 min dried so that an adhesive layer on the surface this fiber paper was formed. Then, the fiber paper was, on which the adhesive layer was formed in a solution dipped, the means of diluting with ion-exchange water of the coating material used in Example 74 for forming a photocatalyst layer to a concentration was prepared of 10% by weight, and pulled out and in 100 ° C for 120 min dried to give a photocatalyst-carrying glass fiber paper (Sample no. 2) was obtained.

Example 76 lenses

A adhesion was on glasses, PC pointal coat TC (+) 1.005 0.0065 0 mm (diameter), prepared formed by Nikon Corporation, by applying a solution, the means of admixing 20% ​​by weight of polysiloxane (Methyl Silicate 51, manufactured by Colcoat Co., Ltd.), based on the mass of the Acryl-silicon resin into a mixed solution of xylene and isopropanol (Mixing ratio 50:50), the exhibiting 10% by weight of 3% by weight of silicon Acrylic-silicon resin was prepared on the lens according to the in Example dipping method described 75 applied, and the coated Lens was heated at 100 ° C for 20 min dried. After cooling, the lens at ambient temperature, a coating material for forming a photocatalyst layer by dispersing of nitric acid and acidified 5% by weight of titanium dioxide containing titanium oxide sol in with nitric acid and acidified 5% by weight of silica-containing silica sol in the presence of a surfactant Substance produced as a photocatalyst. Using this Coating material as a photocatalyst layer and a similar Using the dipping method, a photocatalyst layer by coating the surface this adhesion layer formed with this coating material and at 100 ° C for 20 min dried so that photocatalyst-carrying glasses were obtained for glasses (Sample No. 3).

EXAMPLE 77 Murals of polyvinylchloride

A Solution, prepared by mixing 30% by weight of polysiloxane (Methyl Silicate 51, manufactured by Colcoat Co., Ltd.), based on the mass of Acryl-silicon resin into a mixed solution of xylene and isopropanol (Mixing ratio 50:50), the 25% mass fraction 3% by weight of silicon-containing acrylic-silicon resin contains, was prepared was applied to one of a wallpaper from Polyvinylchloride (SG 5328 manufactured by Sangetsu, Co., Ltd.) in a size of 5 cm × 5 cm cut-out piece and in a thickness of 1 mm using a bar coater no. 7 applied, and the coated wallpaper &lt;?page 35?&gt;was then min at 100 ° C for the 20th dried so that an adhesive layer was achieved. After cooling the Wallpaper at ambient temperature, a coating material for Forming a photocatalyst layer by dispersing with nitric acid acidified and 20% by weight of titanium dioxide containing titanium dioxide sol as Photocatalyst in an acidified with nitric acid and 20% by weight Silica-containing silica sol in the presence of a surfactant Substance produced. This solution was applied to the surface the adhesion layer 7 is applied using a bar coater No.., And the coated wallpaper was dried at 100 ° C for 20 So obtained dried min a photocatalyst-carrying Wallpaper (Sample no. 4).

Example 78 Polyester Films

the in Example 77 used to form an adhesive solution with a mixed solution diluted of xylene and isopropanol (mixing ratio, 50:50), so that the concentration of the mixture to 25% by weight based on solid components was adjusted. The diluted solution was then purified by a Gravure process at a speed of 10 m / min and a dry zone temperature of 130 ° C on a polyester film (Cosmo Shine) A4100, manufactured by Toyobo Co., Ltd., using a Micro-gravure coater (Width: 70 cm) manufactured by Yasui Seiki Co., Ltd., to form a layer with a thickness after drying of 3 microns is applied.

Then was on with an adhesive layer equipped polyester film, the coating material used in Example 77 for forming a photocatalyst layer according to the gravure coating method applied so that by a photocatalyst-supporting polyester film with a 3 microns after drying was obtained thick photocatalyst layer (sample no. 5).

Example 79 protection filter for personal computers

A solution for forming an adhesive layer was prepared by mixing 30% by weight of polysiloxane (Methyl Silicate 51, manufactured by Colcoat Co., Ltd.), based on fixed components based on the weight of acryl-silicon resin into a xylene solution contains 20% by weight of a 20% by weight of silicon containing acryl-silicon resin, and thinning with an isopropanol solution to adjust the concentration to 20% by weight based on solid components prepared. Then, the solution was determined by Immersion on VDT ​​filter, e-filter III, manufactured by Toray Co., Ltd., is applied, and the coated filter was then stirred at 100 ° C for 20 min for forming an adhesive layer on the surface the filter dried. Subsequently, the adhesive layer was a equipped VDT protective filter applied to a dipping process in a solution by thinning of coating material used in example 77 with ion-exchange water was prepared so that the content of solid components in the coating material was 10% by weight, pulled it and at 100 ° C for 20 min dried to give a photocatalyst-carrying VDT filter was obtained (Sample Nos. 6).

Example 80 telephone housing

the in Example 77 used to form an adhesive solution with a mixed solution diluted of xylene and isopropanol (mixing ratio, 50:50), so that the concentration of the solution was adjusted to 20% by weight on the solid component basis. diluted Mixture was prepared by spraying a housing for one Telephone (Type: HIT-1, manufactured by Hitachi Seisakusho Co., Ltd.) using a spray gun (type: RESIST 88 prepared Iwata Tosoki of Kogyo Co., Ltd.). After drying the sprayed housing at 100 ° C for 20 min was used in a coating material for Example 1 Forming a photocatalyst layer by thinning with ion-exchange water to a concentration of 8 wt% adjusted on the basis of solid components, and the diluted coating material was applied as described above by means of spraying. After drying the housing at 100 ° C for 20 min was achieved, a photocatalyst-supporting telephone housing (Sample no. 7).

Example 81 glasses for spectacles

A adhesion was applied to a glass for Glasses, NL70HCCTc (+) 1.0 0.00 OS (70 mm 0), manufactured by Nikon Corporation, by applying a solution prepared by admixing of 20% by weight of polysiloxane (Methyl Silicate 51 manufactured, by Colcoat Co., Ltd.), based on the weight of acryl-silicon resin, in a mixed solution of xylene and isopropanol (mixing ratio 50:50), the 10% mass fraction a 3% by weight of silicon containing acryl-silicon resin contains, according to the glass &lt;?page 36?&gt;the in Example dipping method described 79 made, and the coated glasses were at 100 ° C for 20 min dried. After cooling, the glasses at ambient temperature, a coating material was to form a photocatalyst layer, which by means of dispersing with nitric acid acidified and 15% by weight of titanium dioxide containing titanium oxide sol as Photocatalyst in with nitric acid acidified and 20% by weight Silica-containing silica sol in the presence of a surfactant Substance was prepared for forming a photocatalyst layer applied to the lens. Using this solution for photocatalyst layer and using the same dipping method, a photocatalyst layer by coating the surface this adhesion layer with the solution formed and at 100 ° C for 20 min dried so that a photocatalyst-carrying glass for spectacles was obtained (Sample Nos. 8).

Example 82 Curtains

textiles for curtains, trade name "Hospia" (for use prepared in schools and hospitals), Kawashima Orimono Co., Ltd., 7 cm × 7 cm were cut into a piece the size, and the pieces were added to a solution dipped, prepared by mixing 20% ​​by weight of polysiloxane (Methyl Silicate 51 manufactured by Colcoat Co., Ltd.), based on solid components based on the weight of acryl-silicon resin, in a mixed solution of xylene and isopropanol (mixing ratio 50:50), the 15% mass fraction 3% by weight of silicon-containing epoxy-silicon resin, is prepared was withdrawn therefrom and at 80 ° C for 120 min dried. After cooling of textile products at room temperature, with an adhesive layer provided textile products in a coating material for forming a Photocatalyst layer dipped, the containing means dispersing 10% by weight of titanium dioxide Titania sol, made of ammonia, as ammonia-alkali designated, containing 10 wt% silicon oxide silica sol in the presence of a surfactant Substance was prepared, pulled out there from and dried at 80 ° C for 120 min dried so that photocatalyst-carrying textile products for use as curtains were obtained (sample no. 9).

Example 83 The nonwoven textiles

Unbleached Nonwoven textile products of cotton (trade name: Orcos prepared by Nisshinbo Co., Ltd.) was cut into pieces of a size of 7 cm × 7 cm cut, and each piece was charged with a solution by mixing 30% by weight of polysiloxane (Methyl Silicate 51, manufactured by Colcoat Co., Ltd.), based on the mass of the Acryl-silicon resin, in a mixed solution of xylene and isopropanol (mixing ratio 50:50), the 25% mass fraction 3% by weight of silicon-containing acrylic-silicon resin, is prepared was, using a spray gun (type: RESIST 88, produced Iwata Tosoki of Kogyo Co., Ltd.) sprayed. After drying the sprayed fabric at 100 ° C for 30 min was used in Example 82 for forming a photocatalyst layer solution used applied to this fabric, and the coated fabric then was heated at 100 ° C for 30 min dried so that a photocatalyst-carrying nonwoven fabric made of cotton was obtained for the Surgical gloves, tablecloths, covers for toilet seats, Japan paper, covers for Bedding plants, packing materials Food etc. suitable.

Example 84 Printed Polyester Cloth textiles for umbrellas

Among Use of commercially available printed polyester cloth textiles for umbrellas as substrate were an adhesion layer and a photocatalyst layer according to Example 83 disclosed The method applied. The scoring here photocatalyst-carrying printed polyester cloth-textile products have almost no difference in patterns and feeling to normal cloth textiles on (sample no. 11).

Example 85 wallpaper (textile)

Among Using an unprinted textile fabric, SG 6758 established, of Sangetsu Co., Ltd., as a substrate, an adhesion layer were and a photocatalyst layer according to Example 83 disclosed Process formed on the fabric.

the Photocatalyst-carrying wallpaper textile fabric had no negative Influence on the quality of the fabric (sample no. 12).

&lt;?page 37?&gt;

Example 86 aluminum shutters

A Solution, prepared by mixing 30% by weight of polysiloxane (Methyl Silicate 51, manufactured by Colcoat Co., Ltd.), based on the mass of the containing acryl-silicon resin, in a mixed solution of Xylene and isopropanol (mixing ratio 50:50), the 25% mass fraction 3% by weight of silicon-containing acrylic-silicon resin manufactured was, was determined using a bar coater no. 7 an in pieces a size of 7 cm × 7 applied cm cut window frame plate made of aluminum, and window frames aluminum plate was to form an adhesive layer on the plate at 100 ° C for 60 min dried. After cooling, the plate at ambient temperature, a coating material for forming a photocatalyst layer by dispersing with Nitric acid acidified, 20% by weight of titanium dioxide containing titanium oxide sol in with nitric acid acidified, 20% Mass fraction of silicon oxide-containing silica sol in the presence of a surfactant Substance produced. The coating material was then Using a bar coater no. 7 on the surface of the Adhesion described above applied and the coated plate was at 130 ° C for 10 min dried so that a photocatalyst-carrying aluminum plate scored (sample no. 13).

Example 87 Stainless steel plates

the Example 86 used solution for forming an adhesive layer was determined by diluting with a mixed solution of xylene and isopropanol (mixing ratio, 50:50) to a concentration of 5% by weight adjusted to the solid component basis. A in one piece a size of 7 cm × 7 cm cut stainless steel plate of SUS 316 (thickness: 0.2 mm) was in the solution described above dipped, pulled out there from and for forming an adhesive layer on the surface the stainless steel plate at 120 ° C for 20 min dried. Subsequently with an adhesive layer coated stainless steel plate is immersed in a solution prepared by Adjusting the concentration of the coating material used in Example 86 for a Photocatalyst layer with ion-exchange water to a concentration was prepared from 10% by weight, pulled out of it and at 120 ° C for 20 min dried so that a photocatalyst-supporting stainless scored steel plate (sample no. 14).

Example 88 Tin plates

A 1 mm thick, in one piece a size of 7 cm × 7 cm cut tin plate was dipped in a solution prepared by Mixing 30% by weight of polysiloxane (Methyl Silicate 51 manufactured, by Colcoat Co., Ltd.), based on the weight of acryl-silicon resin into a 20% Mass fraction of a xylene solution a 20% by weight of silicon containing acryl-silicon resin, and subsequent diluting the Mixture with isopropanol solution to a concentration of 20% by weight on the solid component basis was prepared, pulled out there from and for forming an adhesive layer on the tin plate at 100 ° C for 60 min dried. subsequently was associated with an adhesive layer coated tin plate immersed in a solution prepared by Adjusting the concentration of the coating material used in Example 86 for a Photocatalyst layer by diluting with ion-exchange water was prepared in a concentration of 10% by weight, from the solution pulled out and at 100 ° C for 60 min dried to achieve a photocatalyst-carrying tin plate (Sample no. 15).

Example 89 Aperture

After the removal of a 800 mm wide and 700 mm high strip of Aperture, "Silky Curtain "(type 15 mm strip width) T-12 (white) manufactured by Tachikawa Blind Industry Co., Ltd., was a solution that by mixing 30% by weight of polysiloxane (Methyl Silicate 51, manufactured by Colcoat Co., Ltd.), based on the mass of the Acryl-silicon resin into a mixed solution of xylene and isopropanol (mixing ratio, 50:50), the 25% by weight of 3% by weight of silicon-containing acrylic-silicon resin contains, was prepared by spraying using a spray gun, WIDER 88, manufactured by Iwata Tosoki Kogyo Co., Ltd., applied. After drying the sprayed Aperture at 120 ° C for 20 min has also been applied to the diaphragm by means of spraying a solution prepared by thinning of coating material used in Example 86 to form a photocatalyst layer with ion-exchange water to a Concentration of 8% by weight on the solid component basis was prepared (sample no. 16).

&lt;?page 38?&gt;

Example 90 Custom Plywood / Formwork panels

On into a piece size 7 cm × 7 cm cut, printed plywood, Neowood manufactured by Eidai Sangyo Co., Ltd., with a thickness of 2.5 mm, a solution prepared by mixing of 30% by weight of polysiloxane (Methyl Silicate 51 manufactured, by Colcoat Co., Ltd.), based on the weight of acryl-silicon resin, in a mixed solution of xylene and isopropanol (mixing ratio 50:50), the 25% mass fraction 3% by weight of silicon-containing acrylic-silicon resin, is prepared was by using a bar coater no. 7 applied and then to form an adhesive layer on the printed Formwork panel at 100 ° C for 30 min dried. After cooling, the printed form panel at ambient temperature was a Coating material for forming a photocatalyst layer containing by dispersing with nitric acid acidified, 20% by weight of titanium dioxide Titania sol in with nitric acid acidified, 20% by weight of silica-containing silica sol in the presence of a surfactant Substance produced. Using this coating material and a bar coater Nr. 7 the coating material on the surface of the adhesion and applied at 100 ° C for 30 min dried, so that a photocatalyst-carrying printed scored plywood (sample no. 17).

Example 91 A synthetic timber

the Example 90 used solution for forming an adhesive layer was charged with a mixed solution of xylene and isopropanol (mixing ratio, 50:50) to a concentration of 5% by weight of diluted solid component basis.

On in one piece a size of 7 cm × 7 cm cut synthetic lumber, Esron Neolamber FFU 50, manufactured by Sekisui Chemical Industry Co., Ltd., was inserted into the above diluted solution dipped, pulled out there from and for forming an adhesive layer on the surface the timber at 100 ° C for 120 min dried. subsequently was that with an adhesive layer equipped timber in a solution dipped, the means of diluting of coating material used in Example 90 to form a photocatalyst layer with ion-exchange water to a Concentration was prepared from 10% by weight, pulled it and at 100 ° C for 120 min dried so that the photocatalyst-carrying synthetic was achieved timber (sample no. 18).

Example 92 wooden doors

A wooden door for indoor (type 38 RCO202-IR6, Oak pattern) manufactured by Daiken Kogyo Co., Ltd., was in one piece a size of 7 cm × 7 cm cut, and the pieces A solution, prepared by mixing 20% ​​by weight of polysiloxane (Methyl Silicate 51 manufactured, by Colcoat Co., Ltd.), based on the weight of acryl-silicon resin into a mixed solution of xylene and isopropanol (mixing ratio 50:50), the 10% mass fraction 3% by weight of silicon-containing acrylic-silicon resin, is prepared was, for forming an adhesive layer according to the in Example applied immersion method described 91 and at 100 ° C for 20 min dried. After cooling, the track at ambient temperature, a coating material was to form a photocatalyst layer by dispersing acidified with nitric acid, 5% by weight of titanium dioxide containing titanium oxide sol in with nitric acid acidified, 5% by weight of silica-containing silica sol in the presence of a surfactant Substance produced. This coating material was applied to the surface of adhesion applied using the dipping method described above and at 100 ° C for 20 So obtained dried min a photocatalyst-carrying wooden door has been.

Evaluation of the photocatalytic activity

the photocatalytic activity of samples 1 to 19 was evaluated respectively, and the results of the evaluation are shown in Table 9 below.

Industrial use

the Photocatalyst-carrying structure according to the present invention has high photocatalytic activity, and glass, plastics, metallic materials, fabric textile goods, Lumber and wood materials, each with an injury against insensitive and very durable photocatalyst equipped are able for lenses, various kinds of window glass, adhesive films, decorative films, Wallpaper, curtains, Building materials such as aperture, interior, etc. are used. &lt;?page 39?&gt; Table 9 <tables><table frame="all"><tgroup cols="7" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1.20*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><tbody><row><entry colname="2">Total radiolucency</entry><entry colname="3">Aldehyde-decomposing activity</entry><entry colname="4">Salad oil decomposition activity</entry><entry colname="5">Antibacterial activity</entry><entry colname="6">Initial Speaker. adhesion</entry><entry colname="7">durability</entry></row><row><entry colname="1">sample 1</entry><entry colname="2">85%</entry><entry colname="3">A</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10 Points</entry><entry colname="7">10 Points</entry></row><row><entry colname="1">sample 2</entry><entry colname="2">65</entry><entry colname="3">B</entry><entry colname="4">A</entry><entry colname="5">-</entry><entry colname="6">5% or less mass reduction by 10 min ultrasound</entry><entry colname="7">as with an initial. adhesion</entry></row><row><entry colname="1">sample 3</entry><entry colname="2">90</entry><entry colname="3">B</entry><entry colname="4">B</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 4</entry><entry colname="2">-</entry><entry colname="3">B</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 5</entry><entry colname="2">90</entry><entry colname="3">A</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 6</entry><entry colname="2">-</entry><entry colname="3">B</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 7</entry><entry colname="2">-</entry><entry colname="3">B</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 8th</entry><entry colname="2">95</entry><entry colname="3">B</entry><entry colname="4">B</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 9</entry><entry colname="2">-</entry><entry colname="3">A</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">*1</entry><entry colname="7">*1</entry></row><row><entry colname="1">sample 10</entry><entry colname="2">-</entry><entry colname="3">A</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">*1</entry><entry colname="7">*1</entry></row><row><entry colname="1">sample 11</entry><entry colname="2">-</entry><entry colname="3">B</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">*1</entry><entry colname="7">*1</entry></row><row><entry colname="1">sample 12</entry><entry colname="2">-</entry><entry colname="3">B</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">*1</entry><entry colname="7">*1</entry></row><row><entry colname="1">sample 13</entry><entry colname="2">-</entry><entry colname="3">A</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 14</entry><entry colname="2">-</entry><entry colname="3">B</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 15</entry><entry colname="2">-</entry><entry colname="3">A</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 16</entry><entry colname="2">-</entry><entry colname="3">B</entry><entry colname="4">A</entry><entry colname="5">B</entry><entry colname="6">8th</entry><entry colname="7">8th</entry></row><row><entry colname="1">sample 17</entry><entry colname="2">-</entry><entry colname="3">B</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">8th</entry><entry colname="7">8th</entry></row><row><entry colname="1">sample 18</entry><entry colname="2">-</entry><entry colname="3">A</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row><row><entry colname="1">sample 19</entry><entry colname="2">-</entry><entry colname="3">A</entry><entry colname="4">A</entry><entry colname="5">A</entry><entry colname="6">10</entry><entry colname="7">10</entry></row></tbody></tgroup></table></tables><ul><li>* 1: Since the underlying grains Band procedure could not be used, the surface of the adhesive tape was observed, but was no adhesion the photocatalyst layer detected.</li></ul>