DE69637493T2 - CARRIER STRUCTURE WITH PHOTO CATALYST AND PHOTOCATALYTIC COATING MATERIAL - Google Patents

Description

Field of the invention

The The present invention relates to a photocatalyst-carrying one Structure that for Antifouling, water cleaning, deodorization, pasteurization, a treatment of sewage, water degradation, a 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 using ultraviolet radiation energy various chemical Reactions activated, such. During a process of water degradation, Deodorization, pasteurization, water purification, treatment of sewage or the like occurring chemical reactions. It is said that the catalytic activity of a Photocatalyst can generally be high if it is either in Powder or in the form of a suspension in a solvent is used. However, in many cases, such a photocatalyst must used in a form applied to a particular substrate become. To efficiently use ultraviolet radiation energy from light It is advantageous to use a substrate in the form of a paper or paper To bring the leaf that the greater of Light irradiated area can ensure. Furthermore It is also advantageous, the surface of the substrate has a porous structure to give, so the contact surface of the substrate with a reactant with which the progression an actual chemical reaction in the presence of a photocatalyst is desired, is enlarged.

Various photocatalyst-containing substrates have been proposed in the past. For example: (A) a translucent material such as cellulose nitrate, glass, polyvinyl chloride, plastics, nylon, methacrylic resin and polypropylene is in Japanese Patent Publication No. Sho 62-66861 , disclosed; (B) Polypropylene fibers and ceramics are in Japanese Patent Publication No. Hei 2-68190 , disclosed; and (C) glass, ceramics, nylon, acrylic and polyester resins are in the Japanese Patent Publication No. Hei 5-309267 , disclosed.

however From the materials disclosed as above, it is reported that having an organic material as its main component Material has the disadvantage that the organic material due to a caused by the photocatalyst contained in said material catalytic reaction can be decomposed and destroyed, and consequently its durability has been problematic (see 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 is made of an inorganic material such as glass and Ceramics consist, some of the durability characteristic of the substrate solved problems be such. Example, when an organic polymer resin as an adhesive used for fixing a photocatalyst on the substrate is, the photocatalytic activity may be reduced since the surface of photocatalyst particles is covered with such a resin, and the photocatalyst from the substrate due to the decomposing and destructive Effect of said organic polymer resin due to its photocatalytic Activity can peel off.

In order to avoid such problems as described above, a method called a spattering method, wherein no organic materials remain ( Japanese Patent Publication No. Sho 60-044053 ), a process for coating and firing an organic titanate ( Japanese Patent Publication No. Sho 60-118236 ), a method for spraying and firing a titanium sol ( Japanese Patent Publication No. Hei 5-253544 ) and others were used when the substrate used was made of an inorganic refractory material.

however These methods have a problem in that they require a burning process of the substrate at high temperature require preparation and crystallization the photocatalyst particles on the substrate and adhesive property to achieve with the substrate. Consequently, it is difficult to use a photocatalyst to apply in a wide range, and the production according to these Procedure causes very high costs.

For applying a photocatalyst on a glass fiber plate, a method using a metal oxide sol as an adhesive has been proposed (see FIG. Japanese Patent Publication No. Hei 5-309267 ).

The Adhesive property of a metal oxide sol such as a Silica sol, However, it is very weak because it comes from van der Waals forces (s. Fine Ceramics, Vol. 1, pp. 216-223, 1980), so the binding strength and durability of the adhesive were insufficient. Further required the procedure additionally one Burning at high temperature and was therefore not for all types of substrates applicable, inclusive usually used types of resin, which are easily decomposed by heating.

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

however So far there is no report describing that a Substrate, the outstanding adhesive property and durability while retaining the high photocatalytic activity of the photocatalyst, which, as described above, uniformly in a metal oxide sol is distributed.

A method for fixing a photocatalyst using a fluorescein has also been proposed (see FIG. Japanese Patent Publication No. Hei 6-315614 ). However, the price of a fluorescein is high and it is required that the majority of the surface of the photocatalyst particles is covered with the fluorescein to firmly adhere the photocatalyst particles. Accordingly, the catalytic activity of a photocatalyst is lowered from the activity of the same photocatalyst in powder form. Although an example is known (s. EP A1 633.064 ), which suggests to apply a photocatalyst to a substrate by blending the photocatalyst with a binder such as fluororesins and poly-organosiloxane which is resistant to decomposition, is not enough to practically solve these problems of adhesive property and durability to solve.

EP A 633.064 discloses a photocatalyst mixture comprising a substrate provided with a first layer comprising an adhesive containing no photocatalyst particles, said first layer being provided with a second layer comprising a less readily 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 readily degradable adhesive. Example 8 from EP A 633.064 discloses a photocatalyst mixture consisting of a substrate (transparent acrylic plate) provided with a first layer of less readily degradable adhesive without photocatalyst particles, and a second layer of less readily degradable adhesive and 90% by volume photocatalytic titanium oxides.

EP A 684.075 discloses a multifunctional photocatalytic material comprising (a) a support / base layer, (b) a tie layer, and (c) a photocatalytic layer, wherein the photocatalytic layer is disposed on the surface of the base layer by means of the tie layer, and wherein the photocatalytic layer includes an outwardly facing surface layer and a lower layer embedded in the bonding layer, the surface layer consisting of photocatalyst particles. The lower layer of the photocatalytic layer is partially embedded in the bonding layer after the layer aggregate has been heated to a temperature which is above the melting temperature of the bonding layer but below the melting temperature of the base layer.

EP A 792.687 discloses a photocatalyst structure comprising (a) a substrate, (b) an intermediate layer comprising a binder, and (c) a photocatalyst layer. According to Example 2 from EP A 792.687 For example, the intermediate layer may be prepared by coating it with a liquid material comprising a silica sol and trimethoxy-methylsilane in a weight ratio of 3: 1 on an aluminum substrate, followed by drying at 150 ° C, after which the titanium oxide-containing photocatalyst layer is applied.

As described above the following three points as when applying a photocatalyst on a substrate to be solved Problems to be stated: (1) the adhesion between the photocatalyst and the substrate should be good, (2) the photocatalytic activity of the photocatalyst must not lose weight when applied to a substrate, and (3) both the substrate and the adhesive should not due to the presence of the photocatalyst attached thereto destroyed be and the substrate must be its binding ability, durability and catalytic activity can preserve.

In addition, when a photocatalyst-carrying structure is under high-temperature conditions and high humidity, for example, a property of the structure necessary to retain excellent adhesion after immersion in boiling water.

It is for a photocatalyst used for applying a photocatalyst to a substrate Photocatalyst coating material required, a property to show that the photocatalyst coating material neither to increase its viscosity even to his particle sedimentation, not even after his Storage for at least one month and preferably more than three months. As well a property is required that allows a photocatalyst on a substrate, without destroying its photocatalytic activity, if the photocatalyst is applied to a product for practical use becomes.

The Inventors of the present invention have found a method to firmly adhere a photocatalyst to a substrate by placing a photocatalyst specific adhesion layer between a photocatalyst layer and a substrate so that under the adhesion layer provided substrate before its degradation due to the photocatalytic activity of the photocatalyst and the photocatalyst layer firmly adhered to the substrate, and a solution of the above-described To provide problems by making the adhesive layer resistant to destruction due to photocatalytic activity is done.

Disclosure of the invention

The inventors of the present invention found that silicon-modified resin, e.g. Acrylic-silicon resin or epoxy-silicon resin containing 2-60% by mass of silicon, a resin containing 5-40% by mass of colloidal silica, and 3-60% by mass of a polysiloxane-containing resin which is a polycondensation reaction product a compound represented by formula (1) represents: SiCln ₁ (OH) n ₂ R ¹ n ₃ (OR ² ) n ₄ (1), wherein R ^{1 is} an alkyl group having 1-8 carbon atoms which is unsubstituted or substituted with an amino group, a carboxyl group or a chlorine atom, R ^{2 is} an alkyl group having 1-8 carbon atoms or an alkoxy-substituted alkyl group having 1-8 carbon atoms, n _{1 is} 0, 1 or 2, n ₂ and n _{3 are} each independently 0 or one of the integers from 1 to 3, n _{4 is} an integer from 2 to 4, where the sum of n ₁ , n ₂ , n ₃ and n ₄ 4, can firmly adhere a photocatalyst and protect the substrate from photocatalytic activity of the photocatalyst.

In addition, in order to solve the problem with the photocatalyst coating material, the inventors of the present invention found that a photocatalyst coating material containing 0.001-5% by mass of one or more alkoxysilanes represented by a general formula (2): SiR ³ n ₅ (OR ⁴ ) ₄ -n ₅ (2) wherein R ^{3 is} an alkyl group having 1-8 carbon atoms which is unsubstituted or substituted with an amino group, a chlorine atom or a carboxyl group, R ^{4 is} an alkyl group having 1-8 carbon atoms or an alkoxy-substituted alkyl group having 1-8 carbon atoms, n is ₅ , 1 or 2, or the hydrolysis products thereof, 1-30% by weight of a metal oxide sol and / or a metal hydroxide sol based on solid components and 0.1-30% by weight of a photocatalyst as a powder and / or Sol, can be stable for a long time and does not lead to an increase in viscosity and particle sedimentation, and accordingly they have completed the present invention.

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

The The present invention will be described below in detail.

In In the present invention, a resin used to form the adhesion layer to be used in the photocatalyst-carrying structure from a group of silicon modified resin such. B. Acrylic-silicon resin or epoxy-silicon resin containing 2- 60% by mass Silicon, a 5-40% by mass colloidal silica having resin and a 3-60% Mass fraction of polysiloxane-containing resin selected.

If a silicon-modified resin containing silicon in an amount containing less than 2% by weight, such as an acrylic-silicon resin, a resin, the 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 decreases between the adhesion layer and the photocatalyst layer and the adhesion layer is due destroyed the effect of the photocatalyst, wherein the photocatalyst layer tends to flake off easily. On the contrary, when silicon-modified resin, as in an amount is used by more than 60% by weight containing acrylic silicon resin deteriorates the connection between the adhesion layer and the substrate and the abrasion resistance of the structure is due to the sinking of the Hard of the adhesive layer 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 is used as resin containing 40% by weight, the adhesion porous, that under the adhesion layer provided substrate is due to the action of a photocatalyst destroyed and the connection state between the substrate and the adhesion layer deteriorates and the photocatalyst layer tends to be to peel off easily from the substrate.

At the Using a silicon-modified resin, such as an acrylic-silicon resin and an epoxy-silicon resin as an adhesive layer material each silicon-modified resin prepared according to a method for introducing Silicon in the resin, such as. An ester exchange method, transfer reaction method using silicon macromers and reactive silicon monomers, hydrosilylation reaction methods and block copolymerization methods was prepared to be used in the present invention.

When Resin into which silicon is to be introduced is acrylic resins and Epoxy resins the most suitable in terms of their properties Film formation, their resilience and their adhesive properties on Substrate. However, you can other resins such as alkyd resins, urethane resins and polyester resins, as well be used. additionally can these resins either in the form of solutions or emulsions be used. Likewise, it is unproblematic if such a Resin an additive, such. B. contains a cross-linking agent.

A Photocatalyst-carrying structure with improved adhesive property and durability can be achieved if one for forming an adhesion layer used resin is a polysiloxane, wherein the polysiloxane a Hydrolysis product of a 1-5 carbon atoms silicon alkoxide or a product derived from such a hydrolysis product is. When the alkoxy group of the silicon alkoxide has 6 or more carbon atoms contains Such a resin becomes expensive and the adhesive property and durability of the resin are destroyed, because it is difficult, the alkoxide in the resin due to its low Cure hydrolysis rate.

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

When a method of insertion of a polysiloxane in a resin are methods for mixing the same 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 a product obtained by means of partial Hydrolysis of the silicon alkoxide with a resin and subsequent hydrolysis the mixture with moisture in the air at the time of formation a protective film, etc., known. Any process involving uniform mixing allowed with a resin, can be used. A small amount an acidic or basic catalyst may be used to change the Hydrolysis rate of the silicon alkoxide are added.

As examples of a resin suitable for introducing a polysiloxane, there may be mentioned acrylic resins, acrylic-silicon resins, epoxy-silicon resins, silicon-modified resins, urethane resins, epoxy resins, poly ester resins, alkyd resins, etc. are used. However, silicon-modified resins including acrylic-silicon resins and epoxy-silicon resins are the most preferable in terms of their durability property.

If the adhesion layer from 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 becomes in the adhesion layer further destroyed due to the influence of a photocatalyst and the Bonding state between the photocatalyst layer and the adhesion layer is also getting worse. As a method for introducing such colloidal silica in the resin is known that a method for mixing a resin solution with a solution colloidal silica, then applied and then to form an adhesion layer dried, the simplest is. However, a method for Forming an adhesion layer, by allowing a resin to polymerize while colloidal silica in the Resin is dispersed, and then the synthesized resin to apply and to dry, also acceptable. It is also possible colloidal silica after using them with a silane coupler to upgrade the adhesive property and the dispersibility of colloidal silica and a resin was treated.

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

When the colloidal silicic acid can any silica sol, either by carrying out a cation exchange of a sodium silicate solution or by performing a Hydrolysis of a silicon alkoxide is used.

For a goal the destruction one for an adhesion layer used resin to prevent by influence of a photocatalyst and to improve its durability, can be a mixing of the resin with a photostabilizing agent and / or ultraviolet absorber or similar to deliver a good effect. As a suitable photostabilizing Agent, preferably impaired amine compounds are used. However, you can also all other connections are used. triazole can as ultraviolet absorbent can be used. The amount of the ultraviolet absorbent to be added to the resin is in a range of 0.005% by mass to 10% by mass based on the weight of the resin, and preferably 0.01% by weight up to 5% by weight. By treatment of the surface of the adhesion with a silane-containing or titanium-containing coupler, the connection conditions between the adhesion layer and the photocatalyst layer can be improved.

When a method of applying an adhesion layer to a substrate can a method of coating the substrate with a resin solution in accordance with all Printing process, film pressing, sputtering, dipping and Coating method, spin coating method, etc. and then Drying of the coated substrate can be used. The temperature for drying the coated substrate is preferably 150 ° C or less, although they are dependent the type of solvent and the resins varies. If a thickness of an adhesion layer 0.1 μm or is more, is it possible to have one Photocatalyst-carrying structure that bonds with a photocatalyst layer and a substrate can connect and has high durability. In the case of a coating method, such as B. a gravure printing process, which is a process for drying and curing the adhesion layer within a short time, it is also allowed to the adhesive layer material from 0.1% to 10% by weight based on the mass of solid component of the adhesive layer material, dependent from the required curing speed, a curing agent add, such as As a silicon compound or the like.

A metal oxide gel or metal hydroxide gel present in the photocatalyst layer provides an effect of fixing the photocatalyst powder and bonding it firmly to an adhesion layer, and thus exhibits a photocatalyst having such a metal oxide gel and / or metal hydroxide gel supporting structure excellent adhesiveness, durability and weather resistance as shown in the examples of the embodiment of the present invention. In addition, such a metal oxide gel and metal hydroxide gel has a porous structure and adsorbing, and further has an enhancing effect on the photocatalytic activity. The content of such a metal oxide gel or metal hydroxide gel in the photocatalyst layer is between 25% and 95% by mass. If this content is below 25% masses proportion, the compound having an adhesion layer may be insufficient while the photocatalytic activity may be insufficient if this content exceeds 95% by mass.

Further, the above-described compound and the photocatalytic activity can be improved when the specific area of the metal oxide gel or the metal hydroxide gel after drying at 150 ° C is 50 m ² / g or higher, preferably 100 m ² / g or higher.

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

The Adhesive property of a photocatalyst layer after immersion in boiling water can be improved by adding 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 that are insensitive to boiling Water, silicon-aluminum, silicon-titanium, silicon-zirconium, Silicon niobium, aluminum-titanium, aluminum-zirconium, Aluminum niobium, aluminum tantalum, titanium zirconium, titanium niobium, Titanium tantalum, silicon-aluminum-zirconium and silicon-aluminum-titanium as preferable and metal oxide gels and metal hydroxide gels containing metals such as e.g. Silicon-aluminum, silicon-titanium, silicon-zirconium, silicon-titanium-aluminum and silicon-aluminum-zirconium are available as more preferable.

When the specific surface area of these metal oxide gels or metal hydroxide gels is 50 m ² / g or higher, they provide good adhesion property and photocatalytic activity to a photocatalyst layer, with the photocatalyst-carrying structure remaining very high even after immersion in boiling water good adhesion property reserves. In practical use, gels prepared by mixing a sol to form a gel and complex oxide gels prepared by coprecipitation methods or the like can be used. For mixing with a photocatalyst, it is desirable to uniformly mix either a metal oxide or metal hydroxide in a sol state before forming the gel, or to mix in a raw material state before preparing a sol.

When A method of preparing gels may be a method of hydrolyzing a metal salt, a process for decomposing a metal salt by neutralization, a process for exchanging ions, a method for hydrolyzing a metal alkoxide and the like be used. However, you can all methods by which the gel is in a state in which the photocatalyst is uniformly dispersed in the gel is to be used. As the adhesive property and the photocatalytic Activity of one Photocatalyst impaired could be, if many impurities are contained in the gel, it is preferable to use a gel containing less impurities.

Further Is it possible, by either adding a silicon-modified resin or a silane coupler between 10 and 50% by mass to one Photocatalyst layer, To obtain a photocatalyst layer, even after immersion in boiling water for 15 minutes high photocatalytic activity retains and excellent bonding property with more than 6 evaluation points according to the adhesive property test, cross-cut scotch tape test according to JIS K5400.

The silicon-modified resin or a silane coupler to be added to a photocatalyst layer has an improving effect on the adhesive property of the photocatalyst layer on a substrate in boiling water. As the silicon-modified resin, generally available resins such as silicon-acrylic resin and silicon epoxy resin can be used either in a dissolved state in a solvent or as a suspension in water. In contrast, can be used as a silane coupling agent by means of general formulas RSi (Y) ₃ and (R) ₂ Si (Y) ₂ compound represented where R is an organic functional group and Y represents a chlorine atom or an alkoxy group, and the like are 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. are exemplified a substituent represented by R is available. In addition to a chlorine atom, all C ₁ -C ₅ alkoxy groups, such as. Methoxy, ethoxy, beta-methoxyethoxy and beta-ethoxyethoxy, also useful as a substituent represented by Y.

The amount of silicon-modified resin and a silane coupling agent to be added to a photocatalyst layer is preferably from 10% to 50% by weight based on solid components. If this amount is less than 10% by weight, the bonding property of the layer will be lowered after the boiling water test. If the added amount is 50% mass exceeds a significant decrease in photocatalytic activity can be caused. As the method for adding either the silicon-modified resin or the silane coupling agent to a photocatalyst layer, there is a method of adding such a resin to a photocatalyst in either powder or sol form and a method of adding it to either a metal oxide sol or a sol Metal hydroxide sol used to form a metal oxide gel and added with a photocatalyst. The above-described addition of silicon-modified resin in emulsion to the sol is particularly preferable because it can improve the bonding property of a photocatalyst layer in boiling water with almost no reduction in the photocatalytic activity.

As well For example, an additive such as a cross-linking agent may be used with the Silicon modified resin or the silane coupler can be combined.

Of the Photocatalyst of the present invention is in powder form, as a sol or in solution before and can be used when he is with an adhesive layer and can show photocatalytic activity after being added a drying temperature for the photocatalyst layer was dried. If a photocatalyst is used in a sol state, is preferably the particle diameter of 20 nm or less, more preferably 10 nm or less, used because the transparency of a photocatalyst layer improves and their linear permeability increases, which is why It is particularly preferable to use such a photocatalyst for coating of glass substrates and plastic molds that use transparent have to be. Further, a transparent coated with such a photocatalyst is transparent Photocatalyst layer advantageous if color and / or pattern be applied to an underlying substrate, because these no adverse effect on colors and / or patterns of the underlying Have substrates.

As the photocatalyst to be used for the photocatalyst layer according to the present invention, TiO ₂ , ZnO, SrTiO ₃ , CdS, GaP, InP, GaAs, BaTiO ₃ , KNbO ₃ , Fe ₂ O ₃ , Ta ₂ O _s , WO ₃ , SnO ₂ , Bi ₂ O ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₂ , InPb, RuO ₂ , CeO ₂ and the like, and mixtures of these photocatalysts with a metal or a metal oxide, such as. As Pt, Rh, RuO ₂ , Nb, Cu, Sn, Ni and Fe can be used. In addition, any mixtures prepared by adding a metal such as Pt, Rh, RuO ₂ , Nb, Cu, Sn, Ni and Fe to the photocatalyst using a reduction reaction of the photocatalyst are also applicable to the present invention. The photocatalytic activity increases with the increase of the photocatalyst content in the photocatalyst layer. However, it is preferable to leave the content at 75% by mass or less from the viewpoint of maintaining sufficiently good bonding property.

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

As examples of the silicon compound added to the photocatalyst coating material of the present invention, there can be exemplified an alkoxysilane represented by the general formula (2): SiR ³ n ₅ (OR ⁴ ) ₄ -n ₅ (2) wherein R ^{3 is} an alkyl group having 1-8 carbon atoms which is unsubstituted or substituted with an amino group, a chlorine atom or a carboxyl group, R ^{4 is} an alkyl group having 1-8 carbon atoms substituted with an alkyl group having 1-8 carbon atoms or an alkoxy group and n ₅ is 0, 1, 2 or 3, and the mixtures with one or more of the respective hydrolysis products thereof are used. In the general formula (2), methyl, ethyl, vinyl, gamma-glycidoxypropyl, gamma-methacryloxypropyl, gamma- (2-aminoethyl) -aminopropyl, gamma-chloropropyl, gamma-mercaptopropyl, gamma-aminopropyl, gamma-acryloxpropyl and the like are exemplified for substituents represented by R ³ available. C ₁ -C ₈ alkoxy, such as. For example, methoxy, ethoxy, n-propoxy, i -propoxy, n-butoxy, beta -ethoxyethoxy and 2-ethylhexyloxy are preferable as examples of the substituent represented by -OR ⁴ .

When examples for the silicon compounds represented by the general formula (2) can Tetramethoxy-silane, tetraethoxy-silane, methyltrimethoxy-silane, methyltriethoxy-silane and mixtures of one or more hydrolysis products of these The compounds mentioned above are preferably available.

through Add a small amount of the above-described silicon compound to a coating solution For forming a photocatalyst layer, a stable coating material may be used to achieve a photocatalyst layer, resulting in a lower increase in viscosity and particle sedimentation leads, even when stored for a long period of time. In terms of the coating material for forming a photocatalyst layer The amount of silicon compound to be added is preferably between Added 0.001 and 5% by weight based on solids. If such an amount is less than 0.001% by mass, the stability the coating material for forming a photocatalyst layer when stored for a long period decreases while a significant decrease the photocatalytic activity is caused when such an amount to be added over 5% by weight lies. As a method for adding a silicon compound a coating material for forming a photocatalyst layer For example, a method of adding to a photocatalyst solution in either Powder or sol form, a method of adding to a sol of either a metal oxide or a metal hydroxide together be added with a photocatalyst, and the like be used. Alternatively, the coating material may partially hydrolyzed silicon compounds are added. There the coating material for forming a photocatalyst layer to be added silicon compound an increasing effect on the compound property of a photocatalyst in boiling water, it is possible to use the to reduce the amount of silicon compound to be added when the Silane coupler as described above or the like to the coating material was added.

It It is preferable to use a metal oxide sol and / or a metal hydroxide sol in an amount of 0.1-30% by weight and photocatalyst powder and / or sol in an amount of 0.1-30% by mass based on solid constituents, in each case in relation to the mass of the coating material for forming the photocatalyst layer, to add said coating solution.

If a relationship an amount of the metal oxide sol and / or metal hydroxide sol to be added is lower is 0.1% by weight, will the ability connecting a photocatalyst to a substrate insufficient be while, if the ratio more than 30% by weight, reduces the amount of photocatalyst powder and / or sol added simultaneously must be, whereby the photocatalytic activity decrease becomes. The photocatalytic activity will be too low if a ratio of Amount of the photocatalyst powder and / or sol to be added smaller is 0.1% by weight, and a photocatalyst layer will easily peel off the amount of a metal oxide sol and / or metal hydroxide sol to Bonding the layer to a substrate must be reduced if a relationship an amount of photocatalyst powder and / or sol to be added 30% by weight or more.

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

When one for the use in a coating composition for forming an adhesion layer suitable resin is preferred as described above for an adhesion layer To use usable resins, either individually or in a mixture with each other of these resins. Such a coating composition must then preferably either in solution of an organic solvent or in aqueous Emulsion are prepared, and the content of the resin as solid Ingredient should preferably be between 1 and 50% by weight chosen become. When in a coating composition the concentration of the solid content of such a resin is 1% or less the adhesion layer too thin formed and connecting the photocatalyst layer is difficult manufacture. On the other hand, if in a coating composition the concentration of the solid content of such a resin is 50% or is more, becomes the adhesion layer formed too thick and it will be difficult to apply a coating film properly and with a coating composition to handle it properly, because it becomes too viscous.

When a photocatalyst layer is formed on an adhesion layer, a suspension in which a photocatalyst is dispersed in a sol of either a metal oxide or a metal hydroxide can be applied by coating according to a method similar to that for forming an adhesion layer. Alternatively, a photocatalyst in a solution of a precursor of either ei a metal oxide sol or a metal hydroxide sol and is then prepared by a hydrolysis process or neutralizing decomposition during the coating process to either a sol form or a gel form. When the sol prepared as described above is used, a dispersing agent such as e.g. For example, an acid or a base can be added to improve the stability of the sol. Also, it is possible to further improve the adhesive property and ease of use by adding to the sol to 5% by mass or less of a surfactant, a silane coupler or the like, based on the mass of the photocatalyst. The drying temperature at the time when a photocatalyst layer is formed is preferably between 50 and 200 ° C, though it depends on the different substrates and resin materials used for the adhesion layer.

Although a thicker photocatalyst layer provides higher photocatalytic activity, there is no great difference in activity when the thickness exceeds 5 μm. The photocatalyst layer whose thickness is 5 μm or less is preferable because it provides high photocatalytic activity and light transmission, which makes the adhesion layer less conspicuous. However, although the light transmittance is improved in the case of a photocatalyst layer thickness of less than 0.1 μm, it is not expected that high photocatalytic activity will be attained because ultraviolet rays usable by the photocatalyst also penetrate the photocatalyst layer. The total light transmission of a photocatalyst layer and an adhesion layer at a wavelength of 550 nm will be 70% or more when a thickness of the photocatalyst layer is set in a range of 0.1 μm to 5 μm, and a photocatalyst whose particles have a Diameter of 40 nm or less, and either a metal oxide gel or a metal hydroxide gel whose specific surface area is 100 m ² / g or more are used. In the case of a photocatalyst-carrying structure whose total light transmission at a wavelength of 550 nm is 70% or more, visible light passing through the structure can be used for illumination, while such a structure is useful from the decorative viewpoint because it has no Design wasted on a substrate when the substrate of such a structure is opaque.

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

As in the examples of this patent specification described below, is the photocatalyst-carrying structure according to the present invention useful for colors for architectural Use, wall murals, window glass, blackouts, curtains, carpets, Lighting applications, lighting, black lights, colors for one Hull and fishing nets, fillings for water treatment, vinyl chloride films for agricultural use, Foils for preventing the growth of weeds, packing materials etc. In addition can the photocatalyst-carrying structure be made into a structure under conditions of high temperatures and high humidity is usable.

According to the present invention, it is possible to provide an adhesion layer and a photocatalyst layer-bearing structure having high durability property according to a test of adhesive property, so-called cross-cut scotch tape test according to JIS K5400, even after irradiation with an ultraviolet Radiation intensity of 3 mW / cm ² having black light for 500 hours at 40 ° C and 90% relative humidity is expressed with an evaluation point of 6 or higher. In addition, in an accelerated weathering test using a sunshine weathering gauge, a photocatalyst-carrying structure was obtained which was such excellent in a sticking property test for 500 hours according to this cross-cut scotch tape test according to JIS K5400 having an evaluation point of Shows 6 or more reproduced weathering resistance. In addition, a structure exhibiting high resistance to boiling water is obtained, so that the water obtained by dipping in boiling, an electrical conductivity of 200 μS / cm at 20 ° C by means of cross-cut scotch tape test according to JIS K5400 for 15 at least the assessed attribute of the structure with an evaluation score of 6 or more. Since high photocatalytic activity is observed in all samples of these structures, it is believed that the structure according to the present invention As described above has satisfactory properties with respect to various applications.

If a substrate made of glass, the glass can be in all the complex Shapes, like plate-shaped, tubular, spherical and be formed as fibers, and is with said adhesion layer and said photocatalyst layer. Regarding the Size thickness can stably support this glass at a thickness of 10 μm or more. Besides that is it also possible dependent from his application, such as B. in window glass, showcases and Eyeglasses to apply such layers to the processed 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 used are the antibacterial, deodorant and dirt require repellent effects, such as. As cameras and lenses, but also window glass, cover glass for Instruments, lighting applications, lighting, blue fluorescent lamps with black light and filler for water treatment.

A according to the present Invention a photocatalyst-carrying plastic mold can for various Applications are used that are antibacterial, deodorant and require a dirt-repellent effect, such. Eg for cameras and spectacle lenses, but also for Wall murals, shelves for interior decoration, furniture, electrical applications and vehicle parts.

Regarding the Shape of the above-described plastic mold can all complex shapes, such. B. as a film, plate-shaped, tubular, spherical and as a fiber, for producing a structure from a plastic mold with said adhesion layer and said photocatalyst layer. Regarding the Thickness can Such plastic molds such layers at a thickness of 10 μm or wear more stable. Furthermore it is equally possible dependent from the applications such. For building materials, home electrical applications and eyewear, such layers on the plastic mold so that a photocatalyst-carrying plastic mold according to the present Invention is made and therefore it is understood that the Structure of the present invention essentially a wide Has application.

Lots Fabric types can for the Substrate of the present invention can be used; as examples called: fabric, knitwear and non-woven textile products, including 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, a with a water repellent material coated material such. B. a silicon-containing water-repellent material, a fluorine containing water-repellent material including perfluoroalkyl acrylate, zirconium salt containing water-repellent material and ethylene-urea containing Water repellent material, one with both water repellent material as well as with a cross-linking agent such. B. ethyleneimine coated fabric, epoxy and melamine compounds for improvement the resistance, if necessary, an imitation leather made of fuzz complex Polyamide and polyester fibers, and a synthetic leather, wherein a polyurethane resin layer on a substrate such as a fabric, Nonwoven textile goods and knitwear using a polyurethane formed adhesive formed can be used. Likewise, by means of Applying such a water-repellent material and the like on fabrics that are processed into umbrellas, tents, bags, etc. be the photocatalyst-carrying substances according to the present Invention can be achieved.

Of the Photocatalyst carrying in the present invention Fabric is for Usable for various applications that are antibacterial, deodorant and a dirt repellent effect requires, for. B. Interior like curtains and wallpaper, tents, umbrellas, everyday items such as tablecloths, Packaging materials for Food and the like and for agricultural use such. B. Sheets for seedling beds.

For the photocatalyst-carrying metal according to the present invention, an alloy such as stainless steel, brass, aluminum alloy and titanium alloy, and single element metals such as aluminum, iron and copper may be used as a substrate. In addition, if this is considered from the design and quality point of view as a metal to be used, it is also possible to form both an adhesion layer and a photocatalyst layer according to the present invention on the substrate, such as a substrate. B. painted with normal colors metal foil and plate and a colored steel plate or to apply aluminum plate. In this case, it is further preferable that when the light transmittance of both the adhesion layer and the photocatalyst layer is sufficiently good and transparent, these layers do not have a bad influence on the color of the underlying substrate.

Regarding the Design of the metal, there is no difficulty, the metal in any complex shape, such as B. plate-shaped, tubular, spherical, as Fiber and foil-like, to design, so that on this adhesion layer and this photocatalyst layer can be applied. Furthermore The metal can stably carry these layers when its thickness 10 μm or is more. Furthermore, depending on from their use z. For example Windowpanes, showcases and spectacle lenses, all further processed, the photocatalyst-carrying Metal according to the present Invention by applying these layers on the further processed Metals are produced.

The Photocatalyst-carrying metal according to the present invention can for various applications are used which have an antibacterial, deodorizing and dirt repellent effect require, for. B. sieves, Filters and the like also for Windowpanes, furniture, accessories and decoration, paneling for indoor and exterior 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 design, such. B. plate-shaped, tubular, spherical and foil-like. These timbers or wooden materials can be added a thickness of 10 microns or more sufficiently these layers bear on it, and it is possible, a photocatalyst carrying timber or wood material according to the present invention Invention by making these layers on this timber and these wooden ones Materials, such as walls, wood paneling, Columns, Furniture and beams, which were previously prepared, applied become.

The a photocatalyst carrying timber and the wooden ones Materials according to the present invention can for various applications are used which have an antibacterial, deodorizing and dirt repellent effect require, for. For building materials, Furniture, timbers and materials for interior decoration.

through advantageous properties such as a dirt repellent one antibacterial and a deodorizing function can be one with the photocatalyst-carrying structure according to the present invention equipped plastic film are produced as a film, whose Area, which does not carry the photocatalyst, coated with an adhesive is, and these films can on the inner surface of window glass of a building such as cars and various means of transport, buildings, Freezer and refrigerated display cases and greenhouses applied are made possible with this glass, highly translucent glass to provide the decomposition of existing in the interior Traces harmful Substances accelerate and on a glass surface dirt-repellent effect and at its destruction has a preventative effect on the fragmentation of the glass. When the photocatalyst-carrying structure according to the present invention using a thin one Plastic film is produced as a substrate, this can as a wrapping film used for food packaging become. As a for such plastic films usable resin, a resin such. B. Polyethylene telephthalate resin, Polycarbonate resin, polyacrylate ester 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 resulting in a highly translucent synthetic Resin film or film can be pressed, its linear translucence at a wavelength of 550 nm is 50% or more, be used. In addition, the photocatalyst-carrying Structure according to the present Invention, since it is transparent, no negative impact on the surface of the underlying wallpapers and decorative foils printed Design and pattern so that the photocatalyst layer advantageous on the surface an opaque material such. B. wallpaper and decorative films, those with an adhesive layer and a removable film on its back are applied can be.

In these synthetic resin films or resin films described above, it is possible to improve adhesion property of the adhesion layer in the photocatalyst-carrying structure by treating the surface of these films and films having an adhesion layer on the surface thereof while physically carrying out trace amount oxidation by corona Discharge treatment and UV ozone treatment, and those whose contact with an adhesion layer is improved by easy application of a surface treatment agent such as silicon-containing compounds may preferably be be used. In addition, as shown in the examples of the embodiment of the present invention, it is also possible to fix a thin film on the surface or back of such materials to provide reflective and shadowing functions against heat radiation and ultraviolet radiation, thereby providing heat-ray reflection films and UV Radiation interruption films that are simultaneously dirt repellent, antibacterial and deodorizing effect can be achieved. It is to be understood that the photocatalyst-carrying structure according to the present invention has both high durability and photocatalytic activity, and thus it may be an extremely useful and valuable product.

When a method of providing the above-described heat ray reflection function can various methods, such. B. a method for forming a Films on a film surface from an electrically conductive Metal, e.g. Al, Ag, Cu, Cr, Ni, Ti, stainless steel and aluminum alloy, or an electrically conductive Metal oxide, e.g. Indium oxide, tin oxide and tin oxide-indium oxide compound, according to physical Procedures such. As sputtering and vacuum evaporation, a method for forming a film on a film surface by applying and subsequent Drying an electrically conductive Metal oxide solution or sols on the film surface or using either plating method or CVD method and a method for incorporating a material with Heat ray reflection property and / or thermal radiation interruption characteristic to the substrate. Nevertheless, as a method for Providing the interruption function for ultraviolet rays different Procedures are used, such. B. a method for forming a Films on a film surface by applying an ultraviolet radiation absorbing Agent as affected Amine-containing compounds and titanium oxide and an ultraviolet Radiation-reflecting agent and a method for preceding Incorporating an ultraviolet ray absorbing agent into a Film substrate, and are dependent on their intended use and their chemical structures selectable. When titanium dioxide as the ultraviolet ray blocking agent or used as an ultraviolet ray-reflecting agent is preferably used, the one that its photocatalytic activity due to thin Coating the titanium dioxide surface with soluble glass or the like has lost since surrounding organic materials due to the photocatalytic activity decomposed when titanium dioxide is present alone, as in detail is explained in the present invention.

Materials, which is a heat ray-reflecting Have function and an ultraviolet ray blocking function, can be integrated into an adhesive layer on the back a movie is formed to provide these functions. To the Example is a material such as a clear coating agent for Block ultraviolet rays, as in "Convertec", March 1996, page 95, a solvent-dispersible Sort and is for Applicable for the above purpose. Adhesives such as acrylic-like and Silicon containing compounds are normally used. However, it is also possible various types of ultraviolet ray absorbing agents and heat rays blocking Add agents. Considering the one with the remaining adhesive caused contamination at the time of renewal of the photocatalyst-carrying Films, it is recommended to use an adhesive with strong connection property. As a method for Providing an adhesive and a redetachable film on a photocatalyst-carrying film, is a process in which first an adhesive in solution by gravure on the back the film is applied and then the coated film together with a removable one To dry and roll polypropylene film, thereby laminating it, simple and can be preferably used.

Brief description of the drawings

1 Fig. 10 is a diagram showing a cross section of the photocatalyst-carrying structure according to the present invention.

Best method for carrying out the invention

The the present invention is final explained with reference to the examples described below, however The present invention should not be limited to those in these examples described scope are limited.

evaluation procedures

1) Evaluation of photocatalytic activity

A sample carrying a photocatalyst of 70 mm x 70 mm size is placed in a 4 L Pyrex beaker. A gas mixture of air and acetaldehyde was introduced into this beaker and the concentration of acetaldehyde was adjusted to 500 ppm. The specimen was irradiated with black light for 2 hours (Type: FL 15BL-B, manufactured by Matsushita Electric Industry Co., Ltd.) with an ultraviolet irradiation intensity of 2 mW / cm ² . Then, the concentration of the acetaldehyde gas in the vessel was detected by using gas chromatography, and the photocatalytic activity was determined on the basis of the reduced concentration. Criteria for the evaluation were provided as follows. Acetaldehyde gas concentration after 2 hours evaluation ranking <50 ppm A 50-200 ppm B 200-300 ppm C 300-450 ppm D 450 ppm < e

2) Evaluation of the adhesive property

The Evaluation of the adhesive property was made according to the cross-cut scotch tape test according to JIS K5400 carried out. A distance between cross-cut lines was set to 2 mm, and the number of squares is set to 25.

The Evaluation points were given to a criterion described in JIS K5400 ajar.

3) Immersion test in boiling water

tap water with an electrical conductivity in the range between 170 and 230 μS / cm was combined with a small amount of boiling stones in a 1000 mL Pyrex beaker filled, those to a size of 70 mm × 70 mm cut sample was made using a normal clip hanged in boiling water, so that the entire sample after heating and boiling the water immersed in it. After 15 min immersion in boiling water was the sample for Cool for 4 hours at room temperature and allowed to dry, then that described in Section 2) Test of adhesive property carried out, so that evaluation points according to the in JIS K5400 described above.

4) Total light transmission

The total light transmission at one wavelength of 550 nm the one adhesion layer and a photocatalyst layer-carrying sample was used an automatically recording spectrophotometer (type: U-4000, manufactured by Hitachi Seisakusho) compared to a substrate on which no adhesion layer yet and photocatalyst layer was applied.

5) Evaluation of shelf life

The coated sample was exposed for 500 hours to black light irradiation with an ultraviolet radiation intensity of 3 mW / cm ² in a chamber at 40 ° C and 90% RH, then the adhesive property test described in section 2 was performed, so that evaluation points according to the criterion described in JIS K5400.

6) Accelerated weathering test under Using the Sunshine Carbon Arc Weathering Gauge

Accelerated weathering test using the Sunshine Carbon Arc Weathering Gauge provided in JIS K5400 was performed using the same gage (type: WEL-SUN-HCH, manufactured by Suga Shikenki Co., Ltd.) under conditions of test time of 500 hours, Black Panel temperature of 63 ° C, 120 min cycle and 18 min rainfall, performed. 3 pieces of the samples were subjected to the accelerated weathering test, then the samples were visually evaluated for Swelling, cracking, peeling, fading and surface alteration compared to the original test pieces before being subjected to the accelerated weathering test conditions, according to the following criterion. evaluation ranking Criterion for evaluation A All 3 samples showed no change. B 1 or 2 samples showed slight changes. C All 3 samples showed slight changes, or 1 or 2 samples obviously showed strong changes.

To performing This test was subjected to the adhesive property test described in Section 2) Obtained evaluation points according to the method described in JIS K5400 Criterion performed.

7) Test method for antibacterial property

The sample cut into a 5 cm × 5 cm piece is disinfected with 80% ethanol and then dried at 150 ° C., and 0.2 ml of a bacterial suspension of intestinal bacteria previously cultured and diluted to a concentration of 10 ⁵ / ml was added dropwise to the surface of the sample and placed in an incubator. Four samples were provided for the test for each irradiation condition, namely 4 samples for black light irradiation (15 W x 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 another 4 samples were provided for the test without irradiation. After the predetermined time elapsed (after 1, 2, 3 and 4 hours), the samples were taken out and the bacterial solution adhered to the samples was wiped using disinfected gauze soaked in sterilized physiological saline. The sterilized gauze used was placed in 10 mL of sterilized saline and shaken thoroughly. The supernatant of the bacterial solution thus obtained was inoculated into an agar medium prepared in an autoclave-sterilized petri dish of 95 mm in diameter. Then, the number of intestinal bacteria colonies cultured at 36 ° C for 24 hours was counted. Another sample, obtained by the same procedure from the graft drop of the bacterial solution to an incubator, was treated according to the method described above and the number of intestinal bacterial colonies was counted. On the basis of the determined number, the survival rate of the bacteria was calculated after the respective predetermined time for each group, namely without irradiation, irradiation with black light or irradiation with a fluorescent lamp. The evaluation criterion corresponded to the following table. Survival rate (%) of intestinal bacteria after 4 hours evaluation ranking <20% A 20-40% B 40-60% C 60-80% D 80% < e

As an index for evaluating the soil-repellent function of the sample, a decomposed amount of ordinary salad oil mainly composed of linoleic acid was quantitatively determined on a photocatalyst-carrying structure to learn how to quickly degrade adhering fat and oil on the surface. On the surface of a photocatalyst-carrying structure cut into pieces of a size of 5 cm × 5 cm, salad oil was easily applied at a dose of 0.1-0.15 mg / cm ² using a paper. The amount applied was measured from the difference in weight of the structure before and after application of the oil using a precise balance. As an index of the soil-repellent property, decomposed amounts of the salad oil were determined after predetermined times by adjusting the distance between the sample and black light, looking for a point where an ultraviolet radiation intensity on a surface of the sample was 3 mW / cm ² , and calculating the ratio between elapsed time and weight loss after irradiation with black light. Remaining amount (%) of salad oil after 24 hours light irradiation evaluation ranking <10% A 30-10% B 50-30% C 80-50% D 80% < e

Examples

(TA)

Primer-behandelter Polyesterfilm

(TB)

Vinylchlorid-Film

(TC)

Natronkalk-Glasplatte

(TD)

Metall-Aluminium-Platte

(TE)

Hochdichtes Polyethylen-Netz (Faserdicke: 0,2 mm, Maschenweite: 0,6 mm)

(TF)

Polypropylen-Röhre (Innendurchmesser: 30 mm, Außendurchmesser: 36 mm)

The following materials were used as substrate.

(TA)

Primer-treated polyester film

(TB)

Vinyl chloride film

(TC)

Soda-lime glass plate

(TD)

Metal aluminum plate

(TE)

High density polyethylene net (fiber thickness: 0.2 mm, mesh size: 0.6 mm)

(TF)

Polypropylene tube (inner diameter: 30 mm, outer diameter: 36 mm)

(PS-1)

Silizium-Tetramethoxid-Monomer (hergestellt von Shinetsu Chemical Industry Co., Ltd.)

(PS-2)

Polymethoxy-Silan (hergestellt von Colcoat Co., Ltd., Handelsname: Methylsilikat 51)

(PS-3)

Polyethoxy-Siloxan (hergestellt von Colcoat Co., Ltd., Handelsname: Ethylsilikat 40)

As the polysiloxane contained in an adhesion layer, the following materials were used.

(PS-1)

Silicon tetramethoxide monomer (manufactured by Shinetsu Chemical Industry Co., Ltd.)

(PS-2)

Polymethoxy silane (manufactured by Colcoat Co., Ltd., trade name: methyl silicate 51)

(PS-3)

Polyethoxy siloxane (manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 40)

(KS-1)

Handelsname: Cataloid SI-350 (hergestellt von Shokubai Kagaku Co., Ltd., Partikeldurchmesser: 7–9 nm)

(KS-2)

Handelsname: Snowtex ST-XS (hergestellt von Nissan Chemical Industries Co., Ltd., Partikeldurchmesser: 4–6 nm)

As the colloidal silica contained in an adhesion layer, the following materials were used.

(KS-1)

Trade name: Cataloid SI-350 (manufactured by Shokubai Kagaku Co., Ltd., particle diameter: 7-9 nm)

(KS-2)

Trade name: Snowtex ST-XS (manufactured by Nissan Chemical Industries Co., Ltd., particle diameter: 4-6 nm)

(J-1)

3% Massenanteil Silizium enthaltende Acryl-Silizium-Harzlösung in Xylen

(J-2)

10% Massenanteil Silizium enthaltende Acryl-Silizium-Harzlösung in Xylen

(J-3)

20% Massenanteil Silizium enthaltende Acryl-Silizium-Harzemulsion in Wasser

(J-4)

50% Massenanteil Silizium enthaltende Acryl-Silizium-Harzemulsion in Wasser

(J-5)

10% Massenanteil Silizium enthaltende Polyester-Silizium-Harzlösung in Xylen

(J-6)

Acryl-Harzlösung in Xylen

(J-7)

Polyester-Harzlösung in Xylen

(J-8)

3% Massenanteil Silizium enthaltende Epoxy-Silizium-Harzlösung in Methylehtylketon

As the resin solution into which polysiloxane or colloidal silica is introduced, the following materials were used.

(J-1)

3% by weight silicon-containing acrylic-silicon resin solution in xylene

(J-2)

10% by weight silicon-containing acrylic-silicon resin solution in xylene

(J-3)

20% by weight silicon-containing acrylic-silicon resin emulsion in water

(J-4)

50% by weight silicon-containing acrylic-silicon resin emulsion in water

(J-5)

10% by weight silicon-containing polyester-silicon resin solution in xylene

(J-6)

Acrylic resin solution in xylene

(J-7)

Polyester resin solution in xylene

(J-8)

3% by weight silicon-containing epoxy-silicon resin solution in methyl ethyl ketone

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

(C-1)

Feines Pulver von Titandioxid (hergestellt von Nihon Aerozil Co., Ltd., Handelsname: P-25, Durchmesser der Kristallitgröße: 27 nm)

(C-2)

Titandioxid-Sol (Sol angesäuert mit Salpetersäure, Durchmesser der Kristallitgröße: 10 nm)

(C-3)

Titandioxid-Sol (schwach alkalisches Sol mit pH 9,0, Durchmesser der Kristallitgröße: 20 nm)

For the photocatalyst, the following materials were used.

(C-1)

Fine powder of titanium dioxide (manufactured by Nihon Aerozil Co., Ltd., trade name: P-25, diameter of crystallite size: 27 nm)

(C-2)

Titanium dioxide sol (sol acidified with nitric acid, diameter of crystallite size: 10 nm)

(C-3)

Titanium dioxide sol (weakly alkaline sol with pH 9.0, diameter of the crystallite size: 20 nm)

(Z-1)

Kieselsäure-Sol: hergestellt von Shokubai Kasei Co., Ltd., Handelsname Cataloid SI-30, spezifischer Oberflächeninhalt nach dem Trocknen bei 150°C: 180m²/g

(Z-2)

Aluminiumoxid-Sol: hergestellt von Nissan Chemical Industries Co., Ltd., Handelsname: Aluminiumoxid-Sol-200, spezifischer Oberflächeninhalt nach dem Trocknen bei 150°C: 400 m²/g

(Z-3)

Zirkoniumdioxid-Sol: Dieses kann mittels Hydrolysierung von Zirkonium-Tetrabutoxid (TBZR; hergestellt von Nippon Soda Co., Ltd.) in Ethanol, Trocknen bei 150°C, dann Erhitzen auf 300–500°C und anschließendem Dispergieren mit einer verdünnten wässrigen Salpetersäure-Lösung gewonnen werden. Der spezifische Oberflächeninhalt des anschließend bei 150°C getrockneten Produkts des dispergierten Sols liegt im Bereich von 50 bis 80 m²/g.

(Z-4)

Niobiumoxid-Sol: Dieses kann mittels Neutralisierung einer wässrigen Lösung von Niobiumoxalat, hergestellt von CBMM Co., Ltd., mit 10% wässrigem Ammoniak, Trocknens bei 150°C und anschließenden Dispergierens mit einer verdünnten wässrigen Salpetersäure-Lösung gewonnen werden. Der spezifische Oberflächeninhalt des anschließend bei 150°C getrockneten Produkts des dispergierten Sols liegt bei 60 m²/g.

(Z-5)

20% Massenanteil Silizium enthaltende Acryl-Silizium-Harzemulsion in Wasser.

(Z-6)

Silankoppler, tri-(beta-Methoxyethoxy)vinyl-Silan (Handelsname: A-1 72), hergestellt von Nippon Uniker Co., Ltd..

A metal oxide sol or a metal hydroxide sol applied together with a photocatalyst was obtained by drying one of the following materials in sol form.

(Z-1)

Silica sol: manufactured by Shokubai Kasei Co., Ltd., trade name Cataloid SI-30, specific surface area after drying at 150 ° C: 180m ² / g

(Z-2)

Alumina sol: manufactured by Nissan Chemical Industries Co., Ltd., trade name: Alumina Sol-200, specific surface area after drying at 150 ° C: 400 m ² / g

(Z-3)

Zirconia sol: This can be obtained by hydrolyzing zirconium tetrabutoxide (TBZR, manufactured by Nippon Soda Co., Ltd.) in ethanol, drying at 150 ° C, then heating to 300-500 ° C and then dispersing with a dilute aqueous nitric acid Solution can be obtained. The specific surface area of the product of the dispersed sol which is subsequently dried at 150 ° C. is in the range from 50 to 80 m ² / g.

(Z-4)

Niobium oxide sol: This can be obtained by neutralizing an aqueous solution of niobium oxalate manufactured by CBMM Co., Ltd. with 10% aqueous ammonia, drying at 150 ° C, and then dispersing with a dilute aqueous nitric acid solution. The specific surface area of the product of the dispersed sol which is subsequently dried at 150 ° C. is 60 m ² / g.

(Z-5)

20% by weight silicon-containing acrylic-silicon resin emulsion in water.

(Z-6)

Silane coupler, tri- (beta-methoxyethoxy) vinyl-silane (trade name: A-1 72) manufactured by Nippon Uniker Co., Ltd ..

A solution to form 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. The photocatalyst layer was formed by the dipping method when the layer 2 um or less and / or the design of a substrate is other than plate-shaped, while the photocatalyst layer is formed using a doctor blade coater was when the substrate is a plate and its thickness 2 microns or more is. The drying process for the photocatalyst layer was carried out at the same temperature as drying the adhesion layer.

in the Following are in Table 1 to 4 compositions in the examples for the embodiment of the present invention and in comparative examples, wherein type, amount and / or thickness of the materials and / or methods are different for making films, and features the photocatalyst-carrying structure will be described.

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

in the Comparative Example 1 is a photocatalyst layer-supporting Given structure without providing an adhesion layer. In this Case, the photocatalyst layer has no adhesive property and is easily replaced. Further, after the durability test, the surface of the polyester film becomes due to a photocatalytic effect and holes and breaks were observed on the film.

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

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

in the In contrast, as shown in Example 2, a photocatalyst layer was lost despite the use of polysiloxane-containing acrylic-silicon resin for the adhesion layer, their adhesive property and was replaced by the adhesion layer, if the content of polysiloxane in the adhesion layer up to a proportion increased by 70% by weight becomes.

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

in the In contrast, when the content of colloidal silica in the adhesion increased to 50% mass fraction became both the adhesive property and the durability considerably deteriorated.

In Examples 1 to 18 were titania (P-25) produced by Nihon Aerozil Co., Ltd., reported in (C-1), as a photocatalyst used and silica sol was in most cases as a metal oxide sol or metal hydroxide sol as a component of the photocatalyst layer used, and the structures were excellent in all the examples Features equipped. In Examples 8 and 9, the Structures disclosed in which both layers on a substrate are made of polyethylene mesh or polypropylene tube, and it is applied It is shown that these structures are excellent photocatalytic Activity, Have adhesive property and durability. It was also found that this outstanding property after lowering the salary on silica sol in the photocatalyst layer to 30% mass fraction still were noticeable (see Example 6), but both the adhesive property as well as the durability were severely worsened when the salary was reduced to 20% by weight (see Example 4).

In Example 11 used a structure in which alumina sol used instead of silica sol was, and this structure was in their capacity as well excellent as with the use of silica sol.

In Example 17, a structure was used in which a thickness of a adhesion and a photocatalyst layer was adjusted to 0.5 μm and 1 μm, respectively. In this Case, both the adhesive property and the durability were excellent, and the photocatalytic activity turned out to be very high although the thickness of the photocatalyst layer was very thin.

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

Example 19 Use of titania sol

A coating material for use in forming a photocatalyst layer was prepared by adding and dispersing 12% by mass of titania-containing and nitric acid acidified titanium oxide sol, also called titanium (IV) oxide sol or titania sol, which is a substituent of fine particle titanium dioxide (P-25) manufactured by Nihon Aerozil Co., Ltd., into silica gel (trade name Cataloid SI-30, manufactured by Shokubai Kasei Co., Ltd.), adjusting the pH to 1.5, and further adding a surfactant. Meanwhile, a solution for use for an adhesive layer was prepared by adding polymethoxy silane (PS-2) to a resin solution used in Example 10 in a ratio such that the content of silica in a dried adhesion layer is 35% by mass.

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

The achieved 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 according to the same procedure as in Example 19, with the exception that the silica sol in Example 19 by a mixed sol solution from alumina sol manufactured by Nissan Chemical Industries Co., Ltd., and silica sol was produced.

For the received Photocatalyst-carrying structure became high adhesive property and photocatalytic activity detected.

Example 21 Coating according to the gravure printing method

at Use of the gravure printing method has become the solution for forming an adhesion layer and the solution for forming a photocatalyst layer on a polyester film (Trade name: Cosmoshine A4100) manufactured by Toyobo Co., Ltd. at a rate of 10 m / min and at a dry zone temperature of 130 ° C applied, so that the thickness of the layers was 3 microns each. For the Printing process was a micro-gravure coating device with a Width of 70 cm, manufactured by Yasui Seiki Co., Ltd. used.

For the scored Photocatalyst-carrying structure was very high overall light transmittance of 95%.

Example 22 Coating according to the spray method

The solution used in Example 9 for forming an adhesion layer and the solution for forming a photocatalyst layer were used a spray gun (type: WIDER 88, manufactured by Iwata Tosoki Kogyo K.K.) was sprayed onto a soda-lime glass substrate. Both solutions for forming the adhesion layer and the photocatalyst layer were dried at 120 ° C for 30 minutes.

For the scored Photocatalyst-carrying structure became good adhesive property and photocatalytic activity detected.

Example 23 Using Epoxy-Silicon Resin

A Photocatalyst-carrying structure was prepared using the same Materials and the same process as prepared in Example 12, with the exception that the polyester resin solution in xylene by methyl ethyl ketone solution of 3% by mass silicon-containing epoxy resin was replaced.

For the scored Photocatalyst-carrying structure became good adhesive property and photocatalytic activity detected.

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

Examples 24-25

In In Examples 24 and 25, a structure is disclosed in the acrylic-silicon resin for forming an adhesion layer is used, and a mixture that is made and assembled is made of 50% by weight fine-grained Titanium dioxide P-25 (C-1), represented by 25% by weight in (Z-1) Silica sol and 25% by weight in (Z-2) reproduced alumina sol for Forming a photocatalyst layer is used. For the in Structures disclosed in these examples became good adhesive property as well good durability and durability detected under accelerated weathering conditions.

Examples 26-31

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

Examples 32-35

In Examples 32 and 33 show a structure in which either a polyethylene network or polypropylene tube was used as a substrate, the photocatalyst-carrying structure exhibited good photocatalytic activity, adhesive property and Durability was not achieved.

In Examples 32 to 35 discloses structures in which a colloidal silica having been used for forming an adhesion layer, and the photocatalytic activity, adhesive property, durability and durability across from accelerated weathering of these structures were considered outstanding found. In particular, when the structure with colloidal silica in small Particles (KS-2) is produced and the colloidal silica in acrylic-silicon resin emulsion (see examples 34 and 35) were introduced for this Structure type found very good properties.

In Example 29 discloses a structure in which a photocatalyst layer is formed from a coating material by adding 12% by mass 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 adjusted, the pH of the resulting mixture to 1.5 and the mixture a predetermined amount of a surface active Substance is added, and the thickness of an adhesion layer and a photocatalyst layer is set by the dipping method in each case to 0.5 microns or 0.3 microns. For the with the structures described above have become good Adherence and durability as well as high photocatalytic activity were noted despite the thin one Thickness of the photocatalyst layer.

A Structure with excellent physical property also became scored when the total content of silica gel and alumina sol was lowered in a photocatalyst to 30% by weight (s. Example 30).

• *1: % Massenanteil als SiO₂ in einer getrockneten Adhäsionsschicht.
• *2: % Massenanteil von Titandioxid und entweder einem Metalloxid-Gel oder einem Metallhydroxid-Gel insgesamt in einer getrockneten Photokatalysator-Schicht.

Tabelle 5 Photokatalytische Aktivität Adhäsionseigenschaft Adhäsionseigensch. Sunshine Verwitterungs-Messgerät Gesamte Lichtdurchlässigkeit (%) vor Haltbarkeitstest nach Haltbarkeitstest nach Test mit kochendem Wasser Zustand der Oberfläche nach Test Adhäsionseigensch. nach Test Beispiel-36 A 10 Pkt. 8 Pkt. 10 Pkt. A 8 Pkt. 68 Beispiel-37 A 10 8 10 A 8 65 Beispiel-38 A 10 10 8 A 8 63 Beispiel-39 B 10 10 8 A 8 75 Beispiel-40 B 10 10 10 A 8 - *5 Beispiel-41 B 10 8 8 A 6 71 Beispiel-42 C 10 10 10 A 8 82 Beispiel-43 C 10 8 8 A 6 87 Beispiel-44 B - *3 - *3 - *3 A - *3 - *4 Beispiel-45 A 10 10 8 A 8 - *4 Beispiel-46 B 10 8 10 A 6 75 Beispiel-47 B 10 8 8 A 6 70 Beispiel-48 A 10 8 8 A 8 66 Beispiel-49 B 10 8 8 A 8 77 Beispiel-50 B 10 8 10 A 8 - *5 Beispiel-51 B 10 8 10 A 8 83 Beispiel-52 B - *3 - *3 - *3 A - *3 - *4 Beispiel-53 C 10 8 10 A 6 - *4 Vergleichsbeispiel-5 A 2 2 0 C 0 54 Vergleichsbeispiel-6 A 4 2 2 C 2 52 Vergleichsbeispiel-7 A 4 2 2 C 2 48 Vergleichsbeispiel-8 B 4 4 2 C 4 51

• *3: Da der Kreuzschnitt-Scotch-Tape-Test nicht verwendet werden kann, wurde die Beobachtung auf der Oberfläche der klebenden Bandseite unter Verwendung eines Binokulars durchgeführt. Als ein Ergebnis konnte keine Photokatalysator-Schicht angeklebt werden.
• *4: Die Bestimmung der Lichtdurchlässigkeit konnte aufgrund seiner unnormalen Gestaltung nicht durchgeführt werden.
• *5: Die Bestimmung der Lichtdurchlässigkeit konnte aufgrund eines undurchsichtigen Trägers nicht durchgeführt werden.

The photocatalytic activity of the samples prepared in Examples 24 to 35 was measured again after being subjected to durability test under high temperature and high humidity black light, immersion test in boiling water and accelerated weathering test using the sunshine carbon arc weatherometer according to the above-described method, in particular based on the light-decomposed amount of acetaldehyde. As a result, it was found that all the samples showed the same decomposition activity with respect to the initially decomposed amount of acetaldehyde, and it was found that the samples completely retained their initial photocatalytic activity. Table 4 carrier adhesion Photocatalyst layer Adhesion layer thickness (μm) Photocatalyst layer thickness (μm) Type Salary * 1 Resin sol. Titanium dioxide Z-1 Z-2 Z-3 Z-5 Z-6 Type Salary * 2 Salary * 2 Salary * 2 Salary * 2 Salary * 2 Salary * 2 Bsp.-36 TA - - J-1 C-1 50 40 - - 10 - 10 6 Bsp.-37 TB - - J-1 C-1 40 40 - - 20 - 10 6 Bsp.-38 TA PS-1 15 J-1 C-1 40 10 - - 10 - 7 7 Bsp.-39 TB PS-1 30 J-1 C-1 25 - - - 50 - 7 3 Bsp.-40 TC PS one 45 J-2 C-1 20 30 10 10 30 - 3 3 Bsp.-41 TB PS-1 10 J-2 C-1 25 50 - 10 15 - 5 3 Bsp.-42 TA PS 2 20 J-2 C-1 40 30 10 - 10 10 3 1 Bsp.-43 TB PS-2 30 J-8 C-1 40 20 10 - 20 10 0.6 0.2 Bsp.-44 TD PS-2 45 J-7 C-2 50 20 - 10 20 - 5 3 Bsp.-45 TE PS-2 10 J-1 C-2 50 20 10 - - 20 6 6 Bsp.-46 TB PS-2 20 J-8 C-2 25 30 25 - - 20 5 3 Bsp.-47 TB PS-3 30 J-6 C-2 60 10 10 - 15 5 3 3 Bsp.-48 TA KS-1 10 J-3 C-1 30 20 10 - 35 5 10 6 Bsp.-49 TB KS-1 20 J-4 C-1 50 30 10 - 5 5 5 3 Bsp.-50 TC KS-2 30 J-3 C-1 20 30 10 - 30 10 5 3 Bsp.-51 TB KS-2 40 J-4 C-2 30 40 20 - 10 - 3 3 Bsp.-52 TD KS-2 20 J-3 C-2 60 20 - - 20 - 5 3 Bsp.-53 TE KS-2 30 J-3 C-2 20 40 - 10 30 - 5 2 Comp. Bsp.-5 TA - - - C-1 40 30 10 - 20 - 10 10 Comp. Bsp.-6 TB PS-1 70 1-1 C-1 40 30 10 - 20 - 10 6 Comp. Bsp.-7 TA KS-1 50 J-3 C-1 40 30 10 - 20 - 10 6 Comp. Bsp.-8 TB PS-1 30 J-1 C-1 45 30 20 - 5 - 7 3

• * 1:% by mass SiO ₂ in a dried adhesion layer.
• * 2:% by weight of titanium dioxide and either a metal oxide gel or a metal hydroxide gel in total in a dried photocatalyst layer.

Table 5 Photocatalytic activity adhesion Adhäsionseigensch. Sunshine Weathering Gauge Total light transmittance (%) before durability test after durability test after test with boiling water Condition of the surface after test Adhäsionseigensch, after test Example-36 A 10 pts 8 pts 10 pts A 8 pts 68 Example-37 A 10 8th 10 A 8th 65 Example-38 A 10 10 8th A 8th 63 Example-39 B 10 10 8th A 8th 75 Example-40 B 10 10 10 A 8th - * 5 Example-41 B 10 8th 8th A 6 71 Example 42 C 10 10 10 A 8th 82 Example-43 C 10 8th 8th A 6 87 Example-44 B - * 3 - * 3 - * 3 A - * 3 - * 4 Example-45 A 10 10 8th A 8th - * 4 Example-46 B 10 8th 10 A 6 75 Example-47 B 10 8th 8th A 6 70 Example-48 A 10 8th 8th A 8th 66 Example-49 B 10 8th 8th A 8th 77 Example-50 B 10 8th 10 A 8th - * 5 Example-51 B 10 8th 10 A 8th 83 Example-52 B - * 3 - * 3 - * 3 A - * 3 - * 4 Example-53 C 10 8th 10 A 6 - * 4 Comparative Example-5 A 2 2 0 C 0 54 Comparative Example-6 A 4 2 2 C 2 52 Comparative Example 7 A 4 2 2 C 2 48 Comparative Example 8- B 4 4 2 C 4 51

• * 3: Since the cross-cut scotch tape test can not be used, the observation was performed on the surface of the adhesive tape side using a binocular. As a result, no photocatalyst layer could be adhered.
• * 4: The determination of the light transmittance could not be performed due to its abnormal design.
• * 5: The determination of the light transmittance could not be performed due to an opaque support.

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

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

In Examples 36 and 37 disclose a structure in which acrylic-silicon resin for forming an adhesion layer was used and a complex was prepared and assembled 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 sols and 10- 20% by weight Acrylic-silicon resin emulsion and used to form a photocatalyst layer. For the structures disclosed in these examples were subsequently to the implementation the cooking test good adhesive property as well as good durability and durability across from accelerated weathering.

In Examples 38 to 42 discloses a structure in which polysiloxane containing acrylic-silicon resin for forming an adhesion layer was used and the same photocatalyst powder as in Example 36 was used to form a photocatalyst layer, and The type and content of a sol to form a miscible gel were changed. For the Structures made in these examples have been good photocatalytic activity as well as good adhesion, durability and resistance to accelerated Weathering after performing of the test with boiling water. In both cases, in the resin into which polysiloxane has been introduced, from 3% by weight Silicon-Containing Acrylic-Silicon Resin (Examples 38 and 39) or 10% by weight silicon-containing acrylic-silicon resin (Examples 40, 41 and 42), the adhesive property proved to be durable and durability towards accelerated Weathering of the structures as outstanding.

In Examples 44 and 45 disclose a structure in which a adhesion and a photocatalyst layer on either a polyethylene mesh or a polypropylene tube applied will, and for the structures prepared in these examples became good photocatalytic Activity, Adhesive property and durability determined.

These Good physical properties were just as much for the structures observed in which the resin 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 their adhesive property and was replaced when the polysiloxane content in an adhesion layer 70% by mass although polysiloxane-containing acrylic-silicon resin for the adhesion has been used.

In Examples 48 to 53 discloses a structure in which colloidal silica containing resin was used to form an adhesion layer, and for the structures prepared in these examples became good photocatalytic Activity, Adhesive property after performing the test with boiling water, durability and durability across from accelerated weathering. In particular, the structures, in which colloidal silica with small particle diameter (KS-2) and acrylic-silicon resin emulsion, in this colloidal silica (Examples 50 to 53) were used excellent physical properties.

however proved the adhesive property and the durability of the structure, in which the content of colloidal silica in the adhesion layer increased to 50% mass fraction (Comparative Example 7) was greatly deteriorated.

In Examples 44 to 47 discloses a structure in which a adhesion and a photocatalyst layer by the doctor blade coating method and a coating material for forming the photocatalyst layer by dispersing the titania sol, that with nitric acid acidified and containing 12% by weight of titanium dioxide, this 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 by Nippon Soda Co., Ltd., replacing the pH the resulting mixture to 1.5 and adding a predetermined Amount of a surface active Substance was made to this mixture. For those in these examples fabricated structures became good adhesive property and durability as well as high photocatalytic activity despite the relatively thin thickness the photocatalyst layer detected.

In Example 47 has good physical properties Achieved structure despite lowering the total content of acrylic-silicon resin emulsion and silane couplers in a photocatalyst layer to 20% by weight, however, in Comparative Example 8, the adhesive property and the Durability greatly reduced when this total content to 5% by mass was lowered even when adding acrylic-silicon resin emulsion to the photocatalyst layer.

The samples obtained in Examples 36 to 53, all of which were subjected to durability test under irradiation of black light at high temperature and high humidity, immersion test in boiling water, and accelerated weathering test using the Sunshine Carbon Arc Weathering Gauge, and thereafter was again examined for their photocatalytic activity according to the same method as at the beginning of the test based on the decomposition amount of acetaldehyde by light, and it was found that all the samples had the same decomposition amount of acetaldehyde as at the beginning of the test and still retain the initial photocatalytic activity with full capacity.

Example 54

According to the in Example 42 was a sample of a titania photocatalyst layer bearing structure, and the antibacterial activity of the sample evaluated.

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

(S-1)

5% Massenanteil ethanolische Lösung von Tetraethoxy-Silan (Super Reagenz Grad, hergestellt von Wako Pure Chemical Co. Ltd.).

(S-2)

5% Massenanteil ethanolische Lösung von Tetramethoxy-Silan (hergestellt von Shinetsu Chemical Industry Co. Ltd.).

(S-3)

5% Massenanteil ethanolische Lösung von Methyltriethoxy-Silan (Super Reagenz Grad, hergestellt von Wako Pure Chemical Co. Ltd.).

(S-4)

5% Massenanteil ethanolische Lösung von tri(beta-Methoxyethoxy)Vinyl-Silan (hergestellt von Nihon Unikar Co. Ltd., Handelsname: A-172).

As the silicon compound used for a photocatalyst coating material, the following materials were used:

(S-1)

5% by weight ethanolic solution of tetraethoxy-silane (Super Reagent Grade, manufactured by Wako Pure Chemical Co. Ltd.).

(S-2)

5% by mass of ethanolic solution of tetramethoxy-silane (manufactured by Shinetsu Chemical Industry Co. Ltd.).

(S-3)

5% by weight ethanolic solution of methyl triethoxy silane (Super Reagent Grade, manufactured by Wako Pure Chemical Co. Ltd.).

(S-4)

5% by mass ethanolic solution of tri (beta-methoxyethoxy) vinyl silane (manufactured by Nihon Unikar Co. Ltd., trade name: A-172).

• *1: Der Gehalt ist mit % Massenanteil (Gew%) bezogen auf die Masse der getrockneten Beschichtungslösung angegeben.

To a sol solution and a silicon compound solution shown in (Z-1) to (Z-3), either titanium dioxide powder or sol as a photocatalyst was dispersed together with either water or a mixed solvent of water and ethanol, while the pH of the The mixture was adjusted to an appropriate value between 1.5 and 9 depending on the type of the raw materials and the additives, and further, a predetermined amount of a surfactant was added so that a coating material for forming a photocatalyst layer was obtained. The content of the components contained in this coating material and the viscosity and sedimentation state of the particles immediately after the preparation of the coating material and 90 days after the sealing / fusing are shown in Table 6. Table 6 photocatalyst metal dioxide Silicon component at the start after 90 days Type Salary * 1 Type Salary * 1 Type Salary * 1 viscosity sedimentation viscosity sedimentation example wt% wt% wt% cP % cP % 55 C-1 20 Z-1 20 S-1 1 31 100 43 90 56 C-1 10 Z-1 20 S-1 1 14 '' 16 85 57 C-1 5 Z-1 5 S-1 0.2 3 '' 4 95 58 C-2 30 Z-1 10 S-1 2 33 '' 37 100 59 C-2 10 Z-1 10 S-3 0.1 7 '' 9 100 Z-2 0.3 60 C-2 2 Z-1 2 S-3 0.01 1 '' 1 100 Z-2 0.05 61 C-1 0.5 Z-1 0.5 S-2 0.02 1 '' 1 95 62 C-1 0.1 Z-1 0.1 S-2 0,002 1 '' 1 95 63 C-1 3 Z-1 6 S-1 0.2 2 '' 2 90 C-2 3 Z-3 0.2 64 C-3 5 Z-1 7 S-4 0.2 3 '' 5 95 65 C-3 1 Z-1 2 S-3 0.04 2 '' 2 100 66 C-3 0.2 Z-1 0.2 S-1 0.01 1 '' 1 100 Comparative Ex. 9 C-1 5 Z-1 5 - 3 100 12 45 10 C-2 30 Z-1 10 - 33 '' 430 55 11 C-2 10 Z-1 10 - 7 '' 23 65 Z-2 0.3 - 12 C-3 5 Z-1 7 - 3 '' 9 50 13 C-3 1 Z-1 2 - 2 '' 8th 60 NB: Parikelsedimentation was indicated by means of a ratio of the sedimentation volume in relation to the total volume of the coating solution.

• * 1: The content is given by% by weight (% by weight) based on the mass of the dried coating solution.

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. By adding a small amount of a silicon compound was the stability of the photocatalyst coating material after 90 days improved.

In Examples 58 to 60 were used with nitric acid acidified titanium oxide sol as a photocatalyst, Silica gel and alumina sol were combined as the miscible metal oxide sol and methyl triethoxy silane was used as a silicon compound in Examples 59 and 60 used. By means of the use of this method was a remarkable improvement in the durability of the application of this coating material with a film formed thereon across from boiling water, especially the resistance to boiling Water in tap water, scored.

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

In Example 63 provides a photocatalyst-carrying structure, in the titanium dioxide powder (P-25) and titanium oxide sol together as photocatalyst and silica sol and zirconia sol together as a joinable / miscible Metal oxide sol were used, whereby by adding Tetramtheoxy silane to the solution a coating material has been achieved, the good stability and sedimentation property had.

In Examples 64 to 66 will be a photocatalyst-carrying structure discloses a coating material for forming a photocatalyst layer by changing the type of silicon compound was made, and each in Coating material prepared in these examples was added found to be stable in all previously defined amounts to be added.

in the In contrast, in Examples 9 to 13, there was the coating material no silicon compound was added, the viscosity of the coating material drastically increased after 90 days, and the particle sedimentation certainly resulted from it, and therefore, it was difficult to set the conditions for making films to control when using these coating materials, and it was not possible, one stable quality to achieve exhibiting photocatalyst-carrying structure.

Examples 67 to 71

(SA)

Primer-behandelter Polyesterfilm

(SB)

Glasplatte aus Natronkalk

(SC)

Metall-Aluminiumplatte

(SD)

Hochdichtes Polytheylen-Netz (Faserdicke: 0,2 mm, Maschenweite: 0,6 mm)

(SE)

Polypropylen-Netz (Innendurchmesser: 30 mm, Außendurchmesser: 36 mm)

Using the coating materials prepared in Examples 55 to 59, photocatalyst-carrying structures were prepared using the following substrates. The following materials were used as substrates:

(SA)

Primer-treated polyester film

(SB)

Glass plate made of soda lime

(SC)

Metal aluminum plate

(SD)

High density polythene net (fiber thickness: 0.2 mm, mesh size: 0.6 mm)

(SE)

Polypropylene mesh (inner diameter: 30 mm, outer diameter: 36 mm)

• *1: Konzentration fester Bestandteile des Harzes in der Beschichtungslösung.
• *2: Konzentration fester Bestandteile in der Beschichtungslösung.

Tabelle 8 Beispiel Photokatalytische Aktivität Adhäsionseigenschaft Sunshine Verwitterungs-Messgerät Gesamte Lichtdurchlässigkeit (%) vor Haltbar-keits-Test nach Haltbarkeits-Test nach Test mit kochendem Wasser Oberflachenzustand nach Test Adhäsionseigensch. nach Test Beispiel-67 A 10 10 - *6 A 10 63 Beispiel-68 A 10 10 - *6 A 10 75 Beispiel-69 B 10 10 - *6 A 10 - *5 Beispiel-70 B 10 10 - *6 A - *3 - *4 Beispiel-71 B 10 10 10 A 10 82

• *3: Da der Kreuzschnitt-Scotch-Tape-Test nicht verwendet werden konnte, wurde die Oberfläche des Klebebands unter Verwendung eines Binokulars betrachtet, jedoch wurde keine Adhäsion der Photokatalysator-Schicht beobachtet.
• *4: Die Bestimmung konnte aufgrund der unterschiedlichen Gestaltungen nicht durchgeführt werden.
• *5: Die Bestimmung konnte aufgrund eines undurchsichtigen Trägers nicht durchgeführt werden.
• *6: Es wurde keine Evaluation durchgeführt.

The adhesion layer was formed by the dipping method when its thickness was 2 μm or less, or the design of the substrate other than plate-shaped, or by a method using a Baker applicator when the substrate was plate-shaped and its thickness was 2 μm or more , The temperature used to dry the adhesive layer was 80 ° C when the material of the substrate was (SD) or (SE), and for all other cases it was 120 ° C. The photocatalyst layer was formed by the dipping method when its thickness was 2 μm or less, or the shape of the substrate other than plate-shaped, or by a method using a blade coater, when the substrate was plate-shaped and its thickness was 2 μm or more fraud. The drying of the photocatalyst layer was carried out at the same temperature as the drying of the adhesion layer. Hereinafter, the physical properties of the photocatalyst-carrying structures prepared in Examples and Comparative Examples are shown in Tables 7 and 8, wherein the type and content of the above-described materials, the thickness of an applied film, the method of forming the film, etc., respectively was changed. Table 7 example carrier Coating solution for adhesion layer Coating solution for photocatalyst layer Thickness of the adhesion layer (μm) Thickness of the photocatalyst layer (μm) TiO ₂ Z-1 Z-2 Type Salary * 1 Resin sol. Type Salary * 2 Salary * 2 Salary * 2 Example-67 SA PS-1 10 J-1 C-1 20 20 - 3 3 Example-68 SA PS-1 5 J-1 C-1 2 0 - 1 3 Example-69 SC PS-1 20 J-2 C-1 5 5 - 4 2 Example-70 SD PS-2 20 J-2 C-2 30 10 - 5 3 Example-71 SE PS-2 30 J-2 C-2 10 10 0.3 4 2

• * 1: concentration of solid components of the resin in the coating solution.
• * 2: concentration of solid components in the coating solution.

Table 8 example Photocatalytic activity adhesion Sunshine Weathering Gauge Total light transmittance (%) before durability test after durability test after test with boiling water Surface condition after test Adhäsionseigensch. after test Example-67 A 10 10 - * 6 A 10 63 Example-68 A 10 10 - * 6 A 10 75 Example-69 B 10 10 - * 6 A 10 - * 5 Example-70 B 10 10 - * 6 A - * 3 - * 4 Example-71 B 10 10 10 A 10 82

• * 3: Since the cross-cut scotch tape test could not be used, the surface of the adhesive tape was observed using a binocular, but no adhesion of the photocatalyst layer was observed.
• * 4: The determination could not be made due to the different designs.
• * 5: The determination could not be carried out due to an opaque carrier.
• * 6: No evaluation was performed.

The Samples prepared in Examples 67-71 were given a durability test under irradiation with black light at high temperature and high Moisture, an immersion test in boiling water and an accelerated Weathering test using the Sunshine Carbon Arc Weathering Gauge, the photocatalytic activity was each based on the decomposition amount of acetaldehyde by light according to the same Method as tested before the tests described above. From the result, that the same level of decomposition of acetaldehyde as before execution the tests described above for the samples obtained, it is shown that the original photocatalytic activity in the structures completely has been preserved.

Example 72

A Titanium dioxide-containing photocatalyst-carrying structure was according to the in Example 67 and an antibacterial Test was for the structure according to the above described method performed. The survival rate intestinal bacteria on the structure without irradiation with light 92%, 91% and 91% after 1, 2 and 3 hours, respectively, while the survival on the irradiation black-lighted structure 52%, 29% and 11% after 1, 2 or 3 hours. Furthermore was the survival rate intestinal bacteria on the irradiation with a fluorescent lamp 76%, 54% and 22% after 1, 2 and 3 hours respectively, what higher antibacterial activity showed as the structure left in the dark.

Example 73: Adhesive-treated Movies

A solution for forming an adhesion layer was prepared by mixing 30% by weight of polysiloxane (prepared Colcoat Co. Ltd., trade name: methyl silicate 51), based on the mass of acrylic-silicon resin, and 5% by weight of a hardener (silane coupler), based on the mass of acrylic-silicon resin, to a mixed solution from xylene and isopropanol (mixing ratio 50:50), which is 25% by weight Comprising 3% by weight of silicon-containing acrylic-silicon resin, prepared and with methyl ethyl ketone diluted so the concentration is 10% mass fraction based on the solid Constituents was.

The diluted solution was gravure printed on a polyester film (trade name: Cosmoshine 50 μm) A4100, manufactured by Toyobo Co. Ltd., applied so that after drying using a micro gravure coater (width: 70 cm) made by Yasui Seiki Co. Ltd. at a speed of 15 m / s and a dry zone temperature of 13 a 1 micron thicker Movie was formed.

Of the Polyester film on which an adhesion layer was then formed with a coating material to form a photocatalyst layer, which by means of dispersing with nitric acid acidified, 20% by weight of titanium dioxide as the photocatalyst-containing titanium oxide sol in nitric acid acidified, 20% silica-containing silica sol in the presence of a surfactants Substance, and subsequent thinning the dispersion with a mixture of ion exchange water and Ethanol (mixing ratio 50:50) to a concentration of 10% mass fraction based on solid Ingredients was prepared by gravure printing as for the adhesion layer coated, leaving a polyester film with one after drying 1 μm thick Photocatalyst layer was achieved.

After that was on the surface the photocatalyst-carrying structure having the polyester film, on which no photocatalyst had been applied, a solution that by adding 5% by weight based on solid constituents of a thermal radiation blocking agent, STS-500 from Sumitomo Osaka Cement Co. Ltd., to a commercially available adhesive was prepared, applied by using the gravure printing method. The adhesive-provided film became during lamination of the film with a polyethylene film (Pyren film OT 20 μm) P-2161, manufactured by Toyobo Co. Ltd., in a process of drying and winding in the dry area of the gravure device wrapped so that an adhesive layer is provided.

These Kind of films can be used as an adhesive film for window glass for vehicles, House window glass and window glass for medical facilities are used, and they are conveniently by their properties characterized, such. B. antibacterial activity, dirt repellent property and deodorizing property as well as anti-shattering films when breaking glass.

Example 74 glass plate

On a glass plate made of soda lime, also plate glass, which had a thickness of 1 mm and in a piece with an extension of 5 cm × 5 was cut, was a solution by mixing of 30% by weight of polysiloxane (methyl silicate 51, prepared Colcoat Co., Ltd.), based on the mass of acrylic-silicon resin, in a mixed solution from xylene and isopropanol (mixing ratio 50:50), which is 25% by weight Containing 3% by weight silicon-containing acrylic silicon resin, for Forming an adhesion layer applied using the No. 7 blade coater and at 100 ° C for 60 min dried. After the glass plate had cooled at ambient temperature, became 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 acidified with nitric acid, 20% by weight of silica containing silica sol in the presence of a surface-active Substance produced. The resulting solution was then applied to the above described adhesion layer, also using the No. 7 blade coater, and then applied for 60 min at 100 ° C dried so that a photocatalyst-carrying glass plate (sample No. 1).

Example 75 Fiberglass paper

The adhesive layer forming solution used in Example 74 was diluted with a xylene-propanol solution (50:50 mixing ratio) to a solid content based concentration of 5% by mass. A glass fiber paper SAS-030 (mass: 30 g / m ² ) manufactured by Oribest Co., Ltd. was dipped in the diluted solution prepared as described above and then pulled out, allowed to stand at 120 ° C at 100 ° C dried so that an adhesion layer was formed on the surface of this glass fiber paper. Then, the glass fiber paper on which the adhesion layer was formed was dipped in a solution prepared by diluting with ion exchange water of the coating material used in Example 74 to form a photocatalyst layer to a concentration of 10% by mass and dried at 100 ° C for 120 minutes to obtain a photocatalyst-carrying glass fiber paper (Sample No. 2).

Example 76 Spectacle lenses

A adhesion was on eyeglass lenses, PC pointal coat TC (+) 1.005 0.0065 mm 0 (diameter) from Nikon Corporation, formed by applying a solution, by mixing 20% by weight of polysiloxane (methyl silicate 51, manufactured by Colcoat Co., Ltd.) based on the mass of the Acrylic-silicon resin, in a mixed solution of xylene and isopropanol (Mixing ratio 50:50) containing 10% by weight of 3% by weight of silicon Acrylic silicon resin was prepared on the lens after the in Example 75 applied, and the coated Lens became at 100 ° C for 20 min dried. After cooling the lens at ambient temperature became a coating material for forming a photocatalyst layer by dispersing of acidified with nitric acid and 5% by weight titania-containing titania sol in acidified with nitric acid and 5% by weight of silica containing silica sol in the presence of a surface-active Substance produced as a photocatalyst. Using this Coating material as a photocatalyst layer and under similar Using the dipping method became 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 for spectacles were obtained (sample No. 3).

Example 77 Polyvinyl chloride wallpapers

A solution prepared by mixing 30% by weight of polysiloxane (methyl silicate 51, manufactured by Colcoat Co., Ltd.), based on the mass of acrylic-silicon resin, in a mixed solution of xylene and isopropanol (mixing ratio 50: 50) containing 25% by mass of 3% by mass of silicon-containing acrylic-silicon resin was coated on a polyvinyl chloride (SG 5328, manufactured by Sangetsu, Co., Ltd.) in a size of 5 cm × 5 cm cut piece and applied to a thickness of 1 mm using a doctor blade coater # 7, and the coated wallpaper was then at 100 ° C for 20 min. dried so that an adhesion layer was achieved. After the wallpaper was cooled at ambient temperature, a coating material for forming a photocatalyst layer was prepared by dispersing nitric acid-acidified titan dioxide sol containing 20% by weight of titanium dioxide as a photocatalyst in a nitric acid-acidified silica sol containing 20% by mass of silica in the presence of a surfactant Substance produced. This solution was applied to the surface of the adhesion layer using a doctor blade No. 7, and the coated wallpaper was dried at 100 ° C for 20 minutes to obtain a photocatalyst-carrying wallpaper (Sample No. 4).

Example 78 Polyester films

The solution used in Example 77 to form an adhesion layer with a mixed solution from xylene and isopropanol (mixing ratio 50:50) diluted, so that the concentration of the mixture is based on 25% mass fraction solid ingredients was set. The diluted solution was then analyzed by means of a Gravure printing process at a speed of 10 m / min and a dry-range temperature of 130 ° C on a polyester film (Cosmoshine) A4100, manufactured by Toyobo Co., Ltd., using a Micro-gravure coating apparatus (Width: 70 cm), made by Yasui Seiki Co., Ltd., to make a layer with the thickness after drying of 3 microns applied.

Then was on the with an adhesion layer equipped polyester film used the coating material used in Example 77 for forming a photocatalyst layer according to the gravure coating method so as to form a photocatalyst-carrying polyester film with a after drying 3 microns thick photocatalyst layer was obtained (Sample No. 5).

Example 79 Protection filter for personal computers

A solution for forming an adhesion layer was prepared by mixing 30% by weight of polysiloxane (methyl silicate 51, manufactured by Colcoat Co., Ltd.) based on solid components based on the mass of the acrylic-silicon resin, in a xylene solution, the Contains 20% by weight of a 20% by weight silicon-containing acrylic silicon resin, and thinning with an isopropanol solution for adjusting the concentration to 20% by weight based on solid components produced. Then the solution was used Immersion on VDT filter, E-filter III, manufactured by Toray Co., Ltd., and the coated filter was then added 100 ° C for 20 min for forming an adhesion layer on the surface dried of the filter. Subsequently, the one with an adhesion layer equipped VDT protective filter supplied to a dipping process in a solution that by dilution of the ion exchange water coating material used in Example 77 was prepared so that the content of solid components in the coating material was 10% by weight, pulled out of it and at 100 ° C for 20 dried so that a photocatalyst-carrying VDT filter achieved (sample no. 6).

Example 80 Phone Case

The solution used in Example 77 to form an adhesion layer with a mixed solution from xylene and isopropanol (mixing ratio 50:50) diluted, so that the concentration of the solution was adjusted to 20% by weight based on solid constituents. The diluted one Mixture was by spraying on a housing for one Telephone set (Type: HIT-1, manufactured by Hitachi Seisakusho Co., Ltd.) using a spray gun (type: WIDER 88, manufactured by Iwata Tosoki Kogyo Co., Ltd.). After drying of the sprayed housing at 100 ° C for 20 min was a coating material used in Example 1 for Forming a photocatalyst layer by dilution with ion exchange water to a concentration of 8% by weight based on solid components, and the diluted coating material was applied by spraying as described above. After drying of the housing at 100 ° C for 20 A photocatalyst-carrying telephone box housing was achieved (Sample No. 7).

Example 81 glasses for spectacles

An adhesive layer was applied to a glass for spectacles, NL70HCCTc (+) 1.0 OS 0.00 (70 mm O), manufactured by Nikon Corporation, by applying a solution prepared by admixing 20% by weight of polysiloxane (methyl silicate 51, manufactured by Colcoat Co., Ltd.), based on the mass of the acrylic-silicon resin, in a mixed solution of xylene and isopropanol (mixing ratio 50:50), the 10% by weight of a 3% by weight silicon-containing acrylic silicon Resin contains, according to the glass prepared according to the dipping method described in Example 79, and the coated glasses were dried at 100 ° C for 20 min. After the glasses were cooled at ambient temperature, a coating material for forming a photocatalyst layer prepared by dispersing nitric acid-acidified titania-containing titania sol as a photocatalyst in silica acidified with nitric acid and containing 20% by mass of silica was added of a surfactant, is applied to the lens to form a photocatalyst layer. Using this solution for the photocatalyst layer and using the same dipping method, a photocatalyst layer was formed by coating the surface of this adhesion layer with the solution and drying at 100 ° C for 20 minutes to obtain a photocatalyst-carrying glass for spectacles was (Sample No. 8).

Example 82 curtains

textiles for curtains, trade name "Hospia" (for use in schools and hospitals) by Kawashima Orimono Co., Ltd., were cut into a piece of size 7 cm × 7 cm, and the pieces were in a solution immersed, by mixing 20% by weight of polysiloxane (Methyl Silicate 51, manufactured by Colcoat Co., Ltd.) based solid constituents based on the mass of the acrylic-silicon resin, in a mixed solution from xylene and isopropanol (mixing ratio 50:50), which is 15% by weight Contains 3% by weight of silicon-containing epoxy-silicon resin produced was extracted from it and dried at 80 ° C for 120 min. To cooling the textile goods at room temperature were those with an adhesive layer provided textile goods in a coating material for forming a Photocatalyst layer dipped, containing by dispersing 10% by mass titanium dioxide Titania sol, made from ammonia, also as ammoniacal alkali referred to, in 10% by weight of silica-containing silica sol in the presence of a surfactant Substance was prepared, pulled out of it and at 80 ° C for 120 min dried, so that photocatalyst-carrying textile goods for use as curtains achieved (sample no. 9).

Example 83 Nonwoven textile goods

unbleached Cotton nonwoven textile goods (trade name: Orcos, manufactured by Nisshinbo Co., Ltd.) was cut into pieces of size 7 cm × 7 cm, and each piece was having 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, in a mixed solution from xylene and isopropanol (mixing ratio 50:50), which is 25% by weight Contains 3% by weight silicon-containing acrylic silicon resin produced was prepared using a spray gun (type: WIDER 88) from Iwata Tosoki Kogyo Co., Ltd.). After drying the sprayed textile at 100 ° C for 30 min was that in Example 82 to form a photocatalyst layer used solution applied to this textile, and the coated textile was then at 100 ° C for 30 dried so that a photocatalyst-carrying nonwoven fabric made of cotton was achieved for Surgical gloves, tablecloths, covers for toilet seats, Japanese paper, Covers for Seedlings, packaging material for Foods etc. is suitable.

Example 84 Printed polyester fabric for umbrellas

Under Use of commercially available printed polyester cloth textile goods for umbrellas as a substrate became an adhesion layer and a photocatalyst layer according to that disclosed in Example 83 Applied method. The photocatalyst-carrying printed polyester cloths have almost no difference in patterns and feeling to normal cloth-textile goods (sample No. 11).

Example 85 Wallpaper (textile fabric)

Under Use of a plain textile fabric, SG 6758, manufactured from Sangetsu Co., Ltd., as a substrate became an adhesion layer and a photocatalyst layer according to that disclosed in Example 83 Process formed on the fabric.

The Photocatalyst-carrying wallpaper made of textile fabric had no negative Influence on the quality of textile fabric (Sample No. 12).

Example 86 Shutters made of aluminum

A Solution, by means of mixing of 30% by weight of polysiloxane (methyl silicate 51, manufactured by Colcoat Co., Ltd.) based on the mass of the Contains acrylic silicon resin, into a mixed solution Xylene and isopropanol (mixing ratio 50:50), which is 25% by weight 3% by weight silicon-containing acrylic-silicon resin produced was using a doctor blade No. 7 on one in pieces a size of 7 cm × 7 cm cut window frame plate made of aluminum, and the window frame aluminum plate was used to form an adhesion layer on the plate at 100 ° C for 60 min dried. After cooling the plate at ambient temperature became a coating material for forming a photocatalyst layer by dispersing with Nitric Acid Acidified, 20% by weight titania-containing titania sol in acidified with nitric acid, 20% Mass fraction of silica sol containing silica sol in the presence of a surfactants Substance produced. The coating material was then submerged Using a squeegee coating device no. 7 on the surface of Adhesion layer described above applied, and the coated plate was at 130 ° C for 10 min dried, leaving a photocatalyst-carrying aluminum plate achieved (sample no. 13).

Example 87 Stainless steel plates

The solution used in Example 86 for forming an adhesion layer was diluted with a mixed solution from xylene and isopropanol (mixing ratio 50:50) to a concentration of 5% by weight based on solids. A in one piece a size of 7 cm × 7 cm cut stainless steel plate made of SUS 316 (thickness: 0.2 mm) was in the solution described above dipped, pulled out of it and to form an adhesion layer on the surface the stainless steel plate dried at 120 ° C for 20 min. Subsequently was those with an adhesive layer coated stainless steel plate dipped in a solution by means of Adjusting the concentration of the coating material used in Example 86 for one Photocatalyst layer with ion exchange water to a concentration made of 10% by weight, extracted from it and at 120 ° C for 20 min dried, leaving a photocatalyst-carrying stainless Steel plate was achieved (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 immersed in a solution by means of Mixing of 30% by weight of polysiloxane (methyl silicate 51, prepared from Colcoat Co., Ltd.), based on the mass of the acrylic-silicon resin, in a 20% Mass fraction of a xylene solution a 20% by weight silicon-containing acrylic-silicon resin, and subsequent Diluting the Mixture with isopropanol solution to a concentration of 20% by weight based on solid constituents was pulled out of it and to form an adhesion layer on the tin plate at 100 ° C for 60 min dried. Subsequently became the one with an adhesion layer coated tin plate dipped in a solution by means of Adjusting the concentration of the coating material used in Example 86 for one Photocatalyst layer by dilution with ion exchange water to a concentration of 10% by weight the solution pulled out and at 100 ° C for 60 min dried so as to obtain a photocatalyst-carrying tin plate was (sample No. 15).

Example 89 Apertures

To removing a 800 mm wide and 700 mm high strip Aperture, "Silky Curtain "(type with 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 Acrylic-silicon resin, in a mixed solution of xylene and isopropanol (mixing ratio 50:50), the 25% by weight 3% by weight silicon-containing acrylic-silicon resin contains was prepared by spraying using a spray gun, WIDER 88 manufactured by Iwata Tosoki Kogyo Co., Ltd. was applied. After drying the sprayed Aperture at 120 ° C for 20 min was applied to the diaphragm further by spraying a solution by means of thinning of the coating material used in Example 86 to form a photocatalyst layer with ion exchange water on a Concentration of 8% by weight based on solids was prepared (sample no. 16).

Example 90 Printed plywood / shuttering panels

On one in one piece size 7 cm × 7 cm cut, Printed Plywood, Neowood, made by Eidai Sangyo Co., Ltd., with a thickness of 2.5 mm was a solution by mixing of 30% by weight of polysiloxane (methyl silicate 51, prepared Colcoat Co., Ltd.), based on the mass of the acrylic-silicon resin, in a mixed solution from xylene and isopropanol (mixing ratio 50:50), which is 25% by weight Contains 3% by weight silicon-containing acrylic silicon resin produced using a knife coater # 7 applied and then to form an adhesion layer on the printed Shuttering panel at 100 ° C for 30 min dried. After cooling the printed formwork panel at ambient temperature became one Coating material for forming a photocatalyst layer by dispersing nitric acid acidified, containing 20% by weight titanium dioxide Titanium oxide 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 squeegee coating apparatus No. 7, the coating material was applied to the surface of the adhesion applied and at 100 ° C for 30 dried so that a photocatalyst-carrying printed Plywood was scored (sample no. 17).

Example 91 Synthetic timber

The solution used in Example 90 for forming an adhesion layer was mixed with a solution from xylene and isopropanol (mixing ratio 50:50) to a concentration diluted by 5% by weight based on solids.

One in one piece a size of 7 cm × 7 cm cut synthetic lumber, Esron Neolamber FFU-50, manufactured by Sekisui Chemical Industry Co., Ltd., has been incorporated into the diluted as above solution dipped, pulled out of it and to form an adhesion layer on the surface of lumber at 100 ° C for 120 min dried. Subsequently that became with an adhesive layer equipped lumber in a solution dipped by diluting of the coating material used in Example 90 for forming a photocatalyst layer with ion exchange water on a Concentration of 10% mass fraction was prepared, pulled out of it and at 100 ° C for 120 dried so that photocatalyst-carrying synthetic Timber was scored (Sample No. 18).

Example 92 wooden doors

A wooden door for interiors (type 38 RCO202-IR6, oak pattern) manufactured by Daiken Kogyo Co., Ltd., was in one piece a size of 7 cm × 7 cm, and on the piece became a solution which by mixing 20% by weight of polysiloxane (methyl silicate 51, prepared from Colcoat Co., Ltd.), based on the mass of the acrylic-silicon resin, into a mixed one solution from xylene and isopropanol (mixing ratio 50:50), which is 10% by weight Contains 3% by weight silicon-containing acrylic silicon resin produced was used to form an adhesion layer according to the in Example 91 applied immersion method and at 100 ° C for 20 min dried. After cooling of the piece at ambient temperature became a coating material for forming a photocatalyst layer by means of dispersing acidified with nitric acid, 5% by weight titania-containing titania sol in acidified with nitric acid, 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 the adhesion applied using the dipping method described above and at 100 ° C for 20 min dried, so that a photocatalyst-carrying wooden door scored has been.

Evaluation of the photocatalytic activity

The photocatalytic activity Samples 1 to 19 were respectively evaluated, and the results of the evaluation are shown in Table 9.

Industrial use

• *1: Da das zugrunde liegende Körner-Band-Verfahren nicht verwendet werden konnte, wurde die Oberfläche des Klebebandes betrachtet, jedoch wurde keine Adhäsion der Photokatalysator-Schicht erkannt.

The photocatalyst-carrying structure according to the present invention has high photocatalytic activity, and glass, plastics, metallic materials, fabric-textile goods, lumber and wooden materials, each provided with a damage-insensitive and very durable photocatalyst, can be used for lenses, various types of window glass, adhesive films, decorative films, wallpapers, curtains, building materials such as screens, interior decoration, etc. are used. Table 9 Total radiolucency Aldehyde-decomposing activity Salad oil decomposition activity Antibacterial activity Initial Speaker. adhesion durability Sample 1 85% A A A 10 points 10 points Sample 2 65 B A - 5% or less mass reduction by means of 10 min ultrasound how to start adhesion Sample 3 90 B B A 10 10 Sample 4 - B A A 10 10 Sample 5 90 A A A 10 10 Sample 6 - B A A 10 10 Sample 7 - B A A 10 10 Sample 8 95 B B A 10 10 Sample 9 - A A A *1 *1 Sample 10 - A A A *1 *1 Sample 11 - B A A *1 *1 Sample 12 - B A A *1 *1 Sample 13 - A A A 10 10 Sample 14 - B A A 10 10 Sample 15 - A A A 10 10 Sample 16 - B A B 8th 8th Sample 17 - B A A 8th 8th Sample 18 - A A A 10 10 Sample 19 - A A A 10 10

• * 1: Since the underlying grain band method could not be used, the surface of the adhesive tape was observed, but no adhesion of the photocatalyst layer was recognized.

Claims (18)

A photocatalyst-carrying structure comprising: a photocatalyst layer, an adhesion layer and a substrate, characterized in that the adhesion layer is provided between the photocatalyst layer and the substrate and made of a silicon-modified resin containing 2 to 60% by mass of silicon Containing from 5 to 40% by weight of a colloidal silica-containing resin, or from 3 to 60% by weight of a polysiloxane-containing resin, the polysiloxane being a polycondensation product of a compound represented by formula (1): SiCln ₁ (OH) n ₂ R ¹ n ₃ (OR ² ) n ₄ (1), (wherein R ^{1 is} an alkyl group having 1-8 carbon atoms and is optionally substituted with an amino group, a carboxyl group or a chlorine atom, R ^{2 is} an alkyl group having 1-8 carbon atoms or an alkoxy-substituted alkyl group having 1-8 carbon atoms, n _{1 is} an integer of 0 to 2, n ₂ and n _{3 are} each independently an integer of 0 to 3, n _{4 is} an integer of 2 to 4, and n ₁ + n ₂ + n ₃ + n ₄ = 4) ; and wherein the photocatalyst layer is made of a photocatalyst particle complex containing 25 to 95% by mass of either a metal oxide gel or a metal hydroxide gel and 5 to 75% by mass of a photocatalyst, wherein the metal oxide gel or metal hydroxide -Gel at least one of the group of silicon, aluminum, titanium, zirconium, magnesium, niobium, tan talc, tungsten and tin selected metal, and wherein the photocatalyst is in the form of a powder, a sol or a solution. Photocatalyst-carrying structure according to claim 1, characterized in that the used for the adhesion layer, with Silicon-modified resin is an acrylic-silicon resin. Photocatalyst-carrying structure according to claim 1 or claim 2, characterized in that the adhesion layer is composed of the polysiloxane-containing resin, and the Polysiloxane either from a hydrolyzed product of at least a C1-C5 alkoxy group-containing silicon alkoxide or from a made by the hydrolyzed product prepared compound is. Photocatalyst-carrying structure according to one of claims 1 to 3, characterized in that the adhesion layer of a polysiloxane containing silicon-modified resin. Photocatalyst-carrying structure according to one of claims 1 to 4, characterized in that the adhesion layer from the colloidal silica containing resin is made and the diameter of the particles colloidal silica 10 nm or less. Photocatalyst-carrying structure according to one of claims 1 to 5, characterized in that the adhesion layer of a colloidal Silicon-containing, silicon-modified resin is made. Photocatalyst-carrying structure according to one of claims 1 to 6, characterized in that the metal oxide gel or metal hydroxide gel contained in the photocatalyst layer is a porous gel and that its specific surface after drying at 150 ° C 100 m ² / g or more. Photocatalyst-carrying structure according to one of claims 1 to 7, characterized in that the photocatalyst layer a photocatalyst complex is made up of at least two types of metal oxide gel or metal hydroxide gel and a photocatalyst is composed, the adhesion properties of the complex after immersion in boiling water, which has an electrical conductivity of 200 μS / cm at 20 ° C having an evaluation point of 6 or higher according to a Cross cut scotch tape test according to JIS K5400. A photocatalyst-carrying structure according to claim 8, characterized in that the photocatalyst layer is composed of a photocatalyst complex comprising a porous oxide gel or hydroxide gel of one or more of the group of aluminum, titanium, zirconium, niobium and Silicon is selected metals, and has a specific surface area after drying at 150 ° C of 50 m ² / g. Photocatalyst-carrying structure according to one of claims 1 to 9, characterized in that the photocatalyst layer from a photocatalyst complex composed of either a silicon-modified Resin or a silane compound in an amount of 10 to 50% by weight, either a metal oxide gel or a metal hydroxide gel in one Amount of 15 to 85% by weight based on solid constituents, and a photocatalyst in an amount of 5 to 75% by mass contains wherein the photocatalyst complex has an adhesion property with evaluation point 6 or higher represented by the criterion according to the cross-cut scotch tape test according to JIS K5400 after dipping for 15 minutes. in boiling water, which has an electrical conductivity of 200 μS / cm at 20 ° C having. Photocatalyst-carrying structure according to claim 10, characterized in that in the photocatalyst layer contained silicon-modified resin or in the photocatalyst layer contained silane compound, an acrylic-silicon resin, an epoxy-silicon resin or a silane coupler. Photocatalyst-carrying structure according to one of claims 1 to 11, characterized in that the thickness of the adhesion layer 0.1 μm or is more. Photocatalyst-carrying structure according to one of claims 1 to 12, characterized in that the thickness of the photocatalyst layer 0.1 μm to 5 microns. A method of forming a photocatalyst-carrying structure, wherein an adhesion layer is formed on a substrate and a photocatalyst layer is formed on the adhesion layer characterized in that the adhesion layer is formed from a solid constituent mixture consisting of 1 to 50% by mass of a resin, the resin being selected from the group consisting of a silicon modified, 2-60% by mass silicon containing resin 3-60% by weight of polysiloxane-containing resin and a 5-40% by weight of a colloidal silica-containing resin is selected, wherein the photocatalyst layer is formed from a mixture comprising 0.001-5% by weight of a silicon compound, 0.1-30% by weight a solid-based metal oxide sol and / or metal hydroxide sol; and 0.1-30% by weight of a solid-based photocatalyst powder and / or sol, wherein the silicon compound is an alkoxysilane compound which is represented by the following formula (2): SiR ³ n ₅ (OR ⁴ ) ₄ -n ₅ (2) (wherein R ^{3 is} an alkyl group having 1-8 carbon atoms optionally substituted with an amino group, a carboxyl group or a chlorine atom, R ^{4 is} a 1-8 carbon atoms or an alkoxy-substituted alkyl group having 1-8 carbon atoms, n is ₅ 0, 1, 2 or 3), or at least one hydrolyzed product thereof, wherein the metal oxide gel or metal hydroxide gel is at least one selected from the group of silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten and tin Metal has. Method according to claim 14, characterized in that that the resin contained in the mixture for forming the adhesive layer the polysiloxane-containing resin and the polysiloxane is a hydrolyzed product of alkoxysilane having a 1-5 carbon atom alkoxy group or another made from said hydrolyzed product Connection is. Method according to claim 14, characterized in that that the resin contained in the mixture for forming the adhesive layer the colloidal silica containing resin, wherein the diameter of the colloidal silica is 10 nm or less. Method according to claim 14, characterized in that that the resin contained in the mixture for forming the adhesive layer is a silicon-modified, polysiloxane-containing resin. Method according to claim 14, characterized in that that the resin contained in the mixture for forming the adhesive layer a silicon-modified, colloidal silica exhibiting Resin is.