JP2003236979A - Method for manufacturing photocatalyst film and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a photocatalyst film with a photocatalyst layer which can stably and strongly provide a photocatalyst on the surface of a base material for a long time regardless of kind of the base material and a molded article thereof. <P>SOLUTION: The photocatalyst film has the photocatalyst layer characterized by forming an inorganic protective layer and the photocatalyst layer on a transparent base material film in this order and photocatalyst particles in the photocatalyst layer being dispersed and fixed on the surface of the inorganic protective layer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a photocatalyst film and a molded article, and more particularly to a method for producing a photocatalyst film and a molded article having a photocatalyst layer without using a binder.

[0002]

2. Description of the Related Art A photocatalyst represented by titanium oxide produces active oxygen by irradiation with near-ultraviolet light in the presence of oxygen and water, which produces odorous substances and pollutants in the air. Since it decomposes, etc., it exhibits antifouling and antibacterial effects on the surface of an object. Since the photocatalyst is usually present in the form of powder, it is necessary to fix the photocatalyst on the object surface using a binder or the like in order to exert the above-mentioned action on the object surface. However, the action of the photocatalyst decomposes the binder itself, and the photocatalyst cannot be fixed for a long period of time.

On the other hand, for example, Japanese Patent Laid-Open No. 5-253
No. 544 describes a method in which a glaze is applied to the tile surface, a titanium oxide sol is sprayed on the tile surface, and then the photocatalyst particles are fixed in an exposed state on the surface by firing at a high temperature. . But with this method,
The substrate to which the photocatalyst is applied is limited to those that can withstand baking at a high temperature. Under such circumstances, there is a demand for a method capable of uniformly fixing the photocatalyst to any base material and to a surface having a three-dimensional curved surface or fine irregularities. The present invention has been made in view of the above problems, and a method for producing a photocatalyst film and a molded article capable of imparting a photocatalyst to a substrate surface stably and firmly for a long period of time regardless of the type of the substrate. The purpose is to provide.

[0004]

According to the present invention, an inorganic protective layer and a photocatalyst layer are formed in this order on a transparent substrate film, and the photocatalyst particles in the photocatalyst layer are the surface of the inorganic protective layer. Provided is a photocatalyst film having a photocatalyst layer which is dispersed and fixed on a substrate. Further, according to the present invention,
A molded product in which the photocatalytic film having an adhesive layer provided on the surface opposite to the inorganic protective layer on the transparent substrate film is sandwiched in an injection molding die, and a molten resin is injected to the side provided with the adhesive layer. A manufacturing method is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The photocatalyst film of the present invention is mainly constituted by laminating an inorganic protective layer and a photocatalyst layer in this order on a transparent substrate film. The transparent substrate film that can be used in the present invention is not particularly limited as long as it is a transparent film, and a film made of a plastic that can be deformed or bent is suitable.
Specifically, polyester, cellulose acetate, polypropylene, polyethylene, polyamide, polyimide, polyether sulfone, polysulfone, polyvinyl acetal, polyether ketone, polyvinyl chloride, polyvinylidene chloride, polymethyl acrylate, polymethyl methacrylate, polycarbonate. And stretched or unstretched transparent plastic films such as polyurethane. The thickness of the base sheet is not particularly limited,
For example, it is about 3 to 500 μm.

The inorganic protective layer of the present invention is included in the photocatalyst layer.
The transferred photocatalyst protects the transferred material from deterioration.
A layer having a skeleton of an element other than carbon.
It can be formed from a body, metal or inorganic metal oxide, etc.
Wear. For example, the polymer has a siloxane bond.
Examples include polysiloxanes and organopolysiloxanes.
Examples include xanthane and metaloxysiloxane. in
Also, organopolysiloxane is preferable. In addition, Olga
In the case of the nonsiloxane, the organic substituent is lower (C ₁~ C₃)
Examples thereof include alkyl, vinyl and phenyl.

The inorganic protective layer of organopolysiloxane can be obtained by applying a silicone oligomer solution obtained by hydrolyzing and polycondensing an alkoxysilane onto a substrate film and then drying or heat-treating the silicone oligomer solution. It can be formed by applying a solution mixed with a curing agent onto a base film, drying and curing.

The alkoxysilane for forming the inorganic protective layer is not particularly limited, and examples thereof include tetraalkoxysilanes such as tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS).
Methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), ethyltrimethoxysilane (ETMS), phenyltriethoxysilane (PhTE)
S), vinyltriethoxysilane (VTES), n-propyltrimethoxysilane (n-PrTMS), trialkoxysilane such as isopropyltrimethoxysilane (iso-PrTMS), dimethyldiethoxysilane (D)
MDE), diphenyldimethoxysilane (DPhD
M), dialkoxysilane such as methylethyldimethoxysilane (MEDM), trimethylmethoxysilane (T
Examples thereof include monoalkoxysilanes such as MMS). These can be used alone or in combination, but it is preferable to use trialkoxysilane in an amount of about 85% by weight or more, preferably about 87% by weight or more, and further about 90% by weight or more.

The alkoxysilane and water have a molar ratio of, for example, about 1: 1.4 to 4.0, preferably 1: 1.5 to.
It is preferable to mix them so as to be about 2.5 and to carry out hydrolysis and polycondensation reaction. In addition, alkoxysilane is
As a hydrolysis catalyst, a metal chelate compound or an acid may be mixed.

The metal chelate compound is, for example, 1,3-
A metal chelate compound having a β-diketone having a dioxopropylene chain or a macrocyclic polyether as a ligand can be preferably used. Specifically, tris (acetylacetonato) aluminum (III), tris (ethylacetoacetato) aluminum (III), tris (diethylmalonato) aluminum (III), bis (acetylacetonato) copper (II), Tetrakis (acetylacetonato) zirconium (IV), tris (acetylacetonato) chromium (III),
Tris (acetylacetonato) cobalt (III), titanium (II) oxide acetylacetonate [(CH ₃ COCHCOCH
₃ ) ₂ TiO] and other β-diketone metal chelates, rare earth metal β-diketone metal chelates, 18-crown-6-potassium chelate compound salts, 12-crown-4
-Macrocyclic polyether compound metal chelates such as lithium chelate compound salt and 15-crown-5 sodium chelate compound salt. The amount of the metal chelate compound added can be appropriately adjusted according to the catalytic effect, and is usually preferably about 0.001 to 5 mol%, particularly preferably about 0.005 to 1 mol% based on the alkoxysilane.

Examples of the acid include inorganic acids such as nitric acid and hydrochloric acid used in ordinary sol-gel reaction, acetic acid and carboxylic acid esters (eg, methyl acetate, ethyl acetate, ethyl trichloroacetate, ethyl formate, ethyl chloroformate). , Ethyl pyruvate, etc., nitrates (eg, methyl nitrate, ethyl nitrate, etc.), dialkyl sulfates (eg, dimethyl sulfate, diethyl sulfate, etc.), δ-lactones (eg, coumarin, δ-valerolactone, etc.), acid anhydrides Compounds (eg acetic anhydride, propionic anhydride, etc.), acid chlorides (eg, acetyl chloride, chloroacetyl chloride, etc.)
And organic acids such as sulfonyl compounds (eg, methanesulfonyl chloride, benzenesulfonyl chloride, etc.) and the like. The amount of the acid added can be appropriately adjusted according to the catalytic effect, and usually about 0.0001 to 5 mol% relative to the alkoxysilane.

Examples of the curing agent include partial chelate compounds of metal alkoxides such as titanium, zirconium and aluminum, organic tin compounds, amine silane coupling agents, and ammonium salts of carboxylic acids. The silicone oligomer solution is, for example, a flow method, a roll method, a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a dip coating method, a spin coating method, a bar coating method, an extrusion coating method, a screen coating method, a reverse coating method. The inorganic protective layer can be formed by a method known per se such as a roll coating method, a microgravure coating method, and a flexo coating method. The thickness of the inorganic protective layer is, for example, about 1 to 50 μm. Further, in order to increase the hardness of the inorganic protective layer, heat treatment may be carried out in a temperature range of room temperature to 200 ° C. after coating and drying. The inorganic protective layer in the present invention is disclosed in
It includes all organopolysiloxane films that can be formed by the method described in this publication using the coating composition described in 01-49182.

Further, the inorganic protective layer in the present invention may contain a filler as a light scatterer in order to make the photocatalyst film have a low reflection and a matte tone. As the filler, an organic or inorganic filler can be used. Examples of the organic filler include synthetic resin fine particles (low molecular weight polyethylene, low molecular weight polypropylene, acrylic resin, nylon resin, styrene resin beads, etc.) and various formalin resins. Examples of the inorganic fillers include silica, alumina, zirconia, titania, zeolite, kaolin, clay, talc, calcium tansan calcium, barium sulfate, magnesium hydroxide, calcium carbonate, calcium phosphate, titanium dioxide, and powdered glass. These fillers are
For example, the average particle size is about 0.5 to 100 μm, preferably about 0.5 to 10 μm, and more preferably about 1 to 5 μm. The filler is about 1 to 90% by weight, 1 to 50% by weight, and 5 to 40% with respect to the inorganic protective layer.
It is suitable to contain it in about wt%. Further, the inorganic protective layer can be imparted with various functions to the film itself by adding various additives such as a dye, an ultraviolet absorber, an antioxidant and a conductive filler.

The photocatalyst layer in the present invention comprises TiO ₂ , Z
nO, SnO ₂ , SrTiO ₃ , WO ₃ , Bi ₂ O ₃ and F
It is formed by one or more photocatalysts selected from the group consisting of e ₂ O _{3 and the} like. Among them, anatase type titanium oxide is preferable from the viewpoints of photocatalytic ability and chemical durability. The photocatalyst layer can be formed using a dispersion liquid in which a particulate photocatalyst is dispersed in a suitable dispersion medium, a dispersion liquid in which a sol or a metal alkoxide serving as a photocatalyst precursor is dispersed in a suitable dispersion medium, and the like.

The dispersion medium is not particularly limited, and various organic solvents can be used, but it is preferable to use an organic solvent capable of swelling and softening the inorganic protective layer, or to contain it in the dispersion medium. . Examples of the organic solvent capable of swelling and softening the inorganic protective layer include volatile oxygen-containing solvents having a high affinity with the inorganic protective layer and a boiling point of about 200 ° C. or lower, preferably about 170 ° C. or lower. Specifically, alcohols, ethers, ketones, and carboxylic acid esters are particularly preferable. Examples of alcohols include methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, and the like, and ether groups such as 2-methoxyethanol and 2-butoxyethanol. Things are also included. Examples of ethers include diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like. Examples of the ketones include acetone, methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl isobutyl ketone, acetylacetone and the like. Examples of the carboxylic acid esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl acetoacetate, diethyl malonate and the like. These may be used alone or in combination of two or more. The organic solvent may contain an aromatic hydrocarbon such as toluene or xylene. The photocatalyst dispersion liquid contains the photocatalyst in an amount of about 0.05 to 10% by weight, preferably about 1 to 5% by weight, and more preferably about 1 to 2% by weight. Such photocatalyst dispersion liquid, on the inorganic protective layer,
For example, a photocatalyst layer is formed by applying by a known method such as a roll coating method, a spray coating method, a lip coating method, a dip coating method, a spin coating method, a bar coating method, a pressing screen coating method and the like, and drying. can do.

The photocatalyst dispersion may contain a dispersant. Examples of the dispersant include alkylbenzene sulfonate, fatty acid salt, dialkylsulfosuccinate, hydroxyalkyl sulfonate, alkyl sulfonate, polyoxyethylene sulfonate, alkyl sulfate ester salt, alkyl phosphate ester salt, and polyphosphate salt. Examples thereof include oxyethylene alkyl allyl ether sulfate ester salt, alkyl amine salt, tetraalkyl ammonium salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, oxyethylene-oxypropylene copolymer, polyhydric alcohol fatty acid ester and the like. The amount of the dispersant is 0.1 to the entire photocatalyst dispersion liquid.
It is about 20% by weight, preferably about 1 to 10% by weight.

The surface of the photocatalyst may be modified with a chelating agent. As a result, the photocatalyst can be made hydrophobic, aggregation of the photocatalyst due to moisture can be prevented, and a uniform photocatalyst layer can be formed. For chelation, a photocatalyst modified in advance with a chelating agent may be used, or a mixture obtained by adding a chelating agent together with an organic solvent may be used. As the chelating agent, for example,
It is preferable that the complex formation constant be larger than the metal such as Ti, Zn, W, St, and Sn contained in the photocatalyst, and any of generally known chelating agents can be used.

As described above, the photocatalyst layer of the present invention does not substantially contain a binder and a matrix, in particular, what is called an organic binder and a matrix. Here, substantially containing no binder or the like means that the inorganic protective layer does not contain an amount of binder sufficient to firmly hold the photocatalyst particles, and the binder and matrix here. For example, urethane-based, ester-based, acrylic-based, polyvinyl alcohol-based, vinyl acetate-based, silicone-based binders and alkyl silicates are meant. That is, preferably, the photocatalyst particles themselves are fixed to the surface of the inorganic protective layer opposite to the base sheet to form the photocatalyst layer, or the photocatalyst is attached to the surface of the inorganic protective layer opposite to the base sheet. Or the photocatalyst layer is formed by the fact that only a part of the photocatalyst is embedded in the inorganic protective layer.

In the photocatalyst film of the present invention, an antistatic layer, a peeling layer, an anchor layer, a pattern layer, a vapor deposition layer, an antireflection layer, a protective layer, and It may be formed of one kind or a combination of two or more kinds such as an adhesive layer. These layers can be formed by a known method using a material known in the art. Particularly, as the adhesive layer, for example, acrylic resin, chlorinated olefin resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, chlorinated rubber resin, cyclized rubber resin, polyamide resin, It can be formed of malon-indene resin, ethylene-vinyl acetate copolymer resin, polyester resin, urethane resin, styrene resin, or the like. The thickness of the adhesive layer is, for example, about 0.1 to 10 μm. The anchor layer means a kind of adhesive layer, and examples thereof include an adhesive layer made of titanate-based, isocyanate-based, polyethyleneimine-based, or the like. The thickness of the anchor layer is, for example, about 0.1 to 5 μm. The picture layer means a layer in which so-called pictures such as letters and patterns are formed by various printing inks containing known coloring materials such as pigments and dyes. The pattern layer does not need to be uniformly formed on the transparent substrate film, and can be formed with a thickness in the range of, for example, 0 to 50 μm, depending on the pattern, color and the like.

Further, according to the method for producing a molded article of the present invention, an adhesive layer is formed on the transparent substrate film on the side opposite to the side on which the photocatalyst layer is formed, and this film is placed in an injection molding die. It can be realized by sandwiching between the two and injecting a molten resin to the side where the adhesive layer is provided. here,
Examples of the adhesive layer include the same ones as described above. The thickness of the adhesive layer is, for example, about 0.1 to 5 μm. The adhesive layer can be formed by a method known per se.

The film of the present invention is, for example, a word processor,
Various displays such as computers, televisions, display panels, mobile phones, touch panels, etc .; surfaces of polarizing plates used for liquid crystal display devices, etc .; optical lenses such as sunglasses made of transparent plastics, prescription glasses lenses, camera viewfinder lenses, etc .; Display of various instruments;
Window glass of automobiles, trains, etc .; various electric appliances such as rice cookers, lighting fixtures, lighting covers, etc .; road signs, traffic lights, streets, guardrails, highway noise barriers, etc .; Various building materials such as ceilings, inner walls, walls of bathrooms, pools, etc .; signs; equipment for operating rooms, aseptic rooms and food processing rooms, medical equipment, cooking equipment, etc .; automobile parts such as tail lamp covers, foil caps, door mirrors, cups, etc. Jug,
Examples include household products such as cupboards and air purifiers. It should be noted that these molded products can exhibit the same effect as the resin even if they are made of a material other than resin, such as glass, wood, metal, stone, concrete, or ceramic.

As the molten resin, the material is not particularly limited as long as it can form the above products and the like, and examples thereof include acrylic resin and styrene resin (AB
S, AS, polyphenylene oxide / styrene copolymers, etc.), polyolefin resins (polyethylene, polypropylene, etc.), polycarbonate resins, etc. in molten state can be used. Any injection mold can be used as long as it is one that is normally used when manufacturing a resin molded product. The photocatalyst film of the present invention and the method for producing a molded product using the same will be described below.

Example 1 (Preparation of photocatalyst coating composition) 60 parts by weight of ethyl acetate, 10 parts by weight of toluene, 10 parts by weight of isopropyl alcohol and 20 parts by weight of t-butyl alcohol were mixed, and this mixture was mixed. 1 part by weight of acetylacetone and 5 parts by weight of alkanoanatase sol (Taika Corporation)
Manufactured by TKS-251) was added and mixed to prepare a photocatalyst coating composition.

(Preparation of Silicone Oligomer Solution) Methyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-1)
890) 100 parts by weight, tris (acetylacetonato) aluminum (III) (Dojindo Laboratories Co., Ltd.)
02 parts by weight were added. 18 parts by weight of distilled water was further added to this solution at 50 ° C. for reaction for 1 day to obtain a transparent silicone oligomer solution A.

(Preparation of curing agent) 100 parts by weight of titanium tetra-n-butoxide (Kanto Chemical Co., Inc.) were mixed with 29.4 parts by weight of acetylacetone, 9 parts by weight of acetic acid and 170 parts by weight of ethylene glycol monomethyl ether, A curing agent B was obtained.

(Preparation of coating liquid for forming organopolysiloxane layer) 100 parts by weight of the silicone oligomer solution A,
5 parts by weight of the curing agent B and 2 parts by weight of isopropyl alcohol were mixed to prepare an organopolysiloxane layer forming coating liquid.

(Production of Photocatalyst Film) A coating solution for forming an organopolysiloxane layer was applied to a polyethylene terephthalate film (Unitika UT-S) having a thickness of 38 μm and subjected to a single-sided corona treatment, and dried at 170 ° C. for 1 minute. Then, an inorganic protective layer having a thickness of 2.3 μm was formed. Furthermore, the photocatalyst coating composition was applied onto the inorganic protective layer and dried at 170 ° C. for 1 minute to give a dry film thickness of 0.03 μm.
m photocatalyst layer was formed to obtain the photocatalyst film of the present invention.

Comparative Example (Production of Photocatalyst Film) A coating solution for forming an organopolysiloxane layer was applied to a polyethylene terephthalate film (Unitika UT-S) having a thickness of 38 μm and having one side corona treated, and dried at 170 ° C. for 1 minute. Then, the film thickness 1.7
An inorganic protective layer having a thickness of μm was formed. On the obtained base sheet, a binder-containing photocatalyst coating composition (90 parts by weight of isopropyl alcohol, 5 parts by weight of organoanatase sol (TKS-251 manufactured by Teika Co., Ltd.),
Part by weight of silicone resin mixture), 170 ℃
Was dried for 1 minute to form a photocatalyst layer having a dry film thickness of 0.08 μm to obtain a photocatalyst film.

Test Example Regarding the photocatalyst films obtained in Examples and Comparative Examples,
A hydrophilization test was conducted by outdoor exposure to sunlight. First,
The photocatalyst film was exposed outdoors for a predetermined time, and then the photocatalyst film was held horizontally. After dropping enough water to sufficiently wet the entire transfer surface, the photocatalyst film was placed vertically, and the water was poured off at once. Then, the photocatalyst film is allowed to stand for 10 seconds and then returned to the horizontal position. The value of (wet area / total area of photocatalyst film) × 100 when returned to the horizontal direction was calculated as the hydrophilicity ratio. The results are shown in the table below.

[0030]

[Table 1]

Example 2 A photocatalytic film was prepared in the same manner as in Example 1 except that various silica powders were added in various amounts to a coating liquid for forming an organopolysiloxane layer in order to obtain a photocatalytic film having a low reflectance. . The silica powder used was silica powder A.
(Average particle size 0.04 μm, specific surface area 200 m ² / g),
Silica powder B (average particle size 2 μm, specific surface area 190 m ² /
g), silica powder C (average particle size 3.5 μm, specific surface area 3)
00 m ² / g), silica powder D (average particle size 1.55 μ)
m, specific surface area 4.48 m ² / g). 3 parts of silica powder to the coating solution for forming the organopolysiloxane layer
The glossiness of the photocatalyst film obtained by mixing by weight% is shown below.

[0032]

[Table 2] Moreover, the glossiness of the photocatalyst film obtained by mixing 3 to 9% by weight of the silica powder C with the coating liquid for forming the organopolysiloxane layer is shown below.

[0033]

[Table 3]

Example 3 In the photocatalyst film obtained in Example 1, an adhesive layer made of acrylic resin was formed with a thickness of about 1 μm on the transparent base film on the side opposite to the side on which the photocatalyst layer was formed. did. Insert this film in an injection molding die,
An acrylic resin (Acrypet VH, manufactured by Mitsubishi Rayon Co., Ltd.) melted in a temperature range of about 240 ° C. was poured into the mold from the adhesive layer side and allowed to cool. Thereby, a door mirror having a photocatalyst layer formed on the surface thereof was obtained. The obtained molded product had a hydrophilicity improved by a photocatalyst.

[0035]

According to the present invention, it is possible to provide a photocatalyst film having a high photocatalyst content and being firmly fixed, whereby the photocatalyst is firmly fixed to the surface and the degree of exposure thereof. It is possible to provide a product having a large photocatalytic property and capable of sufficiently improving the photocatalytic activity. Moreover, since the inorganic protective layer is disposed on the product side, it is possible to prevent the product itself from being deteriorated by the photocatalyst, and the photocatalyst is formed by attaching the photocatalyst to the inorganic protective layer. It is possible to provide a photocatalyst film capable of providing a photocatalyst layer capable of stably obtaining a photocatalyst effect over a long period of time while avoiding deterioration of a binder and the like. Further, according to the molded product of the present invention, the photocatalyst layer can be easily and strongly applied to the surface of the molded product, the manufacturing process can be simplified and the manufacturing cost can be reduced. The price can be reduced while increasing the value.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobuo Yano             2-21 Hamamatsubara-cho, Nishinomiya-shi, Hyogo Japan Yamamura Glass             Child Co., Ltd. (72) Inventor Akio Konishi             2-21 Hamamatsubara-cho, Nishinomiya-shi, Hyogo Japan Yamamura Glass             Child Co., Ltd. (72) Inventor Hajime Wakabayashi             2-21 Hamamatsubara-cho, Nishinomiya-shi, Hyogo Japan Yamamura Glass             Child Co., Ltd. (72) Inventor Hironori Miyake             87-5 Hiragawa Hirota, Joyo City, Kyoto Prefecture Nakajima Industrial Co., Ltd.             Inside the company (72) Inventor Yuzo Nakamura             87-5 Hiragawa Hirota, Joyo City, Kyoto Prefecture Nakajima Industrial Co., Ltd.             Inside the company F term (reference) 4F100 AA00B AA17C AA21C AA25C                       AA28C AK42 AK79B AR00A                       AR00C BA03 BA07 DE00B                       DE01C EH462 EJ862 GB07                       JL08C JN01A                 4F206 AD08 AD20 AG03 JA07 JB13                 4G069 AA03 AA08 BA04A BA04B                       BA22A BA22B BA48A BB04A                       BB06A BC12A BC22A BC25A                       BC35A BC50A BC60A BC66A                       BE32A BE32B CA01 CA11                       CA17 EA08 EB15Y ED02                       EE01 FA03 FB23 FB57

Claims (9)

[Claims] 1. An inorganic protective layer and a photocatalyst layer are formed in this order on a transparent substrate film, and the photocatalyst particles in the photocatalyst layer are dispersed and fixed on the surface of the inorganic protective layer. A photocatalyst film having a characteristic photocatalyst layer. 2. The photocatalyst film according to claim 1, wherein the photocatalyst particles of the photocatalyst layer are present in a state of being dispersed and attached to the surface of the inorganic protective layer or in a state of only a part thereof being embedded. 3. A photocatalyst layer-forming coating solution containing an organic solvent capable of swelling and softening the inorganic protective layer after forming the inorganic protective layer on the transparent substrate film. The photocatalyst film according to claim 1 or 2, wherein the photocatalyst particles are dispersed and fixed on the surface of the inorganic protective layer by coating and drying. 4. The photocatalyst film according to claim 1, wherein the inorganic protective layer is formed of organopolysiloxane. 5. The photocatalyst film according to claim 4, wherein the organopolysiloxane is produced from trialkoxysilane. 6. The photocatalyst layer comprises TiO ₂ , ZnO, Sn
The photocatalyst film according to claim 1, which is formed by one or more photocatalysts selected from the group consisting of O ₂ , SrTiO ₃ , WO ₃ , Bi ₂ O ₃ and Fe ₂ O _3. . 7. The photocatalyst film according to claim 1, wherein the photocatalyst layer contains substantially no binder. 8. The photocatalyst film according to claim 1, wherein the inorganic protective layer contains a filler. 9. The photocatalyst film according to claim 1, wherein an adhesive layer is provided on the surface of the transparent base film opposite to the inorganic protective layer, and the photocatalyst film is sandwiched in an injection molding die. A method for manufacturing a molded article, which comprises injecting a molten resin to a side provided with an adhesive layer.