JP2003236978A - Method for manufacturing transfer foil and molded article having photo-catalyst layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a transfer foil and a molded article having a photo-catalyst layer which can stably and strongly provide a photo-catalyst on the surface of a base material for a long time regardless of kind of the base material. <P>SOLUTION: The transfer foil has the photo-catalyst layer characterized by forming the photo-catalyst layer, an inorganic protective layer and an adhesive layer on a base material sheet with release characteristics in this order and photo-catalyst particles in the photo-catalyst 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]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer foil having a photocatalyst layer and a method for producing a molded article, and more particularly to a transfer foil having a photocatalyst layer for forming a photocatalyst layer substantially without using a binder. The present invention relates to a method for manufacturing a molded product.

[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 and firmly 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, regardless of the type of substrate, for a long period of time,
An object of the present invention is to provide a transfer foil having a photocatalyst layer capable of stably and firmly applying a photocatalyst to the surface of a substrate, and a method for producing a molded product.

[0004]

According to the present invention, a photocatalyst layer, an inorganic protective layer, and an adhesive layer are formed in this order on a base sheet having releasability, and the photocatalyst particles in the photocatalyst layer are formed. Provided is a transfer foil having a photocatalyst layer which is dispersed and fixed on the surface of an inorganic protective layer. Further, according to the present invention, the transfer foil is sandwiched in an injection molding die, and a molten resin is injected to the adhesive layer side to form a resin molded product, and at the same time, a photocatalyst layer is formed on the surface of the resin molded product. Or the adhesive layer side of the transfer foil is laminated on the resin molded product, and the photocatalyst layer is adhered to the surface of the resin molded product by applying heat pressure from the back surface of the base sheet, and then has releasability. Provided is a method for producing a molded article, which comprises peeling a base sheet.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The transfer foil of the present invention is mainly composed of a photocatalyst layer, an inorganic protective layer, and an adhesive layer formed in this order on the surface of a base sheet. In such a transfer foil, after the photocatalyst layer is transferred to the transfer target, the base sheet is peeled off from the transfer target. The base sheet used for the transfer foil of the present invention may be formed of any material, and a sheet formed of 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,
Examples include stretched or unstretched transparent plastic films of polyurethane and the like. The thickness of the base sheet is not particularly limited and may be, for example, about 3 to 500 μm.

[0006] The substrate sheet has a releasing property such that the photocatalyst layer does not remain on the substrate sheet side at the time of peeling the photocatalyst layer described later from the substrate sheet, or it is necessary to have a releasing layer. . For example, the base sheet itself has releasability by being formed by adding a release agent such as waxes, salts or esters of higher fatty acids, fluorinated alkylated compounds, polyvinyl alcohol, and low molecular weight polyethylene. Or on the substrate sheet,
A release layer may be formed between the photocatalyst layer and the photocatalyst layer.

The release layer should be formed of, for example, a melamine resin, an epoxy resin, an epoxy melamine resin, an aminoalkyd resin, a silicon resin, a fluorine resin, an olefin resin, or a composite resin thereof. You can The release layer is, for example, 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 roll coating method, a micro gravure method. The above material can be formed by coating the above material on the base sheet and drying by a method known per se such as a coating method and a flexo coating method. In this case, the thickness of the release layer is, for example, about 0.1 to 10 μm.

The release layer can transfer irregularities to the surface of the transfer foil by imparting irregularities to the surface,
As a result, the transfer target on which the transfer foil is transferred can have low reflection. The unevenness formed on the release layer is, for example,
It can be provided by including a filler in the release layer. As the filler, an organic or inorganic filler can be used. As the organic filler, for example, synthetic resin fine particles (low molecular weight polyethylene,
Examples thereof include low molecular weight polypropylene, acrylic resin, nylon resin, styrene resin beads) 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 have, for example, an average particle size of 0.5 to 100.
The thickness is about μm, preferably about 0.5 to 10 μm, and more preferably about 1 to 5 μm. The filler is appropriately contained in the release layer in an amount of about 1 to 90% by weight, 1 to 50% by weight, and 5 to 40% by weight.

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 an organic solvent which can swell and soften the inorganic protective layer described later, or
It is preferably contained in the dispersion medium. The organic solvent capable of swelling and softening the inorganic protective layer has a high affinity with the inorganic protective layer and has a boiling point of about 200 ° C. or less, preferably 170.
A volatile oxygen-containing solvent having a temperature of about 0 ° C. or lower can be used. 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 2
Those having an ether group such as -methoxyethanol and 2-butoxyethanol 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 a photocatalyst dispersion liquid is formed on a base sheet 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 and a pressing screen coating method. A photocatalyst layer can be formed by applying and drying.

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, those modified with a chelating agent in advance may be used, or a composition obtained by adding a chelating agent together with an organic solvent may be used. As the chelating agent, for example, those having a complex formation constant larger than those of metals such as Ti, Zn, W, St, and Sn contained in the photocatalyst are preferable, 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 on the side of the base sheet to form the photocatalyst layer, or the photocatalyst is attached to the surface of the inorganic protective layer on the side of the base sheet, or The photocatalyst layer is constituted by the fact that only a part thereof is embedded in the inorganic protective layer.

The inorganic protective layer of the present invention is a layer for protecting the transferred material from deterioration by the photocatalyst contained in the photocatalyst layer, and is, for example, a polymer having an element other than carbon as a skeleton, a metal or an inorganic metal. It can be formed of an oxide or the like. Examples of the polymer include those having a siloxane bond, and examples thereof include polysiloxane, organopolysiloxane, and metaloxysiloxane. Of these, organopolysiloxane is preferable. In the case of organosiloxane, the organic substituent is lower (C ₁ -C ₃ ).
Examples thereof include alkyl, vinyl and phenyl. The inorganic protective layer is preferably formed by applying a coating liquid for forming an inorganic protective layer containing an organic solvent capable of swelling and softening the inorganic protective layer. The organic solvent capable of swelling and softening the inorganic protective layer is as described above.

The inorganic protective layer of organopolysiloxane is applied on the photocatalyst layer by adding an organic solvent capable of swelling and softening organopolysiloxane to a silicone oligomer solution obtained by hydrolyzing and polycondensing alkoxysilane. By drying or heat treatment, or by coating a solution obtained by mixing a curing agent in a silicone oligomer solution with an organic solvent capable of swelling and softening organopolysiloxane, coating on the above-mentioned photocatalyst layer, drying and curing, It can be fixed by adhering or embedding the photocatalyst itself on the surface.

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 may be used alone or in combination, and above all, trialkoxysilane is used in an amount of about 85% by weight or more, preferably about 87% by weight or more, and 90% by weight or more.
It is preferably used in an amount of about wt% 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, 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 may be coated by various coating methods such as a spray method, a dipping method, a flow method and a roll method.
An inorganic protective layer can be used. The thickness of the inorganic protective layer is, for example, about 1 to 50 μm. In addition, in order to increase the hardness of the inorganic protective layer, heat treatment may be performed 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 JP-A-2
It covers all organopolysiloxane films that can be formed by the method described in this publication using the coating composition described in 001-49182. The inorganic protective layer in the present invention may contain a filler as a light scatterer in the inorganic protective layer in order to make the transfer foil have a low reflection and a matte tone. As the filler, an organic or inorganic filler can be used. As the organic filler, for example, synthetic resin fine particles (low molecular weight polyethylene,
Examples thereof include low molecular weight polypropylene, acrylic resin, nylon resin, styrene resin beads) 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 have, for example, an average particle size of 0.5 to 100.
The thickness is about 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 with respect to the inorganic protective layer, 1 to
It is suitable to contain 50% by weight or 5 to 40% by weight. Further, the inorganic protective layer can also be imparted with various functions to the transfer foil or the transferred material by adding various additives such as dyes, ultraviolet absorbers, antioxidants and conductive fillers. .

The adhesive layer of the transfer foil of the present invention is, for example, an acrylic resin, a chlorinated olefin resin, a vinyl chloride-vinyl acetate copolymer resin, a maleic acid resin, a chlorinated rubber resin, a cyclized rubber resin. , Polyamide resin, coumarone indene resin, ethylene-vinyl acetate copolymer resin,
It can be formed of polyester resin, urethane resin, styrene resin, or the like. The thickness of the adhesive layer is, for example, about 0.1 to 10 μm.

In the transfer foil 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 an inorganic antistatic layer are provided between the inorganic protective layer and the adhesive layer. 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. Furthermore, according to the method for producing a molded product of the present invention, the transfer foil is sandwiched in an injection molding die and a molten resin is injected to the adhesive layer side to form a resin molded product. Thereby, the photocatalyst layer can be adhered to the surface of the molded product, and then the photocatalyst layer can be provided on the surface of the molded product by peeling the base sheet having releasability.

Here, the molded product is not particularly limited, but for example, various displays such as word processors, computers, televisions, display panels, mobile phones, and touch panels; polarizing plates used in liquid crystal display devices and the like. Surface: Sunglass lenses made of transparent plastics, optical lenses such as 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. Products; Road and traffic related products such as road signs, traffic lights, streets, guardrails, and soundproof walls for expressways; Straps; various building materials such as tiles, ceilings, inner walls, walls such as bathrooms and pools, signs, operating rooms, Equipment for aseptic room and food processing room, medical equipment, cooking utensils, automobile parts such as tail lamp covers, foil caps, door mirrors, etc. -Up, jugs, cupboards, and the like domestic products, etc. of the air cleaner and the like. Note that these molded products are made of materials other than resin, such as glass, wood, metal,
Even when it is made of stone, concrete, ceramic, or the like, it can exhibit the same effect as the resin.

As the molten resin, the material is not particularly limited as long as it can form the above-mentioned products and the like. For example, acrylic resin, 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.

According to another method for producing a molded product of the present invention, the adhesive layer side of the transfer foil is overlaid on the molded product, and the photocatalytic layer is applied to the surface of the molded product by applying heat pressure from the back surface of the base sheet. Can be adhered, and then the base sheet having releasability is peeled off, whereby the photocatalyst layer can be provided on the surface of the molded product. For example, heat pressure can be applied from above the back surface of the base sheet with a silicone rubber roll or the like. In this case, the temperature of the surface of the silicone rubber roll is 15
It is appropriate that the pressure is about 0 to 250 ° C. and the pressure is about 5 to ²⁰ kg / cm ² . The transfer foil of the present invention and a method for manufacturing a molded product using the transfer foil will be specifically 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. Further, 1 part by weight of acetylacetone and 5 parts by weight of organoanatase sol (TKS-251 manufactured by Teika Co., Ltd.) were 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.) was 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.

(Manufacture of Transfer Foil) A urethane-based release layer is applied to one surface of a polyethylene terephthalate film (Toray F-39) having a film thickness of 38 μm by a reverse coating method to have a releasability of a dry film thickness of 1 μm. A base sheet was obtained. The photocatalyst coating composition was applied onto the release layer of the obtained base sheet and dried at 170 ° C. for 1 minute to form a photocatalyst layer having a dry film thickness of 0.03 μm. Next, a coating liquid for forming an organopolysiloxane layer is applied on the photocatalyst layer and dried at 170 ° C. for 1 minute to give a film thickness of 2.3 μm.
The inorganic protective layer of was formed. Further, an acrylic resin adhesive layer was applied on the inorganic protective layer and dried at 170 ° C. for 3 minutes to form an adhesive layer having a dry film thickness of about 1 μm to obtain a transfer foil of the present invention.

Comparative Example (Production of Transfer Foil) A urethane-based release layer was applied on one side of a polyethylene terephthalate film (Toray F-39) having a film thickness of 38 μm by the reverse coating method to obtain a dry film thickness of 1
A base sheet having a releasability of μm was obtained. A binder-containing photocatalytic coating composition (90 parts by weight of isopropyl alcohol, 5 parts by weight) was formed on the release layer of the obtained base sheet.
Parts by weight of organoanatase sol (manufactured by Teika Co., Ltd., T
KS-251), a mixture of 5 parts by weight of silicone resin)
Is applied and dried at 170 ° C. for 1 minute to give a dry film thickness of 0.0
An 8 μm photocatalyst layer was formed. Then, a coating liquid for forming an organopolysiloxane layer is applied onto the photocatalyst layer, and 1
It was dried at 70 ° C. for 1 minute to form an inorganic protective layer having a film thickness of 1.7 μm. Furthermore, an acrylic resin adhesive layer is applied on the inorganic protective layer and dried at 170 ° C. for 30 seconds,
An adhesive layer having a dry film thickness of about 1 μm was formed to obtain a transfer foil.

Test Example By attaching the acrylic resin adhesive layer side of the transfer foils obtained in Examples and Comparative Examples to the surface of an acrylic plate having a thickness of 1 mm, and by thermocompression bonding at 220 ° C. under pressure, Transfer was performed so that the adhesive layer, the inorganic protective layer, and the photocatalyst layer were laminated in this order on the acrylic plate. Then, the base sheet was peeled off to obtain a synthetic resin composite molded body. The obtained synthetic resin composite molded body was subjected to a hydrophilization test by exposure to sunlight outdoors.

First, the composite molding made of synthetic resin is given a predetermined time,
It was exposed outdoors, and then the synthetic resin composite molded body was held horizontally. After dropping a sufficient amount of water to wet the entire transfer surface, the synthetic resin composite molded body was placed vertically, and the water was drained off at once. Then, the synthetic resin composite molding
Let stand for 2 seconds and return to horizontal. Calculate the (wet area / total area with transfer foil) x 100 when returned to the horizontal,
The hydrophilization rate was used. The results are shown in the table below.

[0035]

[Table 1]

Example 2 (Preparation of Synthetic Silica Dispersion) 0.34 parts by weight of synthetic silica (Cycilia 350, Fuji Silysia Chemical Ltd., average particle size 1.8 μm), TCM-01 medium 100 parts by weight (large) Nippon Ink Chemical Co., Ltd.), xylene 50 parts by weight, methyl isobutyl ketone 25 parts by weight and isopropyl alcohol 25 parts by weight were mixed to obtain a synthetic silica dispersion liquid.

(Production of transfer foil) A synthetic silica dispersion liquid was applied to one side of a polyethylene terephthalate film (Toray F-39) having a film thickness of 38 μm by a gravure coater, and 170
After drying at 45 ° C. for 45 seconds, a releasable base sheet having a film thickness of 1 μm was obtained. A photocatalyst layer, an inorganic protective layer and an adhesive layer were formed on the obtained base sheet in the same manner as in Example 1 to obtain a transfer foil. The glossiness of the obtained transfer foil was 101%.

Example 3 The transfer foil obtained in Example 1 was sandwiched between injection-molding molds so that the adhesive layer was on the cavity side, and the mold was heated to 55 ° C.
Heated to. Acrylic resin (made by Mitsubishi Rayon Co., Ltd.) melted at a temperature of about 240 ° C. using the molding simultaneous transfer method.
Acrypet VH) was injected into the mold at a resin pressure of 300 kg / cm ² and allowed to cool. Then, the base sheet was peeled off to obtain a delicator having a transfer layer having a photocatalyst layer transferred to the surface thereof.

Example 4 An acrylic resin (Acrypet V manufactured by Mitsubishi Rayon Co., Ltd.) was injection-molded on the adhesive layer of the transfer foil obtained in Example 1.
The molded product formed in H) was overlapped and heated and pressed from the base sheet side with a roll of silicon rubber having a hardness of 80 degrees to bond the photocatalyst layer to the molded product. The heating conditions are that the surface temperature of the silicone rubber is 230 ° C and the pressure is 10
It was set to kg / cm2. Then, the base sheet was peeled off to obtain a foil cap having the photocatalyst layer transferred to the surface.

[0040]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a transfer foil having a high photocatalyst content and being firmly fixed, whereby the photocatalyst is firmly fixed on 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 transfer foil capable of providing a photocatalytic layer capable of stably obtaining a photocatalytic effect over a long period of time while avoiding deterioration of a binder and the like. Further, according to the molded article of the present invention,
A photocatalyst layer can be easily and strongly applied to the surface of the molded product, simplifying the manufacturing process and reducing the manufacturing cost, and eventually improve the added value of the molded product while reducing the price. be able to.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 67:02 C08L 67:02 (72) Inventor Kazuhiro Kawabe 2-21 Hamamatsubara-cho, Nishinomiya-shi, Hyogo Japan Yamamura Glass Co., Ltd. (72) Inventor Akio Konishi 2-21 Hamamatsubara-cho, Nishinomiya-shi, Hyogo Japan Yamamura Glass Co., Ltd. (72) Inventor Hajime Wakabayashi 2-21 Hamamatsubara-cho, Nishinomiya-shi Hyogo Japan Yamamura Glass (72) Inventor Hironori Miyake 87-5 Hiragawa Hirota, Joyo-shi, Kyoto Prefecture Nakajima Industrial Co., Ltd. (72) Inventor Yuzo Nakamura 87-5 Hirota Hirakawa, Joyo-shi, Kyoto Prefecture Nakajima Industrial Co., Ltd. F-term ( Reference) 4F006 AA35 AB39 AB74 BA11 BA17 DA04 4F100 AA01C AA21B AA23 AA25 AA28 AA33 AK42 AK52C AR00C AT00A BA04 BA07 BA10A BA10D CA02 CA23A DE01B DE01C EH46 GB07 JL08B JL08C JL11D JA14A 4A 4 AD05 AD10 AD20 AE10 AG03 AH47 AR07 JA07 JB13 JB19 JF05 JF35 JL02 JQ06 JQ81 4G069 AA03 AA08 BA04A BA04B BA48A BB04A BB06A BC12A BC22A BC25A BC35A BC50A BC60A BC66A DA06 EA08 FA03FB03

Claims (10)

[Claims] 1. A photocatalyst layer, an inorganic protective layer, and an adhesive layer are formed in this order on a releasable base sheet,
A transfer foil having a photocatalyst layer, wherein the photocatalyst particles in the photocatalyst layer are dispersed and fixed on the surface of an inorganic protective layer. 2. The transfer foil according to claim 1, wherein the photocatalyst particles of the photocatalyst layer are present in a state where the photocatalyst particles are dispersed and attached to the surface of the inorganic protective layer or in a state where only a part thereof is embedded. 3. An organic solvent capable of swelling and softening an inorganic protective layer on a photocatalyst layer after coating a photocatalyst particle dispersion liquid on a base sheet having releasability and drying the photocatalyst layer. Applying a coating liquid for forming an inorganic protective layer containing
The transfer foil according to claim 1, wherein the photocatalyst particles are dispersed and fixed on the surface of the inorganic protective layer by forming the inorganic protective layer by drying. 4. The transfer foil according to claim 1, wherein the inorganic protective layer is formed of organopolysiloxane. 5. The transfer foil according to claim 4, wherein the organopolysiloxane is produced from trialkoxysilane. 6. The photocatalyst layer comprises TiO ₂ , ZnO, Sn
Transfer foil _{O 2, SrTiO 3, WO 3} , Bi 2 O 3 and Fe according to any one of claims 1 to 5 comprising formed by one or more photocatalysts chosen from the group consisting of ₂ O ₃ . 7. The transfer foil according to claim 1, wherein the photocatalyst layer contains substantially no binder. 8. The release sheet according to claim 1, wherein the release sheet has a release layer on the release sheet, and the release layer contains a filler. Transfer foil. 9. A resin molded product is formed by sandwiching the transfer foil according to any one of claims 1 to 8 in an injection molding die and injecting a molten resin to the adhesive layer side at the same time. A method for producing a molded product, which comprises adhering a photocatalyst layer to the surface of the resin molded product, and then peeling off a base sheet having releasability. 10. The photocatalyst layer on the surface of the resin molded product by stacking the adhesive layer side of the transfer foil according to claim 1 on the resin molded product and applying heat pressure from the back surface of the base sheet. And a base sheet having releasability are then peeled off.