WO2001025362A1 - Sheet for transferring photocatalyst - Google Patents

Abstract

A film or sheet for transferring a photocatalyst which comprises a base material in the form of a film or sheet and, formed thereon in the following order, a photocatalyst layer and an adhesive layer, or, a photocatalyst layer, an inorganic layer and an adhesive layer, characterized in that the adhesive layer comprises a siloxane-crosslinked resin containing 0.5 to 60 wt. % of a silicone; a film or sheet for transferring a photocatalyst which comprises a base material in the form of a film or sheet and, formed thereon in the following order, a photocatalyst layer, an inorganic layer and a resin layer having specific properties; and a method for forming a photocatalyst layer on a substrate which comprises extruding a resin on the film or sheet for transferring a photocatalyst to give a coating laminate, or pressing the film or sheet for transferring a photocatalyst onto a resin during extrusion molding of the resin. The film or sheet for transferring a photocatalyst is free from the occurrence of cracking or omission of transfer and is excellent with respect to the durability of the adhesiveness of the film after being transferred; and the method forming a photocatalyst layer on a substrate can be used as a commercial method for forming a photocatalyst layer which has good appearance and transparency and is excellent in the durability of adhesiveness on any substrate uniformly.

Description

 Specification

 Photocatalytic transfer sheet

Technical field:

 The present invention transfers a photocatalytic film with excellent long-term adhesiveness to any substrate such as plastic film, sheet, board, molded product, paper, wood, metal, etc., and provides antibacterial, deodorant, and harmful substances for photocatalyst. Transfer sheet capable of imparting functions such as decomposition removal of soil, antifouling, antifogging, and droplets, a method for transferring a photocatalyst layer using the transfer sheet, and a photocatalyst layer obtained by the method. Regarding molded products, furthermore, there is no appearance defect such as transparent, film unevenness and non-uniform interference fringes on substrates of any shape such as plate, sheet and film of thermoplastic resin. A photocatalyst that carries a photocatalyst film with excellent long-term adhesiveness and can provide functions such as antibacterial, deodorant, decomposition and removal of harmful substances, antifouling, antifogging, and drip of the photocatalyst. Related to a method for producing a resin having a layer Oh o the prior art:

Conventionally, as a method for producing a resin having a photocatalyst layer, sheet molding, flow coating, roll coating, gravure printing, screen printing, spray spraying, dip coating, brush coating, etc. A method of applying a coating solution containing a photocatalyst using a method such as a spin coating method has been adopted, but a transfer method using a transfer sheet in which a photocatalyst layer has been formed in advance is excellent in mass productivity. Therefore, it is suitable for industrial mass production. Japanese Patent Application Laid-Open No. 91-35889 describes a method of forming a coating layer by transferring a coating containing an optical semiconductor powder laminated on a film to an article via a bonding layer. I have. It is described that the film containing the photosemiconductor powder may contain an adhesive binder, and as the binder, a synthetic resin or an inorganic substance can be used. Further, the bonding layer can be formed on the surface of the article, on the coating containing the optical semiconductor powder, or on both, and can fix the coating containing the optical semiconductor powder on the surface of the article. There is no particular limitation as long as it is a synthetic resin, a silicone resin, and other inorganic substances. JP-A-9-122771 discloses that a release layer is formed on a sheet substrate, a photocatalyst-containing layer is further formed thereon, and a corrosion-resistant intermediate layer is further formed thereon. A transfer sheet is described which is formed and further has a pressure sensitive adhesive or a heat sensitive adhesive formed thereon. It is described that water glass, colloidal silica, polyorganosiloxane, fluoropolymer, acrylic silicone resin, zinc phosphate, cement, and the like can be suitably used for the corrosion resistant intermediate layer. Furthermore, there is described a method of transferring a photocatalyst layer by press-bonding or thermo-compressing a transfer target using the transfer sheet. Japanese Patent Application Laid-Open No. 9-122473 discloses a transfer sheet in which a release material is applied to the surface of a sheet base material, and further overlaid, and a mixture of a photocatalyst and an adhesive is applied thereto, or a release material is applied to the surface of the sheet base material A transfer sheet is described in which a material layer and an adhesive layer are sequentially superposed and applied, and a photocatalyst is embedded in the adhesive layer. Examples of the adhesive include polyvinyl alcohol, starch, a mixture of atarilemargin and water, rubber, vinyl chloride, and phenol resin. Further, there is described a method in which the transfer sheet is placed in a mold, and a resin member is injection-molded to transfer a photocatalyst to the surface of a molded product. DISCLOSURE OF THE INVENTION:

 An adhesive has been proposed as one of the methods for easily fixing the photocatalyst on the substrate.However, since the strong photooxidation of the photocatalyst can easily oxidize and decompose organic substances, the photocatalyst can be used. It is difficult to use an organic resin as an adhesive for the purpose of transferring and adhering to a transfer object, and the main component of the photocatalyst layer was specifically composed of an inorganic substance having a weak adhesive force. Also, a method of transferring and bonding the photocatalyst layer via an adhesive layer has been proposed. In this case as well, when an organic material is used for the adhesive layer, the adhesive at the interface with the photocatalyst layer is used. As a result, there is a problem that the photocatalytic layer is decomposed, and the adhesive strength is reduced in a short time, and the photocatalytic layer is peeled off.

It has been proposed in Japanese Patent Application Laid-Open No. Hei 9-122771 to provide a corrosion-resistant intermediate layer that is strong against the photooxidation action of the photocatalyst between the photocatalyst layer and the organic adhesive layer. However, water glass, colloidal silica, cement In the case of inorganic materials such as zinc phosphate and aluminum phosphate, there is a problem that adhesion to both the photocatalytic layer and the adhesive layer is poor, transfer is incomplete, and the film is peeled off. When using polyorganosiloxane, Since the film is not flexible and has poor adhesion to the organic adhesive layer, there is a problem that the film is cracked or peeled due to mechanical deformation or thermal expansion / contraction during transfer or use. Further, in the case of a fluororesin such as polyvinyl fluoride or polyvinyldene fluoride, both the photocatalyst layer and the organic adhesive layer have poor adhesion, and there is a problem that they are peeled off during transfer and use. Furthermore, there is a description that an acrylic silicon resin can be used, but no specific example is described.

 In addition, the method of producing a resin having a photocatalyst layer by transferring the photocatalyst layer is more advantageous than other methods in that the photocatalyst layer can be formed regardless of the shape of the substrate to be transferred. However, there is no known method of strictly controlling the structure of the photocatalyst layer for industrial mass production. In particular, if the thickness of the photocatalyst layer is l ^ m or more, the wear resistance of the film decreases, such as cracking of the film. Therefore, it is preferable that the thickness be 1 or less. As the film thickness increases, a slight change in the film thickness may cause the appearance of interference colors.Therefore, in order to form a photocatalytic layer on a resin without impairing the appearance, it is necessary to control the film thickness highly uniformly. However, there is no description that such control was performed by the transfer method as in the related art.

The present invention is a transfer film or sheet provided with a photocatalyst layer on a base film or sheet. The transfer film has no cracks or transfer leakage at the time of transfer, and the transferred film exhibits excellent long-term adhesion. Aims to provide a film or sheet, a transfer method using the transfer film or sheet, and a molded article produced by the transfer method, and further have excellent transparency and appearance, and excellent long-term adhesion. It is an object of the present invention to provide an industrial production method for uniformly forming a photocatalyst layer having the above on all substrates. The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a photocatalyst layer and an adhesive layer were provided in this order on a film or sheet substrate surface, and the adhesive layer was 0.5-. Adhesion consists of a photocatalyst layer, an inorganic layer, and an adhesive layer provided on a transfer film or sheet, film or sheet base material, which is a siloxane cross-linkable resin containing 60% by weight of silicone, in this order. A photocatalyst layer, an inorganic layer, a resin having specific properties on a transfer film or sheet whose layer is a siloxane cross-linkable resin containing 0.5 to 60% by weight of silicone, or a film or sheet base material To solve the above problems by using a transfer film or sheet having layers provided in this order. The resin is extruded onto a transfer film or sheet having a photocatalyst layer, and is coated and laminated, and the transfer film or sheet is pressed during the process of extruding the resin. The present inventors have found that a photocatalyst layer having good properties and appearance and having excellent long-term adhesiveness can be industrially supported on a resin, thereby completing the present invention.

 That is, the present invention

 (Constitution 1) In a transfer film or sheet having a photocatalyst layer and an adhesive layer provided in this order on the surface of a film or sheet substrate, the adhesive layer has a silicone content of 0.5 to 60% by weight in terms of silicon dioxide. A transfer film or sheet comprising a siloxane cross-linked resin containing

 (Constitution 2) In a transfer film or sheet in which a photocatalyst layer, an inorganic layer, and an adhesive layer are provided in this order on the surface of a film or sheet substrate, the adhesive layer is 0.5 to 60% by weight in terms of silicon dioxide. A transfer film or sheet characterized by comprising a silicone-containing siloxane cross-linkable resin,

 (Structure 3) The transfer film or the transfer film according to (Structure 1) or (Structure 2), wherein the adhesive layer is made of a siloxane cross-linkable resin containing 20 to 40% by weight of silicone in terms of silicon dioxide. Sheet,

 (Constitution 4) The transfer film or sheet according to any one of (Constitution 1) to (Constitution 3), wherein a primer layer is provided on the adhesive layer.

 (Structure 5) The transfer film or sheet according to (Structure 4), wherein the thickness of the primer layer is in the range of 0.05 to 5 m.

 (Structure 6) The transfer sheet according to (Structure 4) or (Structure 5), wherein the primer layer is made of a resin having a number average molecular weight of 20,000 or more.

 (Structure 7) The primer layer is characterized by comprising a resin having a number average molecular weight of 20,000 or less and a glass transition point of 110 to 100 ° C. (Structure 4) or (Structure 5) Transfer film or sheet according to

(Structure 8) The transfer film or sheet according to (Structure 6) or (Structure 7), wherein the resin is an acrylic silicone resin or an epoxy silicone resin. (Structure 9) Silicone has the formula (I)

S i C 1 n! _{^{(OH) n ^ 1 n 3}} (OR 2) n 4 - (I)

[Wherein, R ¹ represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group, or a chlorine atom), and R ² represents an alkyl group having 1 to 8 carbon atoms. Represents an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group, represents an integer of 0 to 2, n ₄ is an integer of 2 to 4, and 1 ^ + 112 + 113 + 114 = Represents an integer of 4. A transfer film or sheet according to any one of (Configuration 1) to (Configuration 8), which is a polysiloxane that is a polycondensation reaction product of the compound represented by the following formula:

 (Configuration 10) The resin portion of the siloxane cross-linkable resin of the adhesive layer is an acrylic resin, an epoxy resin, an acrylic silicon resin, or an epoxy silicon resin, wherein any of (Configuration 1) to (Configuration 9) is provided. The transfer film or sheet described in

(Structure 11) A photocatalytic layer, an inorganic layer, a resin having a number average molecular weight of 20,000 or more and / or a number average molecular weight of 20,000 or less, and a glass on the surface of a film-like or sheet-like substrate. A transfer film or sheet, wherein a layer made of a resin having a transition point of 10 to 100 ° C is provided in this order,

 (Configuration 12) The transfer film or sheet according to (Configuration 11), wherein the resin is an acrylic silicon resin or an epoxy silicon resin.

 (Structure 13) The inorganic layer is represented by the formula (II)

nS i (OR ₄ — _n … (II)

 (Wherein, R represents an alkyl group which may have a substituent having 1 to 4 carbon atoms, and R! Is an alkyl group which may have a substituent having 1 to 5 carbon atoms or 1 carbon atom. And n represents 0 or 1. n) represents an organoalkoxysilane or a hydrolyzed / condensed product of an alkoxysilane represented by the following formula: A transfer film or sheet according to any one of (Configuration 2) to (Configuration 12),

(Configuration 14) The photocatalyst layer is a photocatalyst particle composite containing 25 to 95% by weight of a metal oxide gel and / or a metal hydroxide gel. Transfer film or sheet according to any of the above, (Constitution 15) The metal oxide gel and / or metal hydroxide gel in the photocatalyst layer is one or two selected from silicon, aluminum, titanium, zirconium, magnesium, diobium, tantalum, tungsten, and tin. A transfer film or sheet according to (Configuration 14), which is at least one kind of metal oxide gel or metal hydroxide gel;

 (Structure 16) The transfer film or sheet according to any one of (Structure 1) to (Structure 15), wherein the thickness of the photocatalyst layer is 1 or less.

 (Structure 17) The transfer film or sheet according to any one of (Structure 2) to (Structure 16), wherein the total thickness of the inorganic layer and the photocatalyst layer is 1 m or less.

 (Constitution 18) The transfer film or sheet according to any one of (Constitution 1) to (Constitution 17), wherein a release layer is provided between the substrate and the photocatalyst layer.

 (Structure 19) A step of preparing the transfer film or sheet according to any one of (Structure 1) to (Structure 18), a step of pressing an adhesive layer surface of the transfer film or sheet against a surface of a transfer target, and A method for transferring a photocatalyst layer, comprising a step of peeling a substrate in a transfer film or a sheet,

 (Constitution 20) The step of pressing the adhesive layer surface of the transfer film or sheet against the surface of the transfer object is a step of pressing the adhesive layer surface of the transfer film or sheet against the surface of the transfer object while applying heat. The method for transferring a photocatalyst layer according to (Configuration 19),

 (Structure 21) The structure according to (Structure 19) or (Structure), wherein a cross-linking reaction of the siloxane cross-linkable resin of the adhesive layer proceeds during the step of pressing the adhesive layer surface of the transfer film or the sheet against the surface of the transfer object. 20) The method for transferring a photocatalyst layer according to

 (Structure 22) The method for transferring a photocatalyst layer according to any one of (Structure 19) to (Structure 21), wherein the shape of the transfer target is a plate, a sheet, or a film.

(Structure 23) A molded article provided with a photocatalytic layer obtained by the method according to any one of (Structure 19) to (Structure 22) is irradiated with light having an ultraviolet intensity of 3 mWZ cm ² for 500 hours, and then subjected to JISK 5400 Of photocatalyst layer by grid tape method specified in Japan A molded article provided with a photocatalyst layer having an evaluation score of 6 or more; (Constitution 24) A photocatalyst layer obtained by the method according to any one of (Constitution 19) to (Constitution 22) A molded article provided with a photocatalyst layer, characterized in that the total light transmittance of the photocatalyst layer and the adhesive layer or the total light transmittance of the photocatalyst layer, the inorganic layer and the adhesive layer to light having a wavelength of 550 nm is 70% or more. Molded products,

 (Structure 25) A method for producing a resin structure having a photocatalyst layer, wherein a resin melted on a transfer film or a sheet having a photocatalyst layer is extrusion-coated and continuously produced,

 (Structure 26) A method for producing a resin structure having a photocatalyst layer, comprising continuously extruding and laminating a molten resin between a transfer film or a sheet having a photocatalyst layer and a substrate to be transferred,

 (Structure 27) Manufacturing of a resin structure having a photocatalyst layer, characterized in that the melt-extruded resin is continuously manufactured by pressing a transfer film or sheet having the photocatalyst layer during the step of cooling on a cooling roll. Method,

 (Constitution 28) The transfer film or sheet having a photocatalyst layer is the transfer film or sheet according to any one of (Constitution 1) to (Constitution 18).

(Structure 26) A method for producing a resin structure having a photocatalyst layer according to any one of (Structure 26) to (Structure 27),

 (Structure 29) The photocatalyst layer according to any one of (Structure 25) to (Structure 28), wherein the resin of the resin structure is a polycarbonate resin, an acrylic resin, a polyvinyl chloride resin, or a polystyrene resin. Resin manufacturing method,

 (Structure 30) The resin structure having a photocatalyst layer according to any one of (Structure 25) to (Structure 29), wherein the resin of the resin structure has a plate shape, a sheet shape, or a film shape. Body manufacturing method,

 About.

The structure of the transfer film or sheet having a photocatalyst layer is a structure in which the structure of the photocatalyst layer 2 alone, the photocatalyst layer 2, and the adhesive layer 3 are laminated in this order on the surface of the substrate 1 on which the structure to be transferred is installed. , A photocatalyst layer 2, an inorganic layer 4, and an adhesive layer 3 laminated in this order, a photocatalyst layer 2, an inorganic layer 4, a resin having a number average molecular weight of 20,000 or more, Alternatively, a structure in which layers 5 made of a resin having a number average molecular weight of not more than 200 and a glass transition point of 110 to 100 ° C. are laminated in this order can be exemplified. Considering the adhesion to the object to be photographed, a structure as shown in Figs. 1-3 is preferred ^ ,.

Base material

 The film-like or sheet-like base material used in the present invention is not particularly limited, and can be appropriately selected from an organic material, an inorganic material, or a composite material thereof. Examples thereof include polypropylene, acrylic resin, polyethylene terephthalate, polyvinyl chloride, polycarbonate, and polystyrene. The thickness of the substrate is preferably in the range of 3 m to 500 m, and more preferably in the range of 16 im to 100 m.

 The surface of the substrate is preferably smooth, and a substrate having a thickness variation of 10% or less is particularly preferable for forming a photocatalytic layer having a uniform thickness. As the adhesive layer, any siloxane crosslinkable resin containing 0.5 to 60% by weight of silicone in terms of silicon dioxide can be used. Acrylic resin, epoxy resin, polyester resin, urethane resin, alkyd resin, etc. can be used as the siloxane cross-linkable resin, but acrylic resin and epoxy resin have the best adhesion to the object to be transferred. Hydrosilylation of a part of the resin directly into the main chain using vinylalkoxysilane, etc., through a siloxane bond, silazane bond, carbon-gay bond, etc., or to an unsaturated bond Accordingly, an acryl silicone resin or an epoxy silicone resin into which a crosslinkable alkoxysilane moiety or a halogenosilane moiety has been introduced can also be suitably used.

 The proportion of the organic moiety in the silicone-containing siloxane crosslinkable resin is preferably at least 40% by weight. In this case, the organic portion means a portion other than silicon equivalent in terms of silicon dioxide. If the amount is less than 40% by weight, the transfer to the transfer target will not be successful, and the long-term adhesiveness of the film will decrease.

In addition, a resin having a larger number of cross-linking points in the siloxane cross-linkable resin has better adhesion to the photocatalyst layer or the inorganic layer. In this case, the crosslinking point is, for example, an ester or carboxylic acid in an acrylic resin, a hydroxyl group, an unsaturated bond, an alkoxy in an epoxy resin. A silane portion and the like can be exemplified.

 When silicone is added as a cross-linking agent to the siloxane cross-linkable resin, the adhesion to the photocatalyst layer or the inorganic layer is improved. The amount of addition is in the range of 0.5 to 60% by weight in terms of silicon dioxide, and the effect is most effective when it is in the range of 20 to 40% by weight. In this case, when a siloxane component is contained in the siloxane cross-linkable resin, the weight ratio indicates a combination of the two. If the amount of the silicone exceeds 60% by weight, the adhesiveness to the transfer object is deteriorated.

 As the silicone, polysiloxane which is a polycondensation reaction product of the compound represented by the formula (I) is particularly preferred. In the formula (I), R represents an alkyl group having 1 to 8 carbon atoms (which may be substituted by an amino group, a carboxyl group, or a chlorine atom). Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, methoxymethyl, dimethylaminomethyl, methoxethyl, dimethylaminoethyl, Examples thereof include a chloroethyl group, a chloropropyl group, and an acetoethyl group.

R ² represents an alkyl group having 1 to 8 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Examples thereof include a butyl group, a t-butyl group, a methoxymethyl group, a methoxethyl group, and an acetoethyl group.

Specific examples of the compound represented by the formula (I) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltriisopropoate. Xysilane, ethyltri-t-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane, n-hexyltrimethoxysilane, n-hexyltri Ethoxysilane, n-hexyltriisopropoxysilane, n-hexynoletrito-ethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyl Dimethoxy silane, dimethyl ethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triisopropoxy silane, vinyl tri Butoxysilane, trifluoropropyl trimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane, 7-glycidoxypropylmethyl dimethoxysilane, fragrance Sidoxypropylmethyl ethoxysilane, 7-glycidoxypropyltrimethoxysilane, 7-glycidoxypropyltriethoxysilane, 7-glycidoxypropyltriisopropoxysilane, α-glycidoxypropyltrit-butoxysilane, ₇ - aminopropyl methyl dimethyl Tokishishi orchid, § one § amino propyl methyl jet silane, § chromatography § amino propyl trimethinecyanine Tokishishiran, § one § amino propyl triethoxysilane, § one Aminopurobiruto Riiso Roboxy silane, 7-Aminopropyltri-t-butoxysilane, 7-Mercaptopropylmethyldimethoxysilane, 7-Mercaptopropylmethylethoxysilane, Amercaptopropyltrimethoxysilane, A_Mercaptopyl Pyrtriethoxysilane, 7— Mercaptopropyltriisopropoxysilane, α-mercaptopropyltri-t-butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxy Examples include silane and the like.

In addition to the silane compounds exemplified above, methyltrichlorosilane, methyltributanesilane, ethyltrichlorosilane, ethyltribromosilane, η-propyltrichlorosilane, η-propyltribromosilane, η-hexyltrichlorosilane, η —Hexyltribromosilane, η-decyltrichlorosilane, η-decyltribromosilane, η-decyltrimethoxysilane, η-decyltriethoxysilane, η-decyltriisopropoxysilane, η-decyltri-t-butoxysilane, n— N-octadecyltrichlorosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltrit-silane Butoxysilane, Enyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, tetrachlorosilane, tetrabutylsilane, dimethyldichlorosilane, dimethyldib Mouth silane, diphenyl Chlorosilane, diphenyldimethoxysilane, diphenyldimethoxysilane, diphenylethoxysilane, phenylmethyldichlorosilane, phenylmethyldimethoxysilane, phenylmethyldimethoxysilane, phenylmethylethoxysilane; trichlorohydrosilane, tribromo Hydrosilane, trimethoxyhydroxysilane, triethoxyhydroxysilane, triisopropoxyhydrosilane, trit-butoxyhydroxysilane, vinyltrichlorosilane, vinyltribromosilane, trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, 7-meta Acryloxypropylmethyldimethoxysilane, methacryloxypropylmethyljetoxysilane, 7-metaaryloxypropyltrimethy Examples thereof include silane compounds such as xylene, 7-methacryloxypropyltriethoxysilane, 7-methacryloxypropyltriisopropoxysilane, and 7-methacryloxypropyltri-t-butoxysilane.

 A light stabilizer and / or an ultraviolet absorber can be mixed in the adhesive layer for the purpose of improving durability. As a light stabilizer which can be used, a hindered amine type is good, but other substances can also be used. As the ultraviolet absorber, a triazole type or the like can be used.

 For the purpose of controlling the siloxane crosslinking reaction, a silane coupling agent, an acid-base catalyst, a metal chelate catalyst or the like can be added.

 For the purpose of improving adhesiveness and operability, various additives such as a surfactant and an antifoaming agent of 5% by weight or less can be added.

 The thickness of the adhesive layer is 1 m or more, preferably 3 m or more. If it is less than l im, the transfer becomes difficult, and the long-term adhesion after the transfer deteriorates.

 To apply the adhesive layer on the substrate sheet coated with the photocatalyst layer, various printing methods such as gravure printing, roll coating method, flow coating method, sheet forming method, spray spraying method, dip coating method, spin coating method A method such as the law can be used.

 The drying temperature varies depending on the material of the base sheet, the type of the solvent and the resin, but is generally preferably 150 ° C. or lower.

In order to improve the transfer and the adhesion to the transfer target, a further brush Preferably, a mer layer is provided. As the primer layer, any material can be used as long as it is generally used, depending on the material of the transfer object. Among them, resins having a number average molecular weight of more than 200,000, Alternatively, the number average molecular weight is not more than 20, 000, and the glass transition point is 110 to 100 ° C, preferably 10 to 80 ° C. C, and more preferably a resin in the range of 30 to 80 ° C. is used. In the case of a resin having a number average molecular weight of more than 200,000, its glass transition point is not restricted. Further, it is preferable to use a resin having an elongation percentage of the coating film dried at room temperature to 60 ° C. in the range of 30 to 150%, particularly preferably in the range of 50 to 130%. Specific examples of the material used for one layer of the polymer include a polyvinyl isobutyl ether, an acrylic ester resin, an olefin chloride resin, a rubber resin, a pressure-sensitive adhesive such as a polyethylene-vinyl acetate copolymer, or a styrene resin. Styrene-acrylic copolymer, acryl resin, phenol resin, epoxy resin, acryl silicone resin, epoxy silicone resin, urethane resin, polyester resin, etc., and acryl silicone resin or epoxy silicone resin is particularly preferable. .

 The thickness of the primer layer is not particularly limited as long as it does not affect properties such as transparency, but is preferably in the range of 0.05 to 5 μm. At 0.05 m or less, there is no effect of improving adhesion, and at 5 μππ or more, the effect of improving adhesion does not change much. The metal oxide gel and / or metal hydroxide gel in the photocatalyst layer not only fixes the photocatalyst and firmly adheres to the siloxane crosslinked resin of the adhesive layer, but also removes the photocatalyst layer from the base film or sheet after transfer. This has the effect of facilitating peeling. In addition, since the gel is porous, it has an adsorptive property and has an effect of enhancing photocatalytic activity. The content of the metal oxide gel and / or metal hydroxide gel in the photocatalyst layer is preferably in the range of 25 to 95% by weight. If it is less than 25% by weight, the adhesion to the adhesive layer will be insufficient, and if it is more than 95% by weight, the photocatalytic activity will be insufficient.

Specific examples of the material of the metal oxide gel and metal or hydroxide gel include gay, aluminum, titanium, zirconium, magnesium, diobium, tantalum, tungsten, and tin. Also, these were mixed As the gel, a composite oxide gel prepared by a method such as a coprecipitation method can be used. In order to mix with the photocatalyst, it is preferable to mix in a sol state before forming a gel, or to mix in a raw material stage before preparing a sol. Gel preparation methods include hydrolysis of metal salts, neutralization decomposition, ion exchange, and hydrolysis of metal alkoxides.The photocatalyst powder is uniformly dispersed in the gel. Any method can be used as long as it can be obtained in the state described above. However, if a large amount of impurities are present in the gel, the adhesiveness and catalytic activity of the photocatalyst will be adversely affected. Therefore, a gel with few impurities is preferred. In particular, if the gel contains more than 5% of organic matter, the photocatalytic activity will decrease.

The photocatalyst of the photocatalyst _{layer, T i 0 2, ZnO,} S rT i 0 3, C d S, G aP, I nP, GaAs, B aT i 0 3, K2Nb0 3, F e 2 0 3, T a ₂ 0 _5, WO _3. SnO There _{B i 2 0 3, N i} O, Cu 2 0, S i C, illustrate the _{S i 0 2, Mo S 2} , I nPb, Ru0 2, C e 0 2 , etc. And an anatase type titanium oxide is particularly preferable. Moreover, these photocatalyst _{P t, Rh, Ru0 2,} Nb, C u, S n, known combinations the addition of metals and metal oxides, such as N i 0 is total and available. As for the content of the photocatalyst in the photocatalyst layer, the larger the content, the higher the catalytic activity becomes.

 To form a photocatalyst layer on a substrate film or sheet, use a suspension in which a photocatalyst is dispersed in a metal oxide sol and Z or a metal hydroxide sol solution.L. Same as forming an adhesive layer The following coating method can be used. The photocatalyst can be dispersed in the state of a precursor solution of a metal oxide sol and a precursor of a metal or metal hydroxide sol, and can be hydrolyzed or neutralized during coating to form a sol or a gel. When using a sol, an acid or alkali peptizer may be added for stabilization. Further, in order to improve the adhesiveness and Z or operability, a surfactant, an antifoaming agent and a silane coupling agent can be added in an amount of 5% by weight or less based on the photocatalyst in the sol suspension. The drying temperature at the time of forming the photocatalyst layer is preferably 50 ° C. or more and 150 ° C. or less, depending on the material of the base film or sheet.

The thickness of the photocatalyst layer is higher when the photocatalyst layer is thicker, but if it is 2 or more, the film may be cracked when the substrate sheet is peeled off after the completion of the transfer. When the value is 1 or less, a transparent film having a total light transmittance of 80% or more and a haze ratio of 2% or less of the film after transfer at a wavelength of 550 nm is obtained, and the appearance of the transfer object is not impaired at all. It is also useful in terms of sex.

Inorganic layer

The inorganic layer has the effect of improving the adhesion between the photocatalyst layer and the adhesive layer, the effect of improving the wear resistance of the photocatalyst layer, and the effect of reducing color development due to interference fringes derived from the photocatalyst layer thickness. For the material of the inorganic layer, the formula (Π) R _n S i (OR,) ₄ _ _n

 (Wherein, R represents an alkyl group which may have a substituent having 1 to 4 carbon atoms, and R, is an alkyl group which may have a substituent having 1 to 5 carbon atoms or 1 carbon atom. And n represents 0 or 1. The main component is an organoalkoxysilane or a hydrolyzed / condensed product of an alkoxysilane represented by the following formula: Specific examples of the silane compound represented by the formula (Π) include those similar to the specific examples of the silane compound represented by the formula (I). For the purpose of controlling the curing speed, preventing cracking of the film, improving the chemical durability, and controlling the refractive index, etc., a silicic acid sol, an alumina sol, a zirconium sol, or the like can be added.

 To form the inorganic layer on the photocatalyst layer, the same coating method as that for forming the adhesive layer can be used. In order to improve adhesion and Z or operability, 5% by weight or less of a surfactant, an antifoaming agent and a silane coupling agent can be added. The drying temperature at the time of forming the inorganic layer varies depending on the material of the base sheet, but is preferably from 50 ° C to 150 ° C.

 The thickness of the inorganic layer is from 0.1 / m to 2 m, and preferably the total film thickness of the photocatalyst layer and the inorganic layer is from 0.1 μπι to 1 / m. If it is more than 2 m, the film may crack when the base sheet is peeled off after transfer is completed.

 Further, the transfer film or sheet of the present invention, the photocatalyst layer, the inorganic layer, a resin having a number average molecular weight of 20,000 or more and / or a number average molecular weight of 20,000 or less, Further, a layer made of a resin having a glass transition point of 110 to 100 ° C. is provided in this order.

When the number average molecular weight is 20,000 or less, a resin having a glass transition point of 1 to 100 ° C, preferably 10 to 80 ° C (: more preferably 30 to 80 ° C) is used. Is preferred. In the case of a resin having a number average molecular weight of 200,000 or more, its glass transition point is not limited, and for example, a resin in the range of 110 to 100 ° C can be used. . Further, it is preferable to use a resin having an elongation percentage of the coating film dried at room temperature to 60 ° C. in the range of 30 to 150%, particularly preferably in the range of 50 to 130%. No. Specifically, pressure-sensitive adhesives such as polyvinyl isobutyl ether, acrylic ester resin, chlorinated olefin resin, rubber resin, polyethylene-vinyl acetate copolymer, or styrene resin, styrene-acrylic copolymer, acrylic Examples thereof include a resin, a phenol resin, an epoxy resin, an acrylic silicone resin, an epoxy silicone resin, a polyurethane resin, and a polyester resin, and an acrylic silicone resin or an epoxy silicon resin is particularly preferred.

 A light stabilizer and / or an ultraviolet absorber can be mixed in the resin layer for the purpose of improving durability. As a light stabilizer that can be used, a hindered amine type is preferable, but other substances can also be used. As the ultraviolet absorber, a triazole type or the like can be used.

 For the purpose of improving adhesiveness and operability, various additives such as a surfactant and an antifoaming agent of 5% by weight or less can be added.

 The thickness of the resin layer is at least Ιμπι, preferably at least 3 m. If it is less than 1 m, transfer becomes difficult, and the long-term adhesion after transfer deteriorates.

 In order to apply the resin layer on the base film or sheet on which the photocatalyst layer and the inorganic layer are applied, the same coating method as when forming the adhesive layer can be used.

 The drying temperature varies depending on the material of the base film or sheet, the type of the solvent and the resin, but is generally preferably 150 ° C. or lower.

Release layer

 A release layer can be provided on the base film or sheet for the purpose of making the base film or sheet easily peelable after the transfer. As the material, melamine, silicon, fluorine, acrylic thermosetting resin alone or a mixture thereof can be used. It is also possible to adjust the peel strength by adding additives such as silicon, fluorine, polyester and polyethylene to the above resin.

Preparing the transfer film or sheet as a transfer method; A method for transferring a photocatalytic layer, which includes a step of pressing the adhesive layer surface of the film or sheet against the surface of the transfer object and a step of peeling off the base material in the transfer film or sheet, can be exemplified. The step of pressing against the transfer object can be performed by any method such as heating and / or pressing. As the method of heating and pressurizing, any method such as an in-mold transfer method for transferring at the time of production of a plastic molded article or a roll transfer method for transferring a film or a plate onto a plane can be used.

 In addition, during the step of pressing the adhesive layer surface of the transfer film or sheet of the present invention against the surface of the transfer object, if the crosslinking reaction of the siloxane cross-linking resin of the adhesive layer proceeds, the adhesion between the adhesive layer and the transfer object is improved. . Methods for maintaining the cross-linking reaction point include reducing the hydrolysis rate of the cross-linking silicon alkoxy group (Si-OR) or replacing the cross-linking alkoxy group with an alkoxy group having a larger number of carbon atoms by an alkoxy exchange reaction. Or increasing the glass transition temperature of the resin part. Further, after the transfer film or the sheet substrate is peeled off, a post-treatment such as heating can be further performed. At this time, even if the crosslinking reaction is advanced in the adhesive layer, the adhesion is similarly improved.

 Further, as another transfer method, a method in which the transfer film or sheet of the present invention is placed in a mold, a resin member is injection-molded, and a photocatalyst is transferred to the surface of a molded product can be exemplified.

 The transfer target can be transferred in a complicated shape by using a method such as vacuum compression bonding. However, a plate, a sheet, or a film is particularly preferable.

 The step of peeling the substrate in the transfer film or sheet is exemplified by a method in which the transfer sheet is peeled by applying shear stress, tensile stress, or the like, or a method in which the transfer sheet is peeled by using the oxidizing power of a photocatalyst by irradiating ultraviolet rays. be able to. After transfer, the sheet substrate also acts as a protective film to prevent damage to the photocatalyst layer unless it is peeled off.

After the molded article obtained by the method of the present invention was irradiated with light having an ultraviolet intensity of 3 mWZ cm ² for 500 hours, the adhesiveness of the photocatalyst layer by the grid tape method specified in JISK540 was evaluated. It is a molded article provided with a photocatalyst layer having 6 or more points.

The molded article obtained by using the present invention comprises a photocatalyst layer and an adhesive layer or a photocatalyst layer. A molded article provided with a photocatalytic layer, wherein the total light transmittance of light having a total wavelength of 550 nm of the inorganic layer and the adhesive layer is 70% or more.

 The method for forming a photocatalyst layer on a resin according to the present invention is characterized in that a molten resin is extrusion-coated on a transfer film or a sheet having a photocatalyst and is continuously manufactured. Extrusion coating can be exemplified by a method in which a molten resin is extruded into a film form from a slit die called a T-die and applied to a substrate. In this case, a film having a three-layer structure including the photocatalyst layer, or a film having a four-layer structure including the photocatalyst and the adhesive layer can be continuously manufactured. In this case, by providing an anchor coat layer on the transfer film or sheet in advance, the adhesiveness can be further increased. In the case of using a tandem radiator in which two T-dies are continuously arranged, it is possible to continuously produce films with four or five layers.

 Another method of forming a photocatalyst layer on a resin according to the present invention is characterized in that a molten resin is extruded and laminated between a transfer film or a sheet having a photocatalyst and a substrate to be transferred, and is continuously manufactured. I do. Extrusion lamination in this case is also called sanguinche lamination, in which molten resin is extruded from a slit die into a film and applied to the substrate, and another substrate is supplied from an unwinder called a sanding machine Then, it shows the method of bonding together. In this case, the transfer film or sheet can be used as a substrate coated with the molten resin or as a substrate supplied from the unwinder. In this case, a three-layer coated film or the like can be manufactured continuously.

Another method for forming the photocatalyst layer of the present invention on a resin is to press-bond a transfer film or sheet having a photocatalyst layer during the step of cooling the melt-extruded resin on a cooling port. It is characterized by being manufactured continuously. This method is used in a method of mixing and heating materials and continuously extruding a molten resin from an extruder through a die, and in a chill roll method in which a resin is extruded and then rapidly cooled by a cooling roll. In this method, in a step of cooling with a cooling roll, a transfer film is laminated on the extruded resin and both are cooled at a time to produce a resin structure having a photocatalyst layer. Resin having photocatalyst layer

 In the present invention, the material of the resin having the photocatalyst layer is not particularly limited as long as it is a thermoplastic resin, and specific examples thereof include a polyethylene resin, a polypropylene resin, and a polyethylene terephthalate resin. However, acrylic resin, polyvinyl chloride resin, polycarbonate resin and polystyrene resin are particularly preferred.

 The shape is not particularly limited, but is preferably a plate, sheet, or film.

 In the case of a film, the thickness is preferably in the range of 3 to 200 m, and more preferably in the range of 16 to 100 m. The film surface should be smooth, but the surface may be uneven for the purpose of patterning during transfer.

 The structure of a transfer film or sheet having a photocatalyst layer is a structure in which a photocatalyst layer alone, a photocatalyst layer, and an adhesive layer are laminated in this order on a substrate surface on which a structure to be transferred is placed, or a photocatalyst layer. An example is a structure in which an inorganic layer, an inorganic layer, and an adhesive layer are laminated in this order. A structure having an adhesive layer is preferable in consideration of the adhesion to the transfer target. Specific examples of the structure, material, and the like are preferably the transfer film or sheet described above. BRIEF DESCRIPTION OF THE DRAWINGS:

 1 to 3 are diagrams schematically showing preferred structures in the transfer film of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples.

 Example 1

A photocatalyst coating liquid (Nippon Soda's Bistreita-1 NDC-1) is prepared by dispersing photocatalyst particles in silica sol on a polyethylene terephthalate film (Toyobo E5001) with a thickness of 2 δ zm that has not been subjected to surface treatment. 30 C: solid content concentration 8%) After coating with a bar coater to a film thickness of 0.5 m, it was dried at 120 ° C to prepare a PET film with a photocatalytic layer (A-1). Further, a polysiloxane-added siloxane-crosslinked acryl resin solution Y (Nippon Soda's Vistreita NRC-300A: solid content concentration 10%) is coated to a film thickness of 5 im, dried at 120 ° C, and transferred to a transfer sheet ( T-1) was created. Then, the acrylic resin plate surface as a transfer object, by superimposing the transfer sheet (T one 1), laminated with a 5 k pressure GZcm ² at 180 ° C, peeling the substrate sheet, the outermost surface Prepared an acrylic resin plate (P-1) consisting of a photocatalyst layer.

Example 2

(A-2) was produced under the same conditions as in Example 1 except that only the film thickness was 0.2 m. Furthermore, a polysiloxane-added siloxane crosslinked acryl resin solution (Nippon Soda's Vistreita -NRC-300A: solid content concentration 10%) is coated to a film thickness of 5 m, dried at 120 ° C, and transferred to a transfer sheet. (T-2) was created. Then, the acrylic resin plate surface as a transferred object, overlapping the transfer sheet (T one 2), laminated with a 5 kg / cm ² of pressure at 180 ° C, by peeling the substrate sheet, the outermost An acrylic resin plate (P-2) with a photocatalytic layer on the surface was prepared.

Example 3

(A-2) was prepared in the same manner as in Example 2, and (A-2) a coating solution of an inorganic layer (a glass power T 2106 solution and a glass power H 501 solution of Nippon Synthetic Rubber: 95: 5 Was coated with a bar coater to a thickness of 0.3 and dried at 120 ° C to produce a PET film (B-1) with an inorganic layer of a photocatalyst layer. Furthermore, a polysiloxane-added siloxane cross-linked acrylic resin solution (Nippon Soda's Vistreta-NRC-300A: solid content concentration 10%) is coated to a film thickness of 5, dried at 120 ° C, and transferred to a transfer sheet (T- 3) was created. Next, the Akuriru resin plate surface as a transfer object, the transfer sheet overlaid one bets (T one 3), laminated with a 5 k pressure GZC m ² at 180 ° C, peeling the substrate sheet one DOO In this way, an acrylic resin plate (P-3) with a photocatalyst layer on the outermost surface was prepared. Example 4

A transfer sheet (T-1) prepared in the same manner as in Example 1 was used as an acrylic resin film. (Kanebuchi Chemical Sanjuren 004NAT, thickness 50 m) and transferred at 140 ° C with a pressure of 5 kg / cm ² using a heating and pressing roll. By peeling the transfer sheet substrate, an acrylic resin film (P-4) with the photocatalyst layer on the outermost surface was created.

Example 5

The transfer sheet (T-3) prepared in the same manner as in Example 3 was overlaid on an acrylic resin film (Sanjuren 004NAT manufactured by Kaneka Chemical Co., thickness 50 / m) and heated at 140 ° C under a pressure of 5 kcm ^2. Transfer was performed using a pressure roll. By peeling off the transfer sheet substrate, an acrylic resin film (P-5) having a photocatalyst layer on the outermost surface was created.

Example 6

The same manner as in Example 1 transfer sheet was adjusted (T-1) a polystyrene resin plate (two Tsu Seo one resin, 2 mm thickness) overlaid, heat and pressure at 5 k gZcm ² pressure at 80 ° C Transfer was performed using a roll. By peeling off the transfer sheet substrate, an acrylic resin film (P-6) with the outermost surface being a photocatalyst layer was prepared.

Example 7

The transfer sheet (T-13) adjusted in the same manner as in Example 3 was placed on a polystyrene resin plate (made of Nippon Resin, 2 mm thick), and at 80 ° C. and a pressure of 5 kg / cm ² . Transfer was performed using a heating and pressing roll. By peeling off the transfer sheet substrate, an acrylic resin film (P-7) having the photocatalyst layer on the outermost surface was created.

Example 8

 On a transfer sheet (T-1) prepared in the same manner as in Example 1, a copolymer polyester solution Byron 300 (manufactured by Toyobo Co., Ltd.) was coated with a bar coater so as to have a film thickness of 0.5 μπι. After drying, the sheet was dried at 120 ° C to prepare a transfer sheet (T-4) with a single primer layer.

Polyester film Cosmo Sunshine A—4100 (manufactured by Toyobo Co., Ltd., 0.5 / m thick), the above transfer sheet (T-14) is superimposed on the surface printed with ink at 140 ° C, 5 kg By laminating at a pressure of / cm ² and peeling off the base sheet, a sheet (P-8) having a photocatalyst layer on the outermost surface was prepared. Example 9

 On a transfer sheet (T-12) prepared in the same manner as in Example 2, an acrylic silicon resin solution ZEMRAC YC 3623 (manufactured by Kanegafuchi Chemical Co., Ltd.) was applied with a bar coater to a thickness of 0.5 m. After coating, it was dried at 120 ° C. to prepare a transfer sheet (T-5) with a primer layer.

The transfer sheet (T-5) is laminated on the surface of the polycarbonate plate, laminated at 150 ° C and a pressure of 5 kg / cm ² , and the substrate sheet is peeled off. P-9) was created.

Example 10

 On a transfer sheet (T-3) prepared in the same manner as in Example 3, an acrylic silicon resin solution Zemurac YC 3623 (manufactured by Kanegafuchi Chemical Co., Ltd.) was applied to the transfer sheet (0.5 mm) to a thickness of 0.5 m. After coating, the resultant was dried at 120 ° C. to prepare a transfer sheet (T-6) with a single primer layer.

A polycarbonate plate surface, overlaid the transfer sheet (T- 6), 150 ° C , 5 laminated at a pressure of KGZ cm ^2, by peeling off the substrate sheet, a polycarbonate plate outermost surface made of a photocatalytic layer (P — Created 10).

Example 11

 A PET film with a photocatalytic layer and an inorganic layer in the same manner as in Example 3 except that Nissan Chemical Snowtex IPA-ST adjusted to 1% solid content with water Z ethanol = 1 Z1 as the inorganic layer coating liquid was used. (B-2), transfer sheet (T-17), and resin plate (P-11) were adjusted.

Example 12

 In the same manner as in Example 3, except that Nissan Chemical Snowtex XS adjusted to a solid content of 1% with water / ethanol = 1 1 was used as the inorganic layer coating liquid, a PET film with an inorganic layer (B-3) ), Transfer sheet (T-8) and resin plate (P-12) were adjusted.

Example 13

In Example 10, acetyl silicone resin solution ZEMRAC YC3623 (Kanebuchi Chemical Co., Ltd.) was replaced with ethyl acetate Zs—butanol / ethanol = 2 2 Transfer sheet with primer layer (T-9), resin in the same manner except that Acryl silicone resin solution Zemurac YC3315 (Kanebuchi Chemical Co., Ltd.) whose solid content concentration was adjusted to 1% in step 6 was used. The plate (P-13) was adjusted.

Example 14

 In Example 10, acryl was prepared by adjusting the solid content concentration to 1% with ethyl acetate s-butanol Z ethanol = 2 to 2 in place of acrylacrylic resin solution ZEMRAC YC 3623 (manufactured by Kaneguchi Chemical Co., Ltd.). A transfer sheet with a primer layer (T-10) and a resin plate (P-14) were prepared in the same manner except that a silicone resin solution ZEMRAC YC5920 (manufactured by Kaneka Chemical Co., Ltd.) was used.

Example 15

 In the same manner as in Example 3, a PET film (B-1) with a photocatalyst layer and an inorganic layer was prepared. Further, the surface is coated with acryl silicone resin solution ZEMRAC YC 3623 (manufactured by Kane-buchi Chemical Co., Ltd.) using a bar coater so that the film thickness becomes 0.

After drying at 120 ° C, a transfer sheet (T-111) was prepared.

Then, the acrylic resin plate surface as a transfer object, the transfer sheet (T - 1 1) a lap, laminated with a 5 k pressure GZC m ² at 180 ° C, by peeling the base sheet, An acrylic resin plate (P-15) with a photocatalyst layer on the outermost surface was prepared.

Comparative Example 1

On a 25 / m-thick polyethylene terephthalate film (Toyobo E5001) with no surface treatment, Ishihara Sangyo Photocatalyst Powder ST-01 is dispersed in ethanol, and then ball-milled to obtain a solid content of 2%. A coating solution having good dispersibility was prepared, and this solution was coated with a bar coater to a thickness of 0.5 / m, and dried at 120 ° C to form a PET film with a photocatalytic layer. A transfer sheet (T-12) was prepared under the same conditions as in 1. Then, the acrylic resin plate surface as a transferred object, overlapping the transfer sheet (T one 12), and laminating over preparative at 5 kg / cm ² of pressure at 180 ° C, by peeling the base sheet Then, an acrylic resin plate (P-16) with a photocatalyst layer on the outermost surface was prepared.

Comparative Example 2 L, a siloxane cross-linkable resin, is coated with an acrylic resin-based transparent ink manufactured by Showa Ink Co., Ltd. as a coating liquid for the adhesive layer (A-1) to a thickness of 5 m on the film, and then dried at 60 ° C. Then, a transfer sheet (T-1 13) was created.

Next, the above-mentioned transfer sheet (T-13) is laminated on the surface of the acrylic resin plate as the transfer object, laminated at 180 ° C under a pressure of 5 kg / cm ² , and the base sheet is peeled off. Then, an acryl resin plate (P-17) having a photocatalyst layer on the outermost surface was prepared.

 [Evaluation method of Examples]

 The characteristics of the test plates (P-1) to (P-17) obtained in the examples were evaluated by the following methods.

 1) Adhesion evaluation

 The adhesiveness was evaluated by a cross-cut tape test specified in JIS K5400. The interval between cuts was 2 mm, and the number of squares was 25. The evaluation score was based on the criteria described in JIS K5400.

 2) Total light transmittance and haze rate

 It was measured with a haze meter (Nippon Denshoku Industries NDH-300A type). The total light transmittance was 80% or more and the haze rate was 3% or less.

 3) Durability evaluation

After irradiating with a black light a light having an ultraviolet intensity of 3 mWZ cm ² for 500 hours, the adhesion was measured by a grid tape method specified in JISK 5400, and the durability was evaluated. The evaluation score is the same as for the adhesiveness evaluation.

 4) Salad oil decomposition activity (antifouling property)

Apply a commercially available salad oil (manufactured by Nisshin Seimitsu Oil Co., Ltd.) on the surface of a sample cut into 5 cm x 5 cm squares or a sample cut so that the photocatalyst application area is approximately 25 cm2 using tissue paper. the amount coated was adjusted to be O.LmgZcm ² sample, the distance between the sample to 15 W black light ultraviolet ray intensity table by arranging one fluorescent lamp three UV-a region is 3 mWZ cm ² The light was adjusted and irradiated, and the weight change during irradiation was weighed and recorded on a precision balance capable of measuring up to 0.1 mg. The evaluation was made based on the residual weight of the applied salad oil after 72 hours. The evaluation criteria are as follows Was.

 Evaluation of salad oil residual rate after 72 hours light irradiation

 10% or less A

 30 ~: L 0% B

 50-30% C

 80-50% D

 80% or more E

 5) hydrophilic

After washing the photocatalyst layer on the sample surface with ethanol, it was dried at 60 ° C for 30 minutes to obtain a hydrophilicity measurement sample. After irradiating the sample with light having an ultraviolet intensity of 2 mWZ cm ² for 24 hours using black light, the contact angle of the surface with distilled water was measured with a contact angle measuring instrument (Elma 360 S type). The evaluation criteria for hydrophilicity were as follows.

 Evaluation of water contact angle after 24 hours light irradiation

 5 ° or less A

 5 0 B

10-30 ^C C

30 ° or more D

Table 1

 * 1: Total light transmittance of acryl resin plate: 93%, haze ratio: 0.3%

 * 2: Cannot be measured due to milky white color. As shown in Table 1, the samples (P-1) to (P_15) of the examples had good appearance, very high total light transmittance, and haze (low haze). A plate with no gaps is obtained. The adhesion of the membrane was satisfactory without any problem at the initial stage and after the durability test, and the photocatalytic activity (decomposition and hydrophilicity of salad oil) was very high.

 On the other hand, in Comparative Example 1, since the metal oxide gel or metal hydroxide gel was not contained in the photocatalyst layer, the transfer was incomplete and the appearance was impaired, as well as the adhesiveness and durability. Only those with poor properties and poor photocatalytic activity were obtained. In Comparative Example 2, since a normal transfer resin was used for the adhesive layer, the resin was decomposed by the photooxidation action of the photocatalyst, and the film was peeled off in the durability test.

 Example 16

A photocatalyst core in which photocatalyst particles are dispersed in silica sol on a 25 / m-thick polyethylene terephthalate film (Toyobo E5001) with no surface treatment Apply a coating solution X (Nippon Soda's bistreiter NDC-130 C: solids concentration 8%) with a mouth coater at a rate of 2 OmZ to a film thickness of 0.3 m at 120 ° C. After drying, a PET film with a photocatalyst layer (A-3) was prepared. Furthermore, a polysiloxane-added siloxane-crosslinked acryl resin solution Y (Nippon Soda's bistreiter -NRC-300A: solid content concentration 10%) was coated at a rate of 2 OmZ using a roll coater to a film thickness of 3 μπι. After drying at 120 ° C, a transfer sheet (T_13) was prepared. Next, the molten polycarbonate is extruded from a die on a transfer sheet (Τ-13), rapidly cooled by a cooling roll, and the base sheet is peeled off. P-18) was created.

 Example 17

 Extruded and laminated with molten polyethylene sandwiched between an acrylic resin film (Sanjuren 004 ΑΤ 鐘, thickness 50 ^ m, manufactured by Kanegabuchi Chemical Co., Ltd., thickness 50 ^ m) and the transfer sheet prepared in Example 16, and peeled the transfer sheet base material. As a result, an acrylic resin film (P-19) having a photocatalyst layer on the outermost surface was prepared.

 Example 18

 In the step of forming the polystyrene into a film using the T-die method and the chill roll method, the transfer sheet (T_13) prepared in Example 16 was laminated on a cooling roll, and the transfer sheet was subjected to the cooling step together with the polystyrene resin. By peeling off the base material, a polystyrene film (20-20) having the photocatalyst layer on the outermost surface was created.

 The characteristics of the test plates (Ρ-18) to (Ρ-20) obtained in Examples 16 to 18 were evaluated by the method described above, and the results are shown in Table 2. Table 2

* 1: Raw material acrylic film total light transmittance 93%, haze ratio 0.6% As shown in Table 2, Examples 16 to 18 had good appearance. In Examples 16 and 17, a photocatalyst-containing acryl film having very high total light transmittance and no haze (low haze ratio) was obtained without impairing the transparency of the acrylic film at all. The adhesion of the membrane has no problem at the initial stage and after the durability test, and a very high photocatalytic activity (decomposition and hydrophilicity of salad oil) has been obtained. Industrial applicability:

 As described above, the photocatalyst layer is firmly adhered to the object to be transferred by using the siloxane cross-linkable resin containing 0.5 to 60% by weight of silicon as silicon dioxide in the adhesive layer. In addition, the strong photooxidation effect of the photocatalyst does not impair its adhesiveness, and in the long term, antibacterial, deodorant, release of harmful substances by photocatalyst, antifouling, antifogging, drip, etc. Function can be maintained. Further, a structure having a similar function can be obtained by transfer without using the above-mentioned adhesive layer and using a resin having specific properties.

 Further, according to the method of the present invention, even plates, sheets, and films having no solvent resistance or heat resistance that cannot directly coat the photocatalyst layer have a problem in surface smoothness. A good photocatalytic layer can be adhered to a plate, sheet, or film whose appearance will be impaired if coated with a photocatalytic layer. Films that can maintain the functions of antibacterial, deodorant, decompose and remove harmful substances, antifouling, antifogging, and drip by photocatalyst for a long time without damage It can be manufactured continuously.

Claims

The scope of the claims  1. In a transfer film or sheet in which a photocatalyst layer and an adhesive layer are provided in this order on the surface of a film or sheet substrate, the adhesive layer contains 0.5 to 60% by weight of silicone in terms of silicon dioxide. A transfer film or sheet comprising a siloxane cross-linkable resin. 2. In a transfer sheet in which a photocatalyst layer, an inorganic layer and an adhesive layer are provided in this order on the surface of a film or sheet substrate, the adhesive layer has a silicon dioxide content of 0.5 to 60% by weight in terms of silicon dioxide. A transfer film or sheet comprising a siloxane cross-linkable resin containing a resin. 3. The transfer film or sheet according to claim 1, wherein the adhesive layer is made of a siloxane-crosslinked resin containing 20 to 40% by weight of silicone in terms of silicon dioxide. 4. The transfer film or sheet according to any one of claims 1 to 3, wherein a primer layer is provided on the adhesive layer. 5. The transfer film or sheet according to claim 4, wherein the thickness of the primer layer is in the range of 0.05 to 5 μπι. 6. The transfer film or sheet according to claim 4, wherein the primer layer is made of a resin having a number average molecular weight of not less than 200,000. 7. The primer layer according to claim 4 or 5, wherein the primer layer is made of a resin having a number average molecular weight of not more than 200,000 and a glass transition point of 110 to 100 ° C. Transfer film or sheet as noted. 8. Make sure that the resin is acrylic silicone resin or epoxy silicone resin 8. The transfer film or sheet according to claim 6, wherein the transfer film or sheet is a sheet. 9. Silicone is formula (I) S i C 1 n! (OH) n ^ ¹ n ₃ (OR ² ) n ₄ … (I) [Wherein, R ¹ represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group, or a chlorine atom), and R ² represents an alkyl group having 1 to 8 carbon atoms. Represents an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group, represents an integer of 0 to 2, n ₄ is an integer of 2 to 4, and 1 ^ + 112 + 113 + 114 = Represents an integer of 4. 9. The transfer film or sheet according to claim 1, which is a polysiloxane which is a polycondensation reaction product of the compound represented by the formula: 10. The transfer film or sheet according to any one of claims 1 to 9, wherein the resin part of the siloxane cross-linkable resin of the adhesive layer is acryl resin, epoxy resin, acrylic silicone resin, or epoxy silicone resin. One. 11. A photocatalytic layer, an inorganic layer, a resin having a number average molecular weight of 20,000 or more and / or a number average molecular weight of 20,000 or less, and a glass transition point of 1 to 100 A transfer film or sheet, wherein layers made of a resin at a temperature of ° C are provided in this order. 12. The transfer film or sheet according to claim 11, wherein the resin is an acrylic silicon resin or an epoxy silicon resin. 13. When the inorganic layer has the formula (II) R _n S i (OR,) ₄ — _n … (II) (Wherein, R represents an alkyl group which may have a substituent having 1 to 4 carbon atoms, and R! Is an alkyl group which may have a substituent having 1 to 5 carbon atoms or 1 carbon atom. Represents an optionally substituted acyl group, and n represents 0 or 1. The transfer film or sheet according to any one of claims 2 to 12, wherein the transfer film or sheet is an inorganic coating film containing an organoalkoxysilane or a hydrolysis-condensation product of an alkoxysilane as a main component. 14. The photocatalyst layer is a photocatalyst particle composite containing 25 to 95% by weight of a metal oxide gel and Z or a metal hydroxide gel. A transfer film or sheet according to any of the above. 15. The metal oxide gel and / or metal hydroxide gel in the photocatalytic layer is one or two selected from silicon, aluminum, titanium, zirconium, magnesium, diobium, tantalum, tungsten, and tin. 15. The transfer film or sheet according to claim 14, wherein the transfer film or sheet is a metal oxide gel or a metal hydroxide gel. 16. The transfer film or sheet according to any one of claims 1 to 15, wherein the thickness of the photocatalyst layer is 1 m or less. 17. The transfer film or sheet according to any one of claims 2 to 16, wherein the total thickness of the inorganic layer and the photocatalyst layer is 1 µπι or less. 18. The transfer film or sheet according to any one of claims 1 to 1, wherein a release layer is provided between the base material and the photocatalyst layer. 19. The step of preparing the transfer film or sheet according to any one of claims 1 to 18, the step of pressing the adhesive layer surface of the transfer film or sheet against the surface of the transfer object, and the step of preparing the transfer film or sheet. A method for transferring a photocatalyst layer, comprising a step of peeling a substrate in a single step. 20. Press the adhesive layer surface of the transfer film or sheet against the transfer target surface 10. The method for transferring a photocatalyst layer according to claim 19, wherein the step is a step of pressing the adhesive layer surface of the transfer film or the sheet while applying heat to the surface of the transfer object. 21. The method according to claim 19, wherein a cross-linking reaction of the siloxane cross-linkable resin of the adhesive layer proceeds during the step of pressing the adhesive layer surface of the transfer film or sheet against the surface of the transfer object. Transfer method of the photocatalyst layer. 22. The method for transferring a photocatalyst layer according to any one of claims 19 to 21, wherein the shape of the transfer target is a plate, a sheet, or a film. 2 3. In the molded article provided with the photocatalyst layer obtained by the method according to any one of claims 19 to 22, after irradiating light having an ultraviolet intensity of 3 mWZ cm ² for 500 hours, JISK 540 A molded article provided with a photocatalyst layer, wherein the adhesiveness of the photocatalyst layer according to the crosscut tape method specified in 0 is 6 or more. 2 4. A molded article provided with the photocatalyst layer obtained by the method according to any one of claims 19 to 22, wherein the photocatalyst layer and the adhesive layer or the photocatalyst layer and the inorganic layer with respect to light having a wavelength of 550 nm are provided. A molded article provided with a photocatalyst layer, characterized in that the total light transmittance of the total of the adhesive layer and the adhesive layer is 70% or more. 25. A method for producing a resin structure having a photocatalyst layer, wherein a resin melted on a transfer film or sheet having a photocatalyst layer is extruded and continuously produced. 2 6. A method for producing a resin structure having a photocatalyst layer, comprising extruding and laminating a molten resin between a transfer film or sheet having a photocatalyst layer and a substrate to be transferred, and continuously producing the resin. 2 7. A resin structure having a photocatalyst layer characterized by being continuously manufactured by pressing a transfer film or sheet having a photocatalyst layer during the step of cooling the melt-extruded resin on a cooling roll. Manufacturing method. 28. The transfer film or sheet having a photocatalyst layer is the transfer film or sheet according to any one of claims 1 to 18, wherein the transfer film or sheet is the transfer film or the sheet according to any one of claims 1 to 18. A method for producing a resin structure having a photocatalyst layer. 29. The production of a resin having a photocatalyst layer according to any one of claims 25 to 28, wherein the resin of the resin structure is a polycarbonate resin, an acrylic resin, a polyvinyl chloride resin, or a polystyrene resin. Method. 30. The method for producing a resin structure having a photocatalyst layer according to any one of claims 25 to 29, wherein the resin of the resin structure has a plate shape, a sheet shape, or a film shape. .