TW201529311A - Laminated body, protection film, and optical lens - Google Patents

Abstract

The present invention provides a laminated body, in which a cured resin layer is formed on a substrate. The cured resin layer shows antimicrobial properties with less additions, and maintains conventional optical properties. For example, a resin composition is coated on two faces or a single face of a substrate, so that a cured resin layer (d) is formed by curing the resin composition. The resin composition includes an antimicrobial compound (a) containing a silver ion, an inorganic oxide microparticle (b) such as silica, and a curable resin (c) which can be cured by heat or light. The laminated body obtained as mentioned above can be suitably used in a protection film such as a touch panel surface, or various types of optical lenses.

Description

Resin composition and laminate

The present invention relates to a laminated body formed with a cured resin layer which is coated with a resin composition containing an antibacterial compound, inorganic fine particles, and a curable resin on one or both sides of a substrate. , to make it hardened and get.

In recent years, it has been used not only for products related to food or daily life, but also for protection of display screens such as membrane switches, microwave ovens, washing machines, and the like, and touch panel displays. The antibacterial property of a member such as a film or a shatter-proof film such as a shatter-proof film is not high.

The conventional antibacterial film is formed into a film shape by uniformly mixing an antibacterial agent into a resin (Patent Document 1), and thus does not exhibit stable antibacterial properties.

Further, in applications that are not used by a large number of people, scratch resistance and abrasion resistance for maintaining the appearance of the product are required. In general, a hard coat film having an antibacterial property is formed by adding an antibacterial agent to the resin by the scratch resistance of the photocurable resin (Patent Document 2).

Among them, about 0.1% to 30% of an antibacterial agent is added to the hard coating films. The hard coating film is required to have transparency or color-equal optical properties, so the antibacterial agent used is used. Ultrafine inorganic antibacterial agent. The "ultra-fine particle inorganic antibacterial agent" is an ultrafine particle which retains a metal complex which exhibits an antibacterial property in a central metal, and is a fine and uniform particle having an average particle diameter of 1.0 μm or less, and has an advantage of being difficult to discolor. . However, it is very expensive. If it is cost-effective, it is preferable to exhibit antibacterial property with a smaller addition amount; and from the viewpoint of suppressing coloration by adding an antibacterial agent, it is also possible to suppress the addition amount of the antibacterial agent. Good research on maintaining antibacterial effects.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Utility Model Kaiping 7-9952

[Patent Document 2] Japanese Patent No. 3577145

The present invention provides a laminate in which a cured resin layer is formed on a substrate, the cured resin layer exhibiting antibacterial properties in a smaller amount of addition, and maintaining the existing optical characteristics.

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, it has been found that the inorganic fine particles are mixed in the curable resin containing the antibacterial compound, whereby the antibacterial property can be improved, and the present invention has been completed. That is, the present invention has the following constitution.

[1] A laminate which is a laminate including a hardened resin layer (d), The cured resin layer (d) is a resin composition containing an antibacterial compound (a), inorganic oxide fine particles (b), and a curable resin (c) applied to two sides or one side of a substrate. The compound (a) having an antibacterial property is an inorganic fine particle containing at least one metal ion selected from the group consisting of gold, silver, copper, tin, zinc, and platinum, and the mixing ratio thereof is The inorganic oxide fine particles (b) have a thickness of 0.01 μm in a total amount of 0.01 parts by weight or more and less than 0.04 parts by weight based on the total of the antibacterial compound (a), the inorganic oxide fine particles (b), and the curable resin (c). The average particle diameter of -1.0 μm is 5 parts by weight to 50 parts by weight based on the total of the antibacterial compound (a), the inorganic oxide fine particles (b), and the curable resin (c). The curable resin (c) is at least one selected from the group consisting of thermosetting resins and active energy ray-curable resins, and the thickness of the cured resin layer (d) is 0.1 μm to 20 μm.

[2] The laminate according to the above [1], wherein the compound (a) having an antibacterial property is an ultrafine inorganic antibacterial agent containing at least one metal complex, the metal complex The center metal is selected from any one selected from the group consisting of gold, silver, copper, tin, zinc, and platinum ions.

[3] The laminate according to the above [1], wherein the inorganic oxide fine particles (b) are selected from the group consisting of cerium oxide, aluminum oxide, zirconium oxide, zirconium silicate, At least one of rutile-type titanium oxide, tin oxide, antimony oxide, magnesium fluoride, and iron oxide is present in groups.

[4] A protective film according to any one of the above [1] to [3].

[5] An optical lens using the laminate according to any one of [1] to [3].

The laminated body of the present invention can increase the antibacterial property by increasing the concentration of the antibacterial agent on the surface by mixing the inorganic fine particles by using the excluded volume effect of the inorganic oxide fine particles, thereby increasing the antibacterial property, thereby reducing the antibacterial property. The amount of the compound having an antibacterial property.

Hereinafter, the laminated body of the present invention will be described.

<Structure of laminated body>

The laminate obtained in the present invention comprises a cured resin layer (d) and a substrate supporting the same, and the cured resin layer (d) is made to contain an antibacterial compound (a) and inorganic oxide fine particles (b). And the resin composition of the curable resin (c) is hardened. Specifically, a two-layer structure in which the cured resin layer (d) is present on one surface of the substrate or a three-layer structure in which the cured resin layer (d) is present on both surfaces of the substrate can be exemplified.

<Antibacterial compound (a)>

Examples of the antibacterial compound include an organic antibacterial agent or an inorganic antibacterial agent. The antibacterial compound can be used as it is, or it can be dispersed (diluted) in a solvent to prepare a dispersion (dilution) solution. One type of the organic antibacterial agent or the inorganic antibacterial agent may be used alone or two or more types may be used in combination.

The amount of the antibacterial compound to be used is 0.01 by weight based on the total amount of the resin composition or the total of the antibacterial compound (a), the inorganic oxide fine particles (b), and the curable resin (c). The amount is not more than 0.04 parts by weight, more preferably 0.015 parts by weight or more and 0.025 parts by weight or less.

The organic antibacterial agent is halogen, phenol, imidazole, thiazole, guanidine, pyridine, organic arsenic, guanamine or amine based metal surfactant, specifically "microbial sterilization. "Bactericidal, anti-mildew technology" (Sanitary Technology Association), "Antibacterial and Mildew Prevention Handbook" (Japan Antimicrobial Society), "Antibacterial and Antifungal Agent Dictionary" (Japan Antimicrobial Society), etc.

The inorganic antibacterial agent may be an antibacterial solid particle (inorganic fine particle) containing at least one metal ion such as gold, silver, copper, tin, zinc or platinum supported on zeolite, hydroxyapatite or calcium phosphate, or may be retained. An ultrafine inorganic antibacterial agent or the like which is a metal complex of the metal ion as a central metal.

The antibacterial solid particles are metal ions such as gold, silver, copper, zinc or platinum which are antibacterial in the zeolite, hydroxyapatite or calcium phosphate. Zeolite is a kind of crystalline aluminosilicate containing aluminum, lanthanum, alkali metal, and contains a crystal structure having pores.

Specific products can be cited as zeomic (manufactured by Pinshen Jiemei Co., Ltd.), SP-200 (manufactured by SANGI Co., Ltd.), SP-1 (manufactured by SANGI Co., Ltd.), Apacider AK (manufactured by SANGI Co., Ltd.), Apacider AW (manufactured by SANGI Co., Ltd.), Apacider Z (manufactured by SANGI Co., Ltd.), PBM-OJ (manufactured by Pacific Beam MOLD Co., Ltd.) ), PBM-OJ Plus (manufactured by Pacific Beam MOLD), and the like.

The ultrafine inorganic antibacterial agent is a structure in which a metal ion such as gold, silver, copper, zinc or platinum having antibacterial property is strongly bonded to an inorganic ion exchanger, and the average particle diameter is 0.5 μm or less. Fine and uniform particles. The ultrafine inorganic antibacterial agent is difficult to discolor, and therefore it is preferably used in an optical film application in which unnecessary coloring is not desired. In particular, in consideration of the influence on the human body, the metal ion is preferably silver.

Specific examples of the product include CS-100 (manufactured by Sumitomo Osaka Cement Co., Ltd.), tribolite (manufactured by Kanae Paint Co., Ltd.), RASPA (manufactured by RASA Industries, Ltd.), and the like.

<Inorganic oxide fine particles (b)>

Specific examples of the inorganic oxide fine particles contained in the resin composition include alumina (alumina), cerium oxide (cerium oxide), zirconium silicate, rutile-type titanium oxide, tin oxide, zirconium oxide, and oxidation. Antimony, magnesium fluoride, iron oxide, zinc oxide, copper oxide, antimony oxide, cryolite, fluorite, apatite, calcite, gypsum and talc. Preferred are cerium oxide, aluminum oxide, zirconium oxide, zirconium silicate, rutile titanium oxide, tin oxide, cerium oxide, magnesium fluoride and iron oxide, and more preferably inexpensive aluminum oxide or cerium oxide. These may be used alone or in combination of two or more. The amount of the inorganic oxide fine particles to be used is a total of the resin composition, and the mixing ratio thereof is based on the total of the antibacterial compound (a), the inorganic oxide fine particles (b), and the curable resin (c). In the case of 5 parts by weight or more and 50 parts by weight or less, in order to maintain good adhesion to the substrate, it is preferably less than 50 parts by weight.

Further, the inorganic oxide fine particles have an average particle diameter of 0.01 μm to 1.0 μm, and preferably have a transparency of the coating film of 0.01 μm to 0.04 μm. Further, in order to impart a design of a dark light hue on the surface of the coating film, it is preferably 0.05 μm to 1.0 μm. Further, in the present application, the average particle diameter of the inorganic fine particles was measured by a dynamic light scattering method using MICROTRAC UPA manufactured by Nikkiso Co., Ltd. It is of course also possible to use the average particle size information provided by the material manufacturer, and a slight difference in the particle size value should be allowed as a mechanical difference.

<Curable resin (c) and resin composition>

The curable resin is at least one selected from the group consisting of a thermosetting resin group and an active energy ray curable resin.

In addition, the "resin composition" in the present invention includes a composition of the antibacterial compound (a), the inorganic oxide fine particles (b), and the curable resin (c), and further adds various additives described later. Composition. That is, it is synonymous with the composition to be applied to the substrate.

Examples of the thermosetting resin or the active energy ray-curable resin include a (meth) acrylate monomer, an unsaturated polyester resin, a polyester (meth) acrylate resin, an epoxy (meth) acrylate resin, and an amine group. A resin having a radical polymerizable unsaturated bond such as a formic acid (meth) acrylate resin. These resins may be used singly or in combination of a plurality of resins.

The (meth) acrylate monomer may, for example, be a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid. For example, polyalkylene glycol di(meth)acrylate, ethylene glycol (meth)acrylate, propylene glycol (meth)acrylate, polyethylene polytrim Hydroxymethylpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy Tris(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxy Tris(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(methyl) Acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylate having a cyclic structure, and the like. Specific examples of the (meth) acrylate having a cyclic structure include dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. Ethyl ester, isobornyl (meth)acrylate, tricyclodecanediyl dimethacrylate, mono(meth)acrylate having a terpene skeleton, and di(meth)acrylic acid An ester or a photopolymerizable monomer such as (meth) acrylate which is modified by ethylene glycol or propylene glycol.

The unsaturated polyester resin may be one obtained by dissolving a condensation product (unsaturated polyester) of an esterification reaction of a polyhydric alcohol with an unsaturated polybasic acid (and optionally a saturated polybasic acid) in a polymerizable monomer.

The unsaturated polyester can be produced by polycondensing an unsaturated acid such as maleic anhydride with a diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid or itaconic acid or an acid anhydride thereof is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, or the like. 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl -1,3-propanediol, A polyol such as cyclohexane-1,4-dimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A is reacted as an alcohol component, and phthalic acid is added as needed. A polybasic acid having no polymerizable unsaturated bond such as formic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid or sebacic acid or an acid anhydride thereof is produced as an acid component.

The polyester (meth) acrylate resin may, for example, be (1) a polyester having a terminal carboxyl group obtained by a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol, and an α,β-unsaturated carboxylic acid. The (meth) acrylate obtained by reacting an epoxy compound of an ester group, (2) reacting a polyester having a terminal carboxyl group obtained by a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol with a hydroxy group-containing acrylate And the obtained (meth) acrylate, (3) (meth) obtained by reacting a polyester having a terminal hydroxyl group obtained by a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol with (meth)acrylic acid Acrylate.

Examples of the saturated polybasic acid used as a raw material of the polyester (meth) acrylate include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, and the like. A polybasic acid or an anhydride thereof having no polymerizable unsaturated bond and a polymerizable unsaturated polybasic acid such as fumaric acid, maleic acid or itaconic acid or an anhydride thereof. Further, the polyol component is the same as the unsaturated polyester.

The epoxy (meth) acrylate resin is produced by ring-opening reaction of a carboxyl group having a glycidyl group (epoxy group) with a carboxyl group of a carboxyl group compound having a polymerizable unsaturated bond such as acrylic acid. The compound (vinyl ester) of a polymerizable unsaturated bond is dissolved in a polymerizable monomer.

The vinyl ester is manufactured by a known method, and the epoxy resin is not An epoxy (meth) acrylate obtained by reacting a saturated monobasic acid such as acrylic acid or methacrylic acid.

Moreover, various epoxy resins can also be reacted with dibasic acids such as bisphenol (for example, type A) or adipic acid, sebacic acid, dimer acid (HARIDIMER 270S; Harima Chemical Co., Ltd.). Give flexibility.

Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether, a high molecular weight homolog thereof, and a novolak type glycidyl ether.

The (meth)acrylic acid urethane resin may, for example, be an oligomer containing a radical polymerizable unsaturated group which can be obtained by reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol. Further, it is allowed to react with a hydroxy (meth) acrylate-containing compound and, if necessary, a hydroxyl group-containing allyl ether compound.

Specific examples of the polyisocyanate include 2,4-toluene diisocyanate and isomers thereof, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, Xylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Burnock D-750 (trade name; manufactured by Di Aisheng Co., Ltd.), CRISVON NK (trade name; Di Aisheng Co., Ltd.) Manufactured), Desmodur L (trade name; manufactured by Sumitomo Bayeramide Co., Ltd.), CORONATE L (trade name; manufactured by Japan Polyurethane Co., Ltd.), Takenate D102 (trade name; Mitsui Takeda Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation).

The polyhydroxy compound may, for example, be a polyester polyol or a polyether polyol, and specific examples thereof include a glycerol-ethylene oxide adduct, a glycerol-propylene oxide adduct, and glycerin- Tetrahydrofuran adduct, glycerol-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trihydroxyl Methylpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol a tetrahydrofuran adduct, a dipentaerythritol-ethylene oxide-propylene oxide adduct, or the like.

Specific examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1 , 3-butanediol, an adduct of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerol, trimethylolpropane, 1,3 -butanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, p-xylene glycol, dicyclohexyl-4,4-diol, 2,6-Decahydronaphthalenediol, 2,7-decahydronaphthalenediol, and the like.

The hydroxyl group-containing (meth)acrylic group-containing compound is not particularly limited, and a hydroxyl group-containing (meth) acrylate is preferable, and specific examples thereof include 2-hydroxyethyl (meth)acrylate and (a) 2-hydroxypropyl acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris(hydroxyethyl) Di(meth) acrylate of isocyanuric acid, pentaerythritol tri(meth) acrylate, and the like.

In the case of using an active energy ray-curable resin, a hardener may be added as needed. In this case, the content of the hardener is preferably from 0.1 part by weight to 10 parts by weight, more preferably from 0.1 part by weight to 5 parts by weight, based on the total amount of the active energy ray-curable resin composition. Particularly preferred is 0.1 part by weight to 4 parts by weight. The hardener can utilize an active energy ray polymerization initiator (photopolymerization initiator). The active energy ray polymerization initiator is not particularly limited as long as it can generate a radical by irradiation with an active energy ray such as ultraviolet rays or visible light. The compounds used as active energy ray polymerization initiators are benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone (Xanthone). ), thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylhydrazine, acetophenone, 2-hydroxy-2-methylpropiophenone, 2 -hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzoxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, ethyl 1,4-dimethylaminobenzoate, 4-di Isoamyl methylaminobenzoate, 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(t-butylperoxycarbonyl) Benzophenone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)- Triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'- Methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)- Homotriazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-di(ethoxycarbonyl) Methyl)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1, 3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(pair two Methylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4, 4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxy Phenylcarbonyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 ,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionate Carbazole, 3,6-bis(2-methyl-2-morpholinopropanyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone Bis (η ⁵ -2,4- cyclopentadien-1-yl) - bis (2,6-difluoro-3- (lH-pyrrol-1-yl) - phenyl) titanium. These compounds can be used singly or in combination of two or more. Of these, preferred are 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(trihexylperoxycarbonyl) Benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxy Carbonyl)-4,3'-bis(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-di(t-butylperoxy Carbocarbonyl) benzophenone and the like.

The thermosetting resin or the active energy ray-curable resin is preferably a curable resin such as an epoxy group-containing resin, and is preferably a carboxylic acid, an amine, an acid anhydride compound or an acid generator, preferably as a release liberator. A resin which is hardened by a double salt of a cerium salt of a sulphuric acid or a derivative thereof. These resins may be used singly or in combination of a plurality of resins.

Examples of the epoxy resin include bisphenol A, bisphenol F, hydroquinone, resorcin, dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)dicyclopentan Alkane, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3-methylbenzene Ether, bis(3,5-dimethyl-4-hydroxyphenyl)ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxy-3-methylphenyl) sulfide, double (3,5-Dimethyl-4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)fluorene, bis(4-hydroxy-3-methylphenyl)fluorene, bis(3,5-di Methyl-4-hydroxyphenyl)indole, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1, 1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxybiphenyl-3,3',5,5'-tetramethylbiphenyl, bis ( Epoxy resin such as hydroxynaphthyl)methane and 1,1'-binaphthol, 1,1'-bis(3-tert-butyl-6-methyl-4-hydroxyphenyl)butane .

Further, examples of the epoxy resin to be formed include a phenol novolak-based epoxy resin which is a glycidyl ether compound of a reaction product of a phenol such as phenol, o-cresol or catechol, or an aldehyde such as formaldehyde; a polyglycidyl ether containing a polyphenol of a trityl skeleton obtained by condensing a phenol such as phenol, cresol or methyl-tert-butylphenol with an aromatic aldehyde such as hydroxybenzaldehyde; a polyglycidyl ether of a polyphenolic novolak containing a trimethyl skeleton as a reaction product of a polyphenol and a formaldehyde in a trityl skeleton; a phenol such as phenol, o-cresol or catechol; a polyglycidyl ether of polyepylene phenol resin which is a reaction product of chloromethylbenzene or (hydroxymethyl)benzene; a phenol such as phenol, o-cresol or catechol, or a hydroxynaphthalene or a phenol An alicyclic hydrocarbon-containing polyphenol resin type epoxy resin or a polynaphthol resin type ring containing a glycidyl ether of a reaction product of a naphthol such as hydroxynaphthalene with an unsaturated alicyclic hydrocarbon such as dicyclopentadiene or limonene Oxygen resin; as a polyphenol resin or polynaphthol containing an alicyclic hydrocarbon Lipids with formaldehyde class a polyphenol novolak resin containing an alicyclic hydrogen or a polyglycidyl ether of a poly naphthol novolak resin; a glycidyl ether of a polyphenol obtained by a condensation reaction of a phenol with an aromatic carbonyl compound a compound; fluoroglycine, tris(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 1,3-bis[(4-hydroxyphenyl) a polyglycidyl ether of a ternary or higher phenolic phenol having a basic skeleton such as methyl]benzene or 1,4-bis[(4-hydroxyphenyl)methyl]benzene; or a cyclic ring such as cup-resorcinol aromatic hydrocarbon a glycidyl ether compound derived from a phenol; etc.; from p-aminophenol, m-aminophenol, 4-amino m-cresol, 6-amino m-cresol, 4,4'-diaminodiphenylmethane , 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxyl) Benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy) Benzene, 2,2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-benzoic acid Amine, m-xylene diamine, 1 , an amine-based epoxy resin derived from 4-cyclohexane bis(methylamine), 1,3-cyclohexane bis(methylamine), N,N-diglycidylaniline or the like; from p-hydroxybenzoic acid a glycidyl ester compound derived from an aromatic carboxylic acid such as m-hydroxybenzoic acid, terephthalic acid or isophthalic acid; and a carbendazim system derived from 5,5-dimethylhydantoin or the like Epoxy compound; 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexane Alkene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane An alicyclic epoxy resin such as a carboxylate ester; an aliphatic epoxy resin obtained by oxidizing a double bond in an unsaturated hydrocarbon compound such as polybutadiene.

Moreover, the epoxy resin formed may also be an alicyclic epoxy resin. Specific examples thereof are an epoxy resin obtained from a polyglycidyl ether of a polyol having at least one alicyclic ring, or an epoxidation of a compound containing a cyclohexene or a cyclopentene ring by an oxidizing agent. The resulting compound containing epoxycyclohexane or epoxycyclopentane.

For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexyl group -3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate Acid ester, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexyl Methyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane -m-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinyl cyclohexene oxide, 4-vinyl epoxy cyclohexane, bis (3,4-epoxy) -6-Methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), bicyclo Pentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl)ether, ethyl bis(3,4-epoxycyclohexanecarboxylate), epoxy hexahydroortho Dioctyl phthalate, di-2-ethylhexyl hexahydrophthalate, 1,2:8,9 bisepoxide limonene (trade name: CEL3000, Daicel Chemical) Company), epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenyl) ester ε- caprolactone-modified (trade name: Epolead GT301, Daicel Chemical Co., Ltd.), epoxidized butane tetracarboxylic acid tetrakis-(3-cyclohexenylmethyl) ester modified ε-caprolactone (trade name: Epolead GT401, Daicel Chemical Co., Ltd.), 2 , 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2-bis(hydroxymethyl)-1-butanol (trade name: EHPE3150, Daicel Chemical Co., Ltd.) Company, 2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct and 3,4-epoxy a mixture of cyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate (trade name: EHPE3150CE, Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexyl methacrylate ( Trade name: Cyclomer A400, Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M100, Daicel Chemical Co., Ltd.), epoxidized polybutadiene ( Trade name: Epolead PB3600, Daicel Chemical Co., Ltd.), epoxy resin represented by epoxidized thermoplastic elastomer (trade name: EPOFRIEND, Daicel Chemical Co., Ltd.).

Further, examples of the epoxy resin include an epoxy resin obtained from a polyglycidyl ether of an aliphatic polyol or an alkylene oxide adduct thereof; an epoxy obtained from a polyglycidyl ester of an aliphatic long-chain polybasic acid a homopolymer synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate; by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate with other vinyl monomers Synthetic copolymers and the like.

Specific examples of the polyglycidyl ether include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerol, and trimethylolpropane. Glycidyl ether, tetraglycidyl ether of sorbitol, dipentaerythritol A glycidyl ether of a polyhydric alcohol such as hexahydroglyceryl ether, diglycidyl ether of polyethylene glycol or diglycidyl ether of polypropylene glycol.

Further, specific examples of the polyglycidyl ester include a polyether polyol obtained by adding one or two or more kinds of alkylene oxides to an aliphatic polyol such as propylene glycol, trimethylolpropane or glycerin. Glycidyl ether, diglycidyl ester of an aliphatic long chain dibasic acid.

Further, examples of the epoxy resin include: a mono-glycidyl ether derived from an aliphatic higher alcohol or phenol, cresol, butylphenol, or a polycondensate obtained by adding the alkylene oxide to the monocondensate Epoxy resin obtained by glycerol ether; epoxy resin obtained from glycidyl ester of higher fatty acid; epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized linseed oil, An epoxy resin obtained by epoxidizing polybutadiene or the like.

As described above, the polymer having a crosslinkable functional group used in the embodiment of the present invention can be used in combination with a monomer forming a matrix resin (for example, an epoxy resin) to use a hardening reaction initiator (for example, an acid generator). .

The curing reaction initiator is not limited, and may be a compound which can release a substance which initiates cationic polymerization by irradiation with an active energy ray or heat energy. Examples of the hardening reaction initiator include a carboxylic acid, an amine, an acid anhydride compound or an acid generator, and the like, and preferably a double salt or a derivative thereof which releases a phosphonium salt of Lewis acid.

Representative examples of the curing reaction initiator include a salt of a cation and an anion represented by the following formula.

[A] ^m+ [B] ^m-

In the above formula, the cation [A] ^{m+ is} preferably a cerium ion, and is represented, for example, by the following formula.

[(α) _a Q] ^m+

α is an organic group having a carbon number of 1 to 60 and may contain atoms other than a plurality of carbon atoms. a is an integer from 1 to 5. Each of a α may be the same or different independently. Moreover, it is preferred that at least one α is an organic group having an aromatic ring.

Q is an atom or an atom group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N.

Further, when the valence of Q in the cation [A] ^m+ is q, m = aq (where N = N is treated as valence 0).

On the other hand, the anion [B] ^{m- is} preferably a halide complex, and is represented, for example, by the following formula.

[LX _b ] ^m-

L is a metal or metalloid (Metalloid) which is a central atom of a halide complex, and is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr. , Mn, Co, etc. X is a halogen atom. b is an integer from 3 to 7.

Further, when the valence of L in the anion [B] ^m- is p, m = bp.

Specific examples of the anion [LX _b ] ^m- represented by the above formula include tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), hexafluoroantimonate (SbF ₆ ), and hexafluoroarsenic acid. Salt (AsF ₆ ), hexachloroantimonate (SbCl ₆ ), and the like.

Further, the anion [B] ^m- can also preferably be represented by the following formula. L, X, and b are the same as described above.

[LX _b-1 (OH)] ^m-

The anion [B] ^m- further includes perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , toluenesulfonic acid anion , trinitrobenzenesulfonic acid anion, and the like.

The hardening reaction initiator in the embodiment of the present invention is more preferably an aromatic onium salt exemplified in the following (A) to (C). One of them may be used alone or in combination of two or more.

(A) an aryldiazonium salt such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate or 4-methylphenyldiazonium hexafluorophosphate.

(B) Diaryl iodonium dichloride such as diphenylphosphonium hexafluoroantimonate, bis(4-methylphenyl)phosphonium hexafluorophosphate or bis(4-tert-butylphenyl)phosphonium hexafluorophosphate salt.

(C) triphenylsulfonium hexafluoroantimonate, tris(4-methoxyphenyl)phosphonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylphosphonium hexafluoroantimonate, two Phenyl-4-thiophenoxyphenylphosphonium hexafluorophosphate, 4,4'-bis(diphenyldihydrothio)phenyl sulfide-bis-hexafluoroantimonate, 4,4' - bis(diphenyldihydrothio)phenyl sulfide-bis-hexafluorophosphate, 4,4'-bis[bis(?-hydroxyethoxy)phenylindenyl]phenyl sulfide-double - hexafluoroantimonate, 4,4'-bis[bis(?-hydroxyethoxy)phenylindenyl]phenyl sulfide-bis-hexafluorophosphate, 4-[4'-(benzamide) Phenylthio]phenyl-bis-(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-[4'-(benzylidene)phenylthio]phenyl-di-(4 Trifluoro sulfonium salt such as -fluorophenyl)phosphonium hexafluorophosphate salt.

Further, the curing reaction initiator in the embodiment of the present invention is a mixture of an iron arene complex or an aluminum complex and a decyl alcohol such as triphenylstanol.

Examples of iron aromatic hydrocarbon complexes include (η ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl) Examples of the aluminum complex such as benzene]-iron-hexafluorophosphate include aluminum tris(acetonitrile), aluminum tris(ethylacetoacetate), aluminum tris(salicylic acid), and the like.

Among these, from the viewpoint of practical use, the curing reaction initiator in the embodiment of the present invention is preferably an aromatic onium salt, an aromatic onium salt, or an iron-aromatic hydrocarbon complex.

The content of the hardening reaction initiator (preferably the acid generator) is preferably 1 mole per 10 moles to 300 moles of the epoxy group contained in the epoxy resin.

The active energy ray-curable resin can be cured by irradiating ultraviolet rays (UV), electron beams, or the like with an active energy ray source.

As an example, a case where the active energy ray-curable resin is irradiated with ultraviolet rays will be described. The active energy ray-curable resin is preferably cured by irradiation with ultraviolet rays in the presence of a photopolymerization initiator. Examples of the photopolymerization initiator include various benzoin derivatives, benzophenone derivatives, phenylketone derivatives, sulfonium salt photoinitiators, organometallic photoinitiators, metal salt cationic photoinitiators, and photodecomposition. Organic decane, latent sulfonic acid, phosphine oxide, etc. The amount of the photopolymerization initiator to be added is preferably from 1 part by weight to 5 parts by weight per 100 parts by weight of the active energy ray-curable resin.

Further, examples of the thermosetting resin include resins such as a melamine resin, a urethane resin, and an epoxy resin. Specifically, examples of the melamine resin include an alkylated melamine resin such as a methylated melamine resin or a butylated melamine resin, a methylol type melamine resin, and an imide type melamine resin. Examples of the urethane resin include a polyether polyurethane resin, a polyester polyurethane resin, a polycarbonate polyurethane resin, and a polyester polycarbonate resin. Polyurethane resin and the like. Examples of the epoxy resin include a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, a polymer of a monomer having ethylene oxide, or a monomer having ethylene oxide. Copolymers of other monomers, and the like. These resins may be used singly or in combination of a plurality of resins.

The hardened resin layer preferably has low refractive index characteristics, high refractive index characteristics, antifouling properties, low abrasion characteristics, and gas barrier properties depending on the application. Additives for imparting the properties can also be used.

Examples of the ultraviolet absorber include benzotriazoles, hydroxyphenyltriazines, benzophenones, salicylates, cyanoacrylates, triazines, or benzhydryl resorcinol. Classes, etc. These ultraviolet absorbers may be used singly or in combination of a plurality of ultraviolet absorbers. The ultraviolet absorber is preferably selected in kind or in combination based on the wavelength of the ultraviolet light to be absorbed.

The antioxidant may, for example, be a monophenol (2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl) -β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, etc.), bisphenols (2,2'-methylenebis(4-methyl-6-third) Butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'- Thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1 -Dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy}ethyl]-2,4,8,10-tetraoxaspiro [5.5] undecane, etc.), polymeric phenols (1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5- Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di- Tributyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butanoic acid]diol, 1 ,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione, tocopherol Etc.), a sulfur-based antioxidant (dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3' - thiodipropionate, etc.), phosphites (triphenylphosphite, diphenylisodecyl phosphite, phenyl diisononyl phosphite, tris(nonylphenyl) sub Phosphate ester, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclopentaerythritol double (ten Octaalkyl) phosphite, cyclopentaerythritol (2,4-di-tert-butylphenyl) phosphite, cyclopentaerythritol (2,4-di-t-butyl- 4-methylphenyl) phosphite, bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, etc.) And oxaphosphorus phenanthrene oxides (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-) Hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphonium Phenanthrene-10-oxide, etc.). These antioxidants may be used singly, but particularly preferably in combination with a phenolic/sulfur or phenol/phosphorus system. Commercially available phenolic antioxidants can be used by using IRGANOX 1010 (trade name) or IRGAFOS 168 (trade name) manufactured by BASF Corporation, respectively, or they can be used in combination.

Examples of the light stabilizer (HALS) include: TINUVIN (registered trademark) 5100 (neutral type HALS) manufactured by BASF, and TINUVIN 292 (compound name: double (1, 2, 2, 6, 6-pentamethyl-4) -piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), TINUVIN 152 (Compound name: 2,4-double [ N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1, 3,5-triazine), TINUVIN 144 (Compound name: bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethyl) Benzyl)-4-hydroxyphenyl]methyl]butylmalonate), TINUVIN123 (Compound name: azelaic acid, bis(2,2,6,6-tetramethyl-1-(octyl) Reaction product of oxy)-4 piperidinyl ester (in the presence of 1,1-dimethylethyl hydroperoxide and octane), TINUVIN111FDL (about 50%, TINUVIN 622, compound name: (succinic acid) In the presence of a polymer (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-yl)ethanol, about 50%, CHIMASSORB119, compound name: N-N'-N"-N'' '-tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4, 7-diazanonane-1,10-diamine), or Aidico shares The Adekastab LA series manufactured by the company, etc., specifically LA-52 ((5)-6116), LA-57 ((5)-5555), LA-62 ((5)-5711), LA-67 ( (5)-5755) In addition, the existing chemical number is in parentheses.

Preferably, the method of imparting low refractive index characteristics is to mix inorganic fine particles such as magnesium fluoride in the hardened resin layer, or to select fluorine sesquivalent oxygen as described in fluorosesquioxanes, WO 2008/072766, and WO 2008/072765. One or more of a compound of the group consisting of an alkane polymer or an acrylate compound containing a fluorine atom.

The method of imparting high refractive index characteristics is preferably mixed in a hardened resin layer. One or more kinds of metal fine particles such as zirconium dioxide, titanium oxide, and zinc sulfide, or an acrylate compound having an anthracene skeleton, an epoxy compound, or an acrylate compound containing a sulfur atom, and an epoxy compound.

A transparent electrode material typified by ITO or a silver nanowire is coated on the cured resin layer having high refractive index characteristics, and patterned by etching, thereby being incorporated into the electrostatic capacitance type touch panel. Used in transparent electrode films. By using a hardened resin layer imparting high refractive index characteristics, a conductive pattern of a transparent electrode material such as ITO or silver nanowire can be made difficult to see.

Further, by laminating the layer having the low refractive index property on the cured resin layer imparting high refractive index characteristics, the first cured resin layer having antireflection properties can be obtained.

Preferably, the antifouling property or the low friction property is imparted by mixing the hardened resin layer with a fluorine half half selected from the group consisting of a ruthenium oxide compound, a fluorine compound, a fluorosilsesquioxane, WO 2008/072766, and WO 2008/072765. One or more compounds of the group consisting of a siloxane polymer.

Examples of the oxygen-containing compound include BYK-UV3500 and BYK-UV-3570 (all trade names; manufactured by BYK-Chemie Co., Ltd.), TEGO Rad 2100, 2200N, 2250, 2500, 2600, and 2700 (both are trade names; Degussa company, X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22- 1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201 X-22-2426, X-22-164A, X-22-164C (all are trade names; Shin-Etsu Chemical Co., Ltd. manufactures) and so on.

The fluorine compound can be exemplified by OPTOOL DAC, OPTOOL DAC-HP, R-1110, R-1210, R-1240, R-1620, R-1820, R-2020, R-5210, R- manufactured by Daikin Industries, Ltd. 5410, R-5610, R-5810, R-7210, R-7310, Megafac RS-75, Megafac RS-72-K, Megafac RS-76-E, Megafac RS-76-NS, Megafac RS-77, Megafac RS-903-3, Megafac RS-914-2, Megafac RS-761-3 (all trade names), and the like.

In the method of imparting a gas barrier property, it is preferable to mix one or more kinds of inorganic components such as layered clay represented by graphene or inorganic components such as cerium oxide, aluminum oxide, and porous glass in the cured resin layer.

In addition, active energy ray sensitizer, polymerization inhibitor, wax, plasticizer, leveling agent, surfactant, dispersant, antifoaming agent, wettability improver, antistatic agent, hardening may be mixed as needed. Various additives such as additives.

The concentration of the nonvolatile component in the resin composition can be adjusted to a viscosity corresponding to a lamination method such as a wet coating method, and can be appropriately selected. The concentration is, for example, preferably from 5% by weight to 80% by weight, more preferably from 10% by weight to 60% by weight. Examples of the solvent include a hydrocarbon solvent (benzene, toluene, etc.), an ether solvent (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), a halogenated hydrocarbon solvent (dichloromethane, chloroform, Chlorobenzene, etc.), ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvent (methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, etc.) , a nitrile solvent (acetonitrile, propionitrile, benzonitrile, etc.), an ester solvent (ethyl acetate, butyl acetate, etc.), a carbonate solvent (ethyl carbonate, propyl carbonate, etc.), hydrazine Amine solvent (N,N-dimethylformamide, N,N-dimethylacetamide), hydrochlorofluorocarbon solvent (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) Solvent (HFCs with carbon number 2 to 4, 5 or more), perfluorocarbon solvent (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvent (fluorocyclopentane, fluorine ring) Butane), a fluorine-containing solvent containing oxygen (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), an aromatic fluorine solvent (α, α, α-trifluorotoluene, hexafluorobenzene), water, and the like. These may be used alone or in combination of two or more. Further, since the curable resin composition can be used as a coating liquid, it is preferably liquid before curing.

<hardened resin layer (d)>

The cured resin layer contains a resin composition containing the antibacterial compound (a), the inorganic oxide fine particles (b), and the curable resin (c). The resin composition is applied onto a substrate to cure the resin composition to form a cured resin layer (d).

The substrate can be molded using various plastic materials or inorganic materials. Examples of the plastic material include a polyester resin, an acetate resin, a polyether oxime resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a polyolefin resin, and (methyl). Acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, cyclic polyolefin resin . Particularly preferred are polyethylene terephthalate (PET), polyethylene naphthalate, triethylene glycol, polyether oxime, polycarbonate, polyarylate, polyetheretherketone, ZEONOR (registered trademark), ZEONEX (registered trademark): manufactured by Japan ZEON, ARTON (registered trademark): JSR Manufactured by the company, APEL (registered trademark): manufactured by Mitsui Chemicals Co., Ltd., Topas (registered trademark): Polyolefins resin manufactured by Polyplastics Co., Ltd., etc. In addition, polyethylene terephthalate (PET) and polyethylene naphthalate have mechanical strength, dimensional stability, heat resistance, chemical resistance, optical properties, etc., and smoothness or handleability of the film surface. Excellent and better. Polycarbonate is more preferable because it is excellent in transparency, impact resistance, heat resistance, dimensional stability, and combustibility. The cyclic polyolefin resin is more preferable because of excellent optical properties such as high transparency and low birefringence, and high heat resistance and low water absorption. If the price and the ease of starting are also considered, polyethylene terephthalate (PET) is particularly preferred.

Examples of the inorganic material include transparent glass substrates such as white plate glass, blue plate glass, and ceria coated green plate glass; metal substrates such as aluminum plates, copper plates, nickel plates, and stainless steel plates; other ceramic plates, semiconductor substrates having photoelectric conversion elements, and tantalum; Wafers, etc.

The shape of the molded article is not particularly limited, and may be determined into a film shape, a plate shape, or the like depending on the application. Further, the molding method is not limited, and the substrate can be obtained by various molding methods such as injection molding, blow molding, and cutting.

It is preferred to use a wet coating method in which a resin composition is uniformly applied to the formation of the laminate. As the wet coating method, a gravure coating method, a die coating method, or the like can be used. In the gravure coating method, a gravure roll having an unevenly engraved surface is immersed in a coating liquid, and the coating liquid adhering to the convex and concave portions on the surface of the gravure roll is scraped off by a doctor blade to store the liquid in the concave portion, thereby accurately Measure the way it is transferred to the substrate. By the gravure coating method, a low viscosity liquid can be applied thinly. The die coating method is a coating head called a mold, and a method of applying a pressure to a liquid and extruding it is applied. formula. High-precision coating can be performed by die coating. Further, since the liquid is not exposed to the outside air at the time of coating, it is difficult to cause a change in the concentration of the coating liquid due to drying or the like. Other wet coating methods include spin coating, bar coat, reverse coating, roll coating, slit coating, dipping, spraying, conformal coating, and reverse bonding. Cloth method, air knife coating method, curtain coating method, rod coating method, and the like.

The method of forming the laminate can be suitably selected from the methods depending on the desired film thickness. Further, in consideration of productivity, by using a wet coating method, it is possible to laminate at a linear velocity of several tens of meters per minute (for example, about 20 m/min), so that it can be produced in a large amount and the production efficiency can be improved.

The method of curing the resin composition will be described. In the case of using thermal energy, it can be carried out in an environment of room temperature to about 200 ° C. In the case of using a substrate formed by a plastic material, in consideration of the heat resistance of the plastic, it is preferably 50 ° C. ~120 °C.

In the case of using an active energy ray polymerization initiator, it may be cured by irradiation of an optically active energy ray or an electron beam by an active energy ray source after coating drying. In the case of using a substrate formed of a plastic material, in view of heat resistance of the plastic, coating drying is preferably from 50 ° C to 120 ° C. The active energy ray source is not particularly limited, and may be exemplified by a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, a gas laser, depending on the nature of the active energy ray polymerization initiator used. Solid laser, electron beam irradiation device, and the like.

The thickness of the hardened resin layer (d) is from 0.1 μm to 20 μm. Hardened tree In the use in which the grease layer requires surface hardness, the thickness of the cured resin layer is preferably from 3 μm to 20 μm, and more preferably from 3 μm to 10 μm in consideration of production cost.

In the case where a volume change such as expansion or contraction occurs after the resin composition is cured, the coating conditions of the resin composition are determined in consideration of the volume change.

The form of the article obtained after hardening is a laminate having a hardened resin layer on one side or two area layers of the substrate. The laminate can be used as a coating material for a membrane switch used in a toilet, a microwave oven, a washing machine, or the like. Further, it is also possible to use a protective film used for a display screen such as a touch panel display or a protective material for various optical lenses. In addition, it is also possible to make full use of excellent antibacterial properties, and to use it in applications such as a coating material for a door handle that is not touched by a plurality of people in a hospital or the like, or a wall coating material.

[Examples]

Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to the embodiments.

<Synthesis of antibacterial compound (fatty acid modified silver ultrafine particles; antibacterial agent A)>

The antibacterial agent A is obtained by performing the synthesis as described below in accordance with the method described in JP-A-2009-226400.

10 ml of polyethylene glycol 400 was preheated to a solution of 220 ° C, and the silver stearate was adjusted to 5 ppm, stirred and mixed at the same temperature, and immediately cooled, and then filtered using a filter. A dispersion is obtained. The obtained dispersion was diluted by methyl ethyl ketone (MEK) to prepare a weight of 0.05. A quantity of fatty acid modified silver ultrafine particles of MEK dispersion (antibacterial agent A).

<Preparation of Photocurable Resin Composition A>

The photocurable resin composition A can be obtained by the following method.

A mixture of photopolymerizable acrylate and oligomer: 39 parts by weight, photopolymerization initiator: 5 parts by weight, cerium oxide microparticles: 11 parts by weight, propylene glycol monomethyl ether: 28.8 parts by weight, butyl acetate 11.7 parts by weight and propylene glycol monomethyl ether acetate: 4.5 parts by weight were mixed, and the mixture was stirred by a disperser, and then the cerium oxide fine particles were dispersed by a bead mill to obtain a photocurable resin composition A. The average particle diameter of the cerium oxide fine particles in the obtained photocurable resin composition A was measured using a laser diffraction/scattering particle size distribution measuring apparatus, and as a result, the average particle diameter of the cerium oxide fine particles was 0.6 μm.

<Preparation of Photocurable Resin Composition B>

The photocurable resin composition B can be obtained by the following method.

A mixture of photopolymerizable acrylate and oligomer: 55 parts by weight, photopolymerization initiator: 5 parts by weight, propylene glycol monomethyl ether: 25.6 parts by weight, butyl acetate: 10.4 parts by weight, propylene glycol monomethyl ether Acetate: 4 parts by weight of the mixture was mixed, and the photocurable resin composition B was obtained by stirring with a disperser.

[Example 1]

MEK-ST (trade name; MEK solvent containing 30% by weight of cerium oxide microparticles, average particle diameter of cerium oxide microparticles: about 15 nm, manufactured by Nissan Chemical Industries, Ltd.): 100 parts by weight, UNIDIC V6810 (product) Name; photopolymerization containing 60% by weight of photocurable acrylate resin and 40% by weight of MIBK solvent Qualitative resin composition, DIC Co., Ltd.): 117 parts by weight, Irgacure 184 (trade name; photopolymerization initiator, manufactured by BASF Corporation): 5 parts by weight, antibacterial agent A: 40 parts by weight, and mixed Resin composition 1 was prepared.

Next, the resin composition 1 was applied on a polyester film (COSMOSHINE A4300, trade name; manufactured by Toyobo Co., Ltd., film thickness: 100 μm) using a bar coater.

The coated film was dried in an oven at a temperature of 80 ° C for 1 minute, and then subjected to an ultraviolet ray of a high pressure mercury lamp using an 8 KW-belt type UV irradiation device (manufactured by EYE GRAPHICS Co., Ltd.) at a peak illuminance of 200 mW/cm. ^{2. The} resin composition 1 was cured under irradiation conditions of an integrated light amount of 300 mJ/cm ² to obtain a layered body 1 having a cured resin layer having a film thickness of 4 μm on a polyester film.

[Embodiment 2]

The resin composition 2 was prepared by mixing 91 parts by weight of the photocurable resin composition A, 83 parts by weight of the photocurable resin composition B, and 40 parts by weight of the antibacterial agent A.

Next, the resin composition 2 was applied on a polyester film (COSMOSHINE A4300, trade name; manufactured by Toyobo Co., Ltd., film thickness: 100 μm) using a bar coater.

The coated film was dried in an oven at a temperature of 80 ° C for 1 minute, and then subjected to the same conditions as in Example 1 by using a conveyor belt type UV irradiation apparatus (manufactured by EYE GRAPHICS Co., Ltd.) by ultraviolet rays of a high pressure mercury lamp. The resin composition 2 was cured to obtain a coated laminate 2 having a cured resin layer having a film thickness of 4 μm on a polyester film.

[Example 3]

MEK-ST (trade name; MEK solvent containing 30% by weight of cerium oxide microparticles, average particle diameter of cerium oxide microparticles: about 15 nm, manufactured by Nissan Chemical Industries, Ltd.): 133 parts by weight, photocurable resin Composition A: 55 parts by weight, photocurable resin composition B: 50 parts by weight, and antibacterial agent A: 40 parts by weight were mixed to prepare a resin composition 3.

Next, the resin composition 3 was applied on a polyester film (COSMOSHINE A4300, trade name; manufactured by Toyobo Co., Ltd., film thickness: 100 μm) using a bar coater.

The coated film was dried in an oven at a temperature of 80 ° C for 1 minute, and then subjected to the same conditions as in Example 1 by using a conveyor belt type UV irradiation apparatus (manufactured by EYE GRAPHICS Co., Ltd.) by ultraviolet rays of a high pressure mercury lamp. The resin composition 3 was cured to obtain a laminate 3 having a cured resin layer having a thickness of 4 μm on a polyester film.

[Example 4]

MEK-ST (trade name; MEK solvent containing 30% by weight of cerium oxide microparticles, average particle diameter of cerium oxide microparticles: about 15 nm, manufactured by Nissan Chemical Industries, Ltd.): 100 parts by weight, UNIDIC V6810 (product) Name: Photopolymerizable resin composition containing 60% by weight of a photocurable acrylate resin and 40% by weight of MIBK solvent, Di Ai Sheng Co., Ltd.): 117 parts by weight, Irgacure 184 (trade name; photopolymerization initiator, BASF Corporation manufactured: 5 parts by weight, antibacterial agent A: 20 parts by weight, and mixed to prepare a resin composition 4.

Next, the resin composition 4 was applied on a polyester film (COSMOSHINE A4300, trade name; manufactured by Toyobo Co., Ltd., film thickness: 100 μm) using a bar coater.

The coated film was dried in an oven at a temperature of 80 ° C for 1 minute, and then subjected to the same conditions as in Example 1 by using a conveyor belt type UV irradiation apparatus (manufactured by EYE GRAPHICS Co., Ltd.) by ultraviolet rays of a high pressure mercury lamp. The resin composition 4 was cured to obtain a layered body 4 having a cured resin layer having a thickness of 4 μm on a polyester film.

[Comparative Example 1]

UNIDIC V6810 (photopolymerizable resin composition containing 60% by weight of photocurable acrylate resin and 40% by weight of MIBK solvent, Di Ai Sheng Co., Ltd.): 167 parts by weight, Irgacure 184 (photopolymerization initiator, BASF) Manufactured by the company: 5 parts by weight, antibacterial agent A: 40 parts by weight, and mixed to prepare a resin composition 5 containing no inorganic oxide fine particles.

Next, the resin composition 5 was applied on a polyester film (COSMOSHINE A4300, trade name; manufactured by Toyobo Co., Ltd., film thickness: 100 μm) using a bar coater.

The coated film was dried in an oven at a temperature of 80 ° C for 1 minute, and then subjected to the same conditions as in Example 1 by using a conveyor belt type UV irradiation apparatus (manufactured by EYE GRAPHICS Co., Ltd.) by ultraviolet rays of a high pressure mercury lamp. The resin composition 1 was cured to obtain a layered body 5 having a cured resin layer having a thickness of 4 μm on a polyester film.

[Comparative Example 2]

MEK-ST (trade name; MEK solvent containing 30% by weight of cerium oxide microparticles, average particle diameter of cerium oxide microparticles: about 15 nm, manufactured by Nissan Chemical Industries, Ltd.): 100 parts by weight, UNIDIC V6810 (product) Name: Photopolymerizable resin composition containing 60% by weight of a photocurable acrylate resin and 40% by weight of MIBK solvent, Di Ai Sheng Co., Ltd.): 117 parts by weight, Irgacure 184 (trade name; photopolymerization initiator, Prepared by BASF Corporation: 5 parts by weight, MEK: 40 parts by weight, and mixed to prepare a resin composition 6 containing no antibacterial agent.

Next, the resin composition 6 was applied on a polyester film (COSMOSHINE A4300, trade name; manufactured by Toyobo Co., Ltd., film thickness: 100 μm) using a bar coater.

The coated film was dried in an oven at a temperature of 80 ° C for 1 minute, and then subjected to the same conditions as in Example 1 by using a conveyor belt type UV irradiation apparatus (manufactured by EYE GRAPHICS Co., Ltd.) by ultraviolet rays of a high pressure mercury lamp. The resin composition 6 was cured to obtain a layered body 6 having a cured resin layer having a thickness of 4 μm on a polyester film.

[Comparative Example 3]

The photocurable resin composition A: 91 parts by weight, the photocurable resin composition B: 83 parts by weight, and butyl acetate: 40 parts by weight were mixed to prepare a resin composition 7 containing no antibacterial agent.

Next, the polyester film (COSMOSHINEA 4300, trade name; manufactured by Toyobo Co., Ltd., film thickness: 100 μm) was coated with a bar coater. Resin composition 7.

The coated film was dried in an oven at a temperature of 80 ° C for 1 minute, and then subjected to the same conditions as in Example 1 by using a conveyor belt type UV irradiation apparatus (manufactured by EYE GRAPHICS Co., Ltd.) by ultraviolet rays of a high pressure mercury lamp. The resin composition 7 was cured to obtain a layered body 7 having a cured resin layer having a thickness of 4 μm on a polyester film.

<Antibacterial properties>

The antibacterial test was carried out in accordance with the specifications of JIS Z 2801. The sample bacteria were carried out by S. aureus and Escherichia coli. In addition, this test was carried out in the middle of the central oracle test of the quality of the fiber products of the general corporation. The results of the antimicrobial activity values are shown in Tables 1 and 2.

<Total light transmittance>

The total light transmittance is implemented in accordance with the specifications of JIS K 7156. The laminate was measured using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Tables 1 and 2.

<Haze>

The haze is implemented in accordance with the specifications of JIS K 7156. The laminate was measured using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Tables 1 and 2.

<hue (b*)>

The hue (b*) is implemented in accordance with the specifications of JIS Z 8722. The laminated body was measured using a spectroscopic color meter (SD500, manufactured by Nippon Denshoku Industries Co., Ltd.) set. The results are shown in Tables 1 and 2.

According to the results of Table 1, it was found that the inorganic oxide fine particles were mixed in the curable resin containing the ultrafine inorganic antibacterial agent, and the antibacterial property was improved (comparison between Example 1 and Comparative Example 1). Further, when Example 1 and Comparative Example 2 and Example 2 were compared with Comparative Example 3, it was found that there was no optical property (total light transmittance, haze, hue) due to the addition of the ultrafine inorganic antibacterial agent. The change.

[Industrial availability]

The laminate of the present invention is a resin composition having a good antibacterial effect even in the case where the amount of the compound having less antibacterial property is smaller than that of the prior art. Further, the cured resin layer obtained by curing the resin composition also has good antibacterial properties and also has good optical properties, and thus is formed on the substrate. The laminate of the cured resin layer is very useful as a protective film for a membrane switch or a touch panel display.

Claims (5)

A laminate comprising a cured resin layer (d) containing a compound (a) having an antibacterial property, inorganic oxide fine particles (b), and a curable resin (c) The resin composition is applied to both surfaces or one surface of the substrate to be cured, and the antibacterial compound (a) is selected from the group consisting of gold, silver, copper, tin, zinc, and platinum. The mixing ratio of the inorganic fine particles of at least one metal ion in the group is 0.01 parts by weight based on the total of the antibacterial compound (a), the inorganic oxide fine particles (b), and the curable resin (c). In the above, less than 0.04 parts by weight, the inorganic oxide fine particles (b) have an average particle diameter of 0.01 μm to 1.0 μm, and the mixing ratio thereof is relative to the compound (a) having an antibacterial property, the inorganic oxide fine particles (b), and the curability. The total amount of the resin (c) is from 5 parts by weight to 50 parts by weight, and the curable resin (c) is at least one selected from the group consisting of thermosetting resins and active energy ray-curable resins, and a cured resin layer. The thickness of (d) is from 0.1 μm to 20 μm. The laminate according to claim 1, wherein the antibacterial compound (a) is an ultrafine inorganic antibacterial agent comprising at least one metal complex selected from the group consisting of gold Any one of the groups consisting of silver, copper, tin, zinc, and platinum ions is a center metal. The laminate according to claim 1 or 2, wherein the inorganic oxide fine particles (b) are selected from the group consisting of cerium oxide, aluminum oxide, zirconium oxide, zirconium silicate, rutile titanium oxide, and tin oxide. , cerium oxide, magnesium fluoride and iron oxide in groups One less. A protective film using the laminate according to any one of claims 1 to 3. An optical lens using the laminate according to any one of claims 1 to 3.