TW201706127A - Laminate with transparent conductive film and laminate manufacturing method having hard coat property and sealability resistant to harsh active energy ray radiation - Google Patents

Abstract

This invention provides a transparent conductive film with hard coat property and sealability resistant to harsh active energy ray radiation as manufacturing the transparent conductive film. The subject is solved by the following laminate. The laminate has a resin layer made by curing an active energy ray curable composition containing compound (A) on a substrate as a polyester film, wherein compound (A) contains a fluorene structure and/or a biphenyl structure and two or more (meth)acryloyl groups, and the laminate further comprises the transparent conductive film.

Description

Laminated body having transparent conductive film and method of manufacturing laminated body

The present invention relates to a laminate having a substrate, a resin layer obtained by curing an active energy ray-curable composition, and a transparent conductive film, and a method for producing the same.

Conventionally, a transparent conductive laminated body provided with a transparent conductive film on a substrate such as polyester has been used for touch panel applications and the like. The transparent conductive film is usually a film of a metal oxide such as indium tin oxide (ITO), and is deposited on the substrate by sputtering or vacuum deposition. As a mode of operation of the touch panel, the resistive film type is the mainstream, but in recent years, the electrostatic capacitance type has rapidly expanded. The laminate having transparent conductivity used in the resistive film type touch panel generally includes an unpatterned transparent conductive film. On the other hand, in a capacitive touch panel, a transparent conductive laminated body in which a patterned transparent conductive film is laminated is generally used.

The laminate having transparent conductivity used in the capacitive touch panel is usually patterned by photolithoetching or the like, and the pattern portion and the non-pattern portion of the transparent conductive film are present in a plan view. As described above, the capacitive touch panel having a transparent conductive film patterned with a transparent conductive film has a problem that a so-called "perspective" phenomenon in which a pattern portion of the transparent conductive film is visible becomes a problem, and is used as a display device. The quality is declining. For example, Patent Document 1, Patent Document 2, and the like have proposed fluoroscopy for suppressing a pattern of a transparent conductive film. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-84075 [Patent Document 2] Japanese Patent No. 5110226

[Problems to be Solved by the Invention] In recent years, a single layer or both surfaces of a substrate are multilayered depending on the use of the laminate, and a large amount of active energy rays are irradiated when these layers are formed or when the transparent conductive film is patterned. In the technique of Patent Document 1 or Patent Document 2, the effect of suppressing the fluoroscopy of the transparent conductive film pattern is exhibited. However, when the resin layer receives a large amount of active energy rays, the adhesion to the substrate is lowered. . Further, in order to secure the adhesion between the substrate and the resin layer, if the layer configuration is to be designed such that the integrated light amount of the active energy ray does not become large, the layer structure of the laminate is limited. Therefore, an object of the present invention is to provide a laminate having transparency and transparency and transparency to a large amount of active energy ray irradiation when producing a laminate having transparent conductivity. [Means for solving the problem]

The present invention relates to a laminate having a resin layer on a substrate as a polyester film and further having a transparent conductive film, the resin layer comprising a fluorene structure and/or a biphenyl structure, and two or more ( The active energy ray-curable composition of the methyl (meth) fluorenyl group-containing compound (A) is cured.

Further, the present invention relates to the laminate, wherein the resin layer is a composition which further contains a compound (X) having three or more (meth) acryloyl groups (excluding the case of the compound (A)) a layer of hardened material.

Further, the present invention relates to the laminate, wherein the compound (A) having a fluorene structure and/or a biphenyl structure and two or more (meth) acryl fluorenyl groups has three or more (meth) groups The content of the compound (A) is from 10% by weight to 90% by weight based on 100% by weight of the total solid content of the compound (X) of the acrylonitrile group (excluding the case of the compound (A)).

Furthermore, the present invention relates to the layered product, wherein the compound (A) is a compound (A1) represented by the following formula (1). General formula (1):

[Chemical 1] (In the formula (1), at least one of R ₁ and R ₃ is a tetravalent or monovalent organic residue shown below, and R ₂ represents a monovalent organic residue having a (meth) acrylonitrile group) [ 2] [Chemical 3]

Furthermore, the present invention relates to the laminate, wherein the compound (A) is a compound (A2) represented by the following formula (2). General formula (2): R ₅ -OR ₄ -OR ₅ (In the formula (2), R ₄ is a divalent organic residue shown below, and R ₅ represents a monovalent group having a (meth)acryl fluorenyl group. Organic residue)

[Chemical 4]

Further, the present invention relates to the laminate, wherein the base is measured by an adhesion cross-cut method according to JIS K5600-5-6 in the case of irradiating an active energy ray having an integrated light amount of 2000 mJ/cm ² or more. The adhesion of the material to the resin layer is less than 5% of the peeling area per unit area.

Further, the present invention relates to the laminate, wherein the composition further comprises a metal oxide. Furthermore, the invention relates to the laminate, wherein the metal oxide comprises titanium and/or zirconium atoms.

The present invention relates to a method for producing a laminate comprising: coating a compound having a fluorene structure and/or a biphenyl structure and two or more (meth) acryl fluorenyl groups on a substrate as a polyester film The active energy ray-curable composition of (A), a step of irradiating an active energy ray to cure the resin layer, and a step of forming a transparent conductive film. [Effects of the Invention]

According to the present invention, it is possible to provide a laminate having transparency and transparent conductivity which is also resistant to irradiation with a large amount of active energy rays.

In the laminate of the present invention, a resin layer as an active energy ray-curing film and a transparent conductive film are sequentially provided on one surface or both surfaces of a base film.

In the following, each component constituting the laminate having the base material as the polyester film, the resin layer obtained by curing the active energy ray-curable composition, and the transparent conductive film of the present invention will be described in detail.

<Polyester film> The polyester film of the present invention has a refractive index of 1.61 to 1.70, and a polyethylene terephthalate film is particularly preferably used. The refractive index of the polyester film is preferably in the range of from 1.62 to 1.69, particularly preferably in the range of from 1.63 to 1.68, particularly preferably in the range of from 1.64 to 1.67.

The thickness of the polyester film is suitably in the range of 20 μm to 300 μm, preferably in the range of 50 μm to 250 μm, and more preferably in the range of 50 μm to 200 μm.

The polyester film of the present invention may further have a layer containing an organic substance or an inorganic substance on its surface, and specific examples thereof include an easy-adhesion layer for improving adhesion to other layers.

A commercial product of a polyester film provided with an easy-adhesion layer can be exemplified by Toray Co., Ltd.: Lumirror series, manufactured by Toyobo Co., Ltd.: Cosmoshine series, and the like. It is particularly preferably manufactured by Toray Co., Ltd., which has high transparency and is used in optical applications: Lumirror UH13, U48 series.

<Resin layer> The resin layer of the present invention is obtained by curing an active energy ray-curable composition containing a compound (A) having a fluorene structure and/or a biphenyl structure and two or more (meth) acryl fluorenyl groups. Layer.

When the compound (A) has one or more fluorene structures and/or a biphenyl structure and two or more (meth) acrylonitrile groups in the structure, the compound (A) is adhered to the polyester film. Excellent sex.

Preferable specific examples of the compound (A) include the compound (A1) represented by the following formula (1). The compound (A1) can be suitably used because it has excellent hard coat properties.

General formula (1): [Chemical 1] In the formula (1), at least one of R ₁ and R ₃ is a tetravalent or monovalent organic residue having a fluorene structure or a biphenyl structure, and R ₂ represents a monovalent organic residue having a (meth) acryl fluorenyl group. .

In the general formula (1), R ₁ is not particularly limited as long as it has an anthracene structure or a biphenyl structure, and specific examples thereof include the tetravalent organic residues shown below. It is preferably a residue having a biphenyl structure.

[Chemical 2]

In the general formula (1), in the case where R ₃ has a fluorene structure or a biphenyl structure, R ₁ may not have a fluorene structure or a biphenyl structure. The above is not particularly limited, and specific examples thereof include tetravalent organic residues shown below. It is preferably a residue having an aromatic ring. [Chemical 3]

In the general formula (1), R ₃ is not particularly limited as long as it has a fluorene structure or a biphenyl structure, and specific examples thereof include the monovalent organic residues shown below. [Chemical 4]

In the general formula (1), in the case where R ₁ has a fluorene structure or a biphenyl structure, R ₃ may not have a fluorene structure or a biphenyl structure. The above is not particularly limited, and examples thereof include a hydrogen atom or a monovalent organic residue shown below. [Chemical 5]

In the general formula (1), R ₂ is not particularly limited as long as it has a (meth) acrylonitrile group, and specific examples thereof include the monovalent organic residues shown below. [Chemical 6]

When the compound (A1) represented by the formula (1) has two or more fluorene structures and/or a biphenyl structure, it is preferable because it has excellent adhesion to a substrate, and further preferably R ₁ and R _{3 .} It has a fluorene structure or a biphenyl structure.

The (meth) acrylonitrile group of the compound (A) must be two or more. In the case of two or less, the adhesion between the obtained active energy ray-curable film and the substrate as the polyester film is lowered. Further, since the resin layer is excellent in hard coatability, the number of (meth)acryl fluorenyl groups is preferably 3 or more, and particularly preferably 6 or more.

In the compound (A1) represented by the formula (1), the compound (A1-1) wherein R ₃ is a hydrogen atom can be selected, for example, by a dianhydride (b1) having a tetracarboxylic acid having a structure represented by R ₁ . It is obtained by reacting at least one compound (b2) of 2-hydroxyethyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. The compound (A1-2) having R ₃ other than a hydrogen atom can be, for example, selected from the carboxyl group contained in the compound obtained in the reaction, and selected from the group consisting of biphenyl glycidyl ether, glycidyl methacrylate, and acrylic acid 4- At least one epoxy group-containing compound (b3) in the group consisting of hydroxybutyl ester glycidyl ether is obtained by a reaction.

The tetracarboxylic dianhydride (b1) is not particularly limited as long as it has a fluorene structure or a biphenyl structure, and specific examples thereof include 3,3',4,4'-biphenyl having a biphenyl skeleton. The carboxylic acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) phthalic anhydride having an anthracene skeleton, and the like are preferably those having a biphenyl structure. In the case where the epoxy group-containing compound (b3) has a fluorene structure or a biphenyl structure, the tetracarboxylic dianhydride (b1) may not have a fluorene structure or a biphenyl structure. The above is not particularly limited, and specific examples thereof include 1,2,4,5-benzenetetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride, and preferably have an aromatic ring. By.

Among these tetracarboxylic dianhydrides, 3,3',4,4'-biphenyltetracarboxylic dianhydride is particularly preferable because it has both a hard coat property of a cured film and a good dispersibility of a metal oxide.

From the viewpoints of photocurability and hard coatability, the compound (b2) is preferably pentaerythritol triacrylate and dipentaerythritol pentaacrylate. Specific commercial products of pentaerythritol triacrylate and dipentaerythritol pentaacrylate include Viscoat #300 (made by Osaka Organic Chemical Industry Co., Ltd.) and KAYARAD PET30 (Japan) Pharmaceutical (stock) manufacturing), Petia (PETIA) (Daicel UCB (share) manufacturing), Aronix (Aronix) M305 (made in East Asia Synthetic (stock)), NK ester (NK Ester) A- TMM-3LMN (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Light Acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-444 (manufactured by Sartomer Co., Ltd.) , Light Acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD DPHA (manufactured by Nippon Chemical Co., Ltd.), Aronix M402 (East Asian Synthetic) (share) manufacturing) and so on.

These commercially available products each contain about 5% by weight to 15% by weight of pentaerythritol diacrylate having two hydroxyl groups and dipentaerythritol tetraacrylate as an accessory component. Therefore, in the reaction of the tetracarboxylic dianhydride (b1) with pentaerythritol triacrylate or dipentaerythritol pentaacrylate, in addition to the compound (A1) represented by the formula (1), a subcomponent is simultaneously produced. The reactant and the polymer which is further polymerized.

The reaction between the tetracarboxylic dianhydride (b1) and the compound (b2) is a reaction between two carboxylic anhydride groups of the tetracarboxylic dianhydride and a hydroxyl group of the compound (b2), and a conventionally known method can be used. Come on. For example, tetracarboxylic dianhydride (b1) and compound (b2) can be used in an organic solvent such as cyclohexanone such as 1,8-diazabicyclo[5.4.0]-7-undecene. The reaction is carried out at a temperature of from 50 ° C to 120 ° C in the presence of a catalyst such as. In this case, a polymerization inhibitor such as methyl hydroquinone (2-METHYLHYDROQUINONE) may be added to the reaction system.

The reaction product of the compound (A1-1) containing R _{3 which} is a hydrogen atom obtained in the above reaction may be purified, and the compound (b3) may be further reacted.

The reaction of the compound (A1-1) with the compound (b3) is a reaction between a carboxyl group of the compound (A1-1) and an epoxy group of the compound (b3), and can be carried out by a conventionally known method. For example, the reaction can be carried out at a temperature of from 50 ° C to 120 ° C in the presence of an amine catalyst such as dimethylbenzylamine or the like.

These reactions can be carried out in the absence of a solvent or in a solvent inert to the reaction. Examples of the solvent include a hydrocarbon-based solvent such as n-hexane, benzene or toluene; a ketone-based solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; and an ester-based solvent such as ethyl acetate or butyl acetate; An ether solvent such as diethyl ether, tetrahydrofuran or dioxane; a halogen-based solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or perclene; acetonitrile, N, N-di A polar solvent such as methylformamide, N,N-dimethylacetamide or N,N-dimethylimidazolidinone. These solvents may be used in combination of two or more kinds.

When a solvent is added, it is preferable to carry out a hardening process after volatilizing a solvent. The solvent is not particularly limited, and various known organic solvents can be used. Specific examples thereof include cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, etidyl acetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, and Propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, 2- Ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate And 2-ethoxyethyl acetate, butyl acetate, isoamyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, methyl pyrrolidone and the like. These organic solvents may be used in combination of two or more kinds.

Preferable specific examples of the compound (A) include the compound (A2) represented by the following formula (2). General formula (2): R ₅ -OR ₄ -OR ₅

In the formula (2), R ₄ is a divalent organic residue having a fluorene structure or a biphenyl structure, and R ₅ represents a monovalent organic residue having a (meth) acryl fluorenyl group.

In the general formula (2), R ₄ is not particularly limited as long as it has an anthracene structure or a biphenyl structure, and specific examples thereof include the divalent organic residues shown below. It is preferably a residue having a fluorene structure.

[Chemistry 7]

In the general formula (2), R ₅ is not particularly limited as long as it has a (meth) acrylonitrile group, and specific examples thereof include the monovalent organic residues shown below. [化8]

The compound (A2) is, for example, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene or the like. In addition, commercially available products include NK Ester A-BPEF manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and Ogsol EA series manufactured by Osaka Gas Chemicals Co., Ltd., and the like.

The active energy ray-curable composition may further comprise a photopolymerization initiator. The photopolymerization initiator has a function of initiating a function of vinyl polymerization of a (meth)acryl fluorenyl group for forming an active energy ray-curing film by photoexcitation, and is not particularly limited. For example, it is possible to use: A monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, a mercaptophosphine oxide compound, an amine carbonyl compound, or the like.

Specifically, the monocarbonyl compound may, for example, be benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, or 4 -Phenylbenzophenone, 4-(4-methylphenylthio)phenyl-ethanone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(1,3 -propenyl-1,3,3'-dimethyl-4-methoxy)benzophenone, 4-(1,3-propenyl-1,4,7,10,13-pentaoxy Tridecyl)benzophenone, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 4-benzylidene-N,N,N-trimethyl 1,-1-propanylamine hydrochloride, 4-benzylidene-N,N-dimethyl-N-2-(1-oxo-2-propenyloxyethyl)methylammonium oxalate , 2-/4-isopropylthioxanthone, 2,4-diethylthiazinone, 2,4-dichlorothiazinone, 1-chloro-4-propoxythiazinone 2-Hydroxy-3-(3,4-dimethyl-9-oxo-9H-thianonanone-2-oxy-N,N,N-trimethyl-1-propanamine hydrochloride , benzhydrylmethylene-3-methylnaphtho(1,2-d)thiazoline, and the like.

The dicarbonyl compound may, for example, be 1,2,2-trimethyl-bicyclo[2.1.1]heptane-2,3-dione, benzil, 2-ethylhydrazine, 9,10- Phinethrenequinone, methyl-α-oxophenyl acetate, 4-phenylbenzil, and the like. Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-benzene. Propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2 -diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 1-phenyl -1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, 3,6-bis(2-methyl-2-morpholinyl-propenyl)-9-butylcarbazole, and the like.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether. The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 4-n-propylphenyl-bis(2,6-dichlorobenzhydryl)phosphine oxide. Wait.

The aminocarbonyl compound may, for example, be methyl 4-(dimethoxyamino)benzoate, ethyl 4-(dimethylamino)benzoate or 4-(dimethylamino)benzoic acid 2-positive Butoxyethyl ester, isoamyl 4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl benzoate, 4,4'-bis-4-dimethylamino Benzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,5'-bis(4-diethylaminobenzylidene)cyclopentanone, and the like. Commercial products of the photopolymerization initiators include: Irgacure 184, 651, 500, 907, 127, 369, 784, 2959 manufactured by Ciba Specialty Chemicals Co., Ltd., BASF ( BASF) company's Lucirin TPO, Japan's Nihon Siber Hegner (Esacure) ONE and so on.

The photopolymerization initiator is not limited to the compound, and may have any ability to initiate polymerization by ultraviolet rays. These photopolymerization initiators may be used in combination of two or more kinds in addition to one. The amount of use of the photopolymerization initiator is not particularly limited, and is preferably the total amount of the active energy ray-curable compound containing the compound (A) (in the case of a photocurable compound other than the compound (A), The total amount of the compound (A) and the photocurable compound other than the compound (A) is 100 parts by weight, and is used in the range of 1 part by weight to 20 parts by weight. A well-known organic amine etc. can also be added as a sensitizer. Further, in addition to the initiator for radical polymerization, an initiator for cationic polymerization may be used in combination.

The active energy ray-curable composition may further contain a compound (X) having three or more (meth) acrylonitrile groups (except for the case of the compound (A)). The hard coat property of the resin layer can be further improved by the compound (X). From the viewpoint of coating film strength and scratch resistance, the compound (X) can be suitably used as a poly(methyl) group such as a polyurethane poly(meth)acrylate or a polyepoxy poly(meth)acrylate. Acrylates, polyfunctional acrylates. The polyepoxy poly(meth)acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth)acrylic acid, and setting the functional group to a (meth)acrylonitrile group, and having a bisphenol A type. A (meth)acrylic acid addition product of an epoxy resin, a (meth)acrylic acid addition product to a novolac type epoxy resin, or the like.

The polyurethane poly(meth) acrylate is, for example, obtained by reacting a diisocyanate with a (meth) acrylate having a hydroxyl group; and the polyol and the polyisocyanate are in an excess of an isocyanate group. The isocyanate group-containing urethane prepolymer obtained by the reaction is obtained by reacting with a (meth) acrylate having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyhydric alcohol with a polyisocyanate under a condition that a hydroxyl group is excessive may be obtained by reacting with a (meth) acrylate having an isocyanate group.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, and Triol, trimethylolpropane, polytetramethylene glycol, polycondensate of adipic acid and ethylene glycol, and the like.

Examples of the polyisocyanate include methylphenyl diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and pentaerythritol. Acrylate, dipentaerythritol penta (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, and the like. Examples of the (meth) acrylate having an isocyanate group include 2-(meth)acryloxyethyl isocyanate and (meth) propylene decyl isocyanate.

Commercially available products of the photocurable compound can be exemplified below. East Asian synthetic (stock) manufacturing: Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, Aronis (Aronix) M-7100, Aronix M-8030, Aronix M-8060; Osaka Organic Chemical Industry (Stock) Manufacturing: Viscoat #400; Chemical Shado Made by Sartomer (SR): SR-295; Daicel UCB (manufacturing): DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602; manufactured by Xinzhongcun Chemical Industry Co., Ltd.: NK Ester A-TMMT, NK Oligo EA-1020, NK oligomerization ( NK Oligo) EMA-1020, NK Oligo EA-6310, NK Oligo EA-6320, NK Oligo EA-6340, NK Oligo MA-6 NK Oligo U-4HA, NK Oligo U-6HA, NK Oligo U-324A; Made by BASF: Laromer EA81; San Nopco (stock) manufacturing: Photomer 3016, Arakawa Chemical Industry (stock) manufacturing: Beamset 371, Beamset 575, Beamset 577, Beamset 700, Beamset 710; Roots Industrial (stock) manufacturing: Art Resin UN-3320HA, Art Resin (Art Resin)UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin HDP, Art Resin HDP-3, Art Resin H61; Japan Synthetic Chemical Industry Co., Ltd.: Violet UV-7600B, Violet UV-7610B, Violet UV -7620EA, Violet UV-7630B, Violet UV-1400B, Violet UV-1700B, Violet UV-6300B; Produced by Gongrongshe Chemical Co., Ltd.: Light Acrylate PE-4A, Light Acrylate DPE-6A, UA-306H, UA-306T, UA-306I; manufactured by Nippon Chemical Co., Ltd.: Kaya De (KAYARAD) DPHA, Kaya rad (KAYARAD) DPHA2C, Kaya rad (KAYARAD) DPHA-40H, Kaya rad (KAYARAD) D-310, Kaya rad (KAYARAD) D-330.

The compound (X) having three or more (meth) acrylonitrile groups may be used singly or in combination of two or more. Further, in general, a product of pentaerythritol triacrylate or dipentaerythritol pentaacrylate which can be used as the compound (b2) is a pentaerythritol tetraacrylate having no hydroxyl group or dipentaerythritol hexaacrylate. Therefore, in the case where pentaerythritol triacrylate or dipentaerythritol pentaacrylate is used in the compound (b2), pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate contained in these compounds are used as the compound (X) to contribute to hard coating. Sexual improvement.

a compound (A) having an anthracene structure and/or a biphenyl structure, and two or more (meth)acrylonyl groups, and a compound (X) having three or more (meth)acrylonyl groups (wherein The content of the compound (A) is preferably 10% by weight to 90% by weight, particularly preferably 20% by weight to 80% by weight, based on 100% by weight of the total solid content of the compound (A). The reason for this is that the adhesion between the polyester base material and the resin layer and the hard coat property are excellent in the above range.

The active energy ray-curable composition may contain a metal oxide in order to adjust the refractive index of the resin layer as the cured film. The D50 particle diameter of the metal oxide is preferably from 0.005 μm to 0.200 μm. The D50 particle diameter of the metal oxide can be measured, for example, using "Nnotrac UPA" manufactured by Nikkiso Co., Ltd. using a dynamic light scattering method. In the case of a metal oxide composition having a D50 particle diameter of less than 0.005 μm, the cohesive force of the fine particles is extremely large, and thus the dispersibility of the primary particle level having high transparency tends to decrease. On the other hand, when the particle diameter of D50 exceeds 0.200 μm, since the particle diameter is large, light such as visible light is likely to be scattered, and turbidity tends to occur in the cured film.

The metal oxide is preferably one containing at least one atom selected from the group consisting of titanium, zinc, zirconium, hafnium, and aluminum. In particular, a metal oxide containing any atom of titanium and/or zirconium is more preferable. Specific examples thereof include titanium oxide, zinc oxide, zirconium oxide, cerium oxide, aluminum oxide, and barium titanate. These metal oxides can also be treated with organic or inorganic materials. Further, these metal oxides may be used in combination of two or more kinds.

When the metal oxide is contained, the content thereof is preferably 10% by weight to 80% by weight, and more preferably 30% by weight to 60% by weight, based on the solid content of the curable composition. The metal oxide can be adjusted using a dispersion which contains the compound (A) in advance. It is preferred to use a dispersion of the compound (A1).

Next, a method of producing a resin layer obtained by curing an active energy ray-curable composition will be described. The method for producing a resin layer includes, for example, applying an active energy ray-curable resin composition onto a substrate as a polyester film, and irradiating an active energy ray to cure the active energy ray-curable composition on the substrate. More specifically, the resin composition can be applied to a substrate as a polyester film after the film thickness after drying is preferably 0.02 μm to 30 μm, more preferably 0.02 μm to 20 μm. And formed by hardening treatment.

A known method can be used for the coating method, for example, a method using a rod or a wire bar, or a micro gravure, a gravure, a mold, a curtain, a lip, a slit (slot) ) or various coating methods such as rotation. The hardening treatment can be carried out by using a known technique such as irradiation of an ultraviolet ray, an electron beam, or an active energy ray having a wavelength of from 400 nm to 500 nm. For ultraviolet light and a line source (light source) of visible light having a wavelength of 400 nm to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used. A thermal electron ray gun, an electrolysis lance, or the like can be used in the electron beam source.

The amount of the active energy ray to be irradiated is preferably in the range of 50 mJ/cm ² to 1000 mJ/cm ² in terms of ease of management in the step. In the irradiation of these active energy rays, heat treatment using infrared rays, far infrared rays, hot air, high frequency heating, or the like can be used in combination.

The cured film may be formed by applying an active energy ray-curable composition to a substrate, allowing it to be naturally or forcedly dried, followed by curing treatment, or may be applied and hardened, and then naturally or forcibly dried, but preferably Hardening after natural or forced drying. In particular, in the case of hardening by an electron beam, in order to prevent hardening by water or to reduce the strength of the coating film caused by the residual of the organic solvent, it is more preferable to carry out the hardening treatment after natural or forced drying. The timing of the hardening treatment may be at the same time as the application, or may be after application.

Since the obtained cured film is excellent in transparency and adhesiveness, it can be suitably used as an optical material. The thickness of the cured film is preferably 0.02 μm to 30 μm. Further, the refractive index of the cured film is preferably in the range of 1.4 to 2.0, and more preferably in the range of 1.5 to 1.9.

The composition for obtaining the active energy ray-curing film of the present invention may further contain various additives within a range not impairing the object or effect of the present invention. Specific examples thereof include a photocurable compound other than the compound (A) or the compound (X), a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an antibacterial agent, an anti-caking agent, and plasticization. Agent, ultraviolet absorber, infrared absorber, antioxidant, decane coupling agent, conductive polymer, conductive surfactant, inorganic filler, pigment, dye, and the like.

<Transparent Conductive Film> The material of the transparent conductive film can use a known material used in the electrode of the touch panel. For example, metal oxides such as tin oxide, indium oxide, antimony oxide, zinc oxide, indium tin oxide (ITO), and antimony tin Oxide (ATO) may be mentioned. Among these metal oxides, ITO is preferably used.

For example, from the viewpoint of ensuring good electrical conductivity of the surface resistance value of 10 ³ Ω/□ or less, the thickness of the transparent conductive film is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 20 nm or more. On the other hand, when the thickness of the transparent conductive film is too large, the transparency may be lowered. Therefore, the upper limit of the thickness of the transparent conductive film is preferably 60 nm or less, more preferably 50 nm or less, and particularly preferably Below 40 nm.

The refractive index of the transparent conductive film is 1.81 or more. Further, the refractive index of the transparent conductive film is preferably 1.85 or more, and more preferably 1.90 or more. The upper limit is preferably 2.20 or less, and more preferably 2.10 or less.

The method for forming the transparent conductive film is not particularly limited, and a conventionally known method can be used. Specifically, for example, a dry process such as a vacuum deposition method, a sputtering method, or an ion plating method can be used.

The transparent conductive film of the present invention is patterned. For example, a transparent conductive film formed in the manner described above is patterned. Patterning can form various patterns depending on the application to which the transparent conductive film is applied. Further, the pattern portion and the non-pattern portion are formed by patterning of the transparent conductive film, and the shape of the pattern portion may be, for example, a stripe shape or a lattice shape.

Patterning of the transparent conductive film is usually performed by etching. For example, a pattern-shaped anti-etching film is formed on a transparent conductive film by a photolithography method, a laser exposure method, or a printing method, and then an etching treatment is performed to pattern the transparent conductive film.

The etching solution is known to those skilled in the art. For example, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, phosphoric acid, organic acids such as acetic acid, and mixtures of these acids, and aqueous solutions thereof are used.

The laminate of the present invention may have a base material as a polyester film, a resin layer as an active energy ray-curing film, and a transparent conductive film, and the base material may be adjacent to the resin layer. The layer other than the layer is arbitrary, and a film or an adhesive layer having a different refractive index may be provided on one surface of the substrate or the resin layer as needed.

Hereinafter, some preferred configuration examples of the laminate of the present invention are listed, but the present invention is not limited to these configuration examples. Further, in the following configuration example, the transparent conductive film is a patterned transparent conductive film. Other layers than the transparent conductive film are not patterned. (I) Substrate/Resin Layer/Transparent Conductive Film (II) Substrate/Resin Layer/(M)/Transparent Conductive Film (III) (M)/Substrate/Resin Layer/Transparent Conductive Film (IV) (M) / Substrate / Resin Layer / (M) / Transparent Conductive Film (V) (M) / Resin Layer / Substrate / Resin Layer / Transparent Conductive Film (VI) Resin Layer / / Substrate / Resin Layer / Transparent Conductive Film (M) comprises any layer of a film or an adhesive layer having a different refractive index.

The film having a different refractive index is a function other than the function of the resin layer of the present invention. The method for forming the film is not particularly limited and is formed by a known method. For example, a dry coating method such as vapor deposition or sputtering, a method using a rod or a wire bar, a wet coating method such as a micro gravure, a gravure, a mold, a curtain, a lip, a slit, and a rotation can be used. The material to be used is not limited, and an information recording function, an anti-glare function, an anti-Newton ring function, an adhesive function, a specific wavelength interruption, a color tone correction, and the like can be used as needed. Any of more than one material.

In the production of the laminate of the present invention, the active energy ray is irradiated when the resin layer or any layer is cured or when the transparent conductive film is patterned. In this manufacturing process, even if the total amount of active energy rays irradiated to the resin layer is 2,000 mJ/cm ² or more, the adhesion between the base material of the polyester film and the resin layer as the active energy ray-curable film is excellent. Further, the so-called integrated light amount also includes an integrated light amount at the time of initial hardening for forming a resin layer as an active energy ray-curing film.

[Adhesiveness] The adhesion of the laminate having the polyester film as the base material, the resin layer as the active energy ray-curable film, and the transparent conductive film of the present invention is adhered according to JIS K5600-5-6. The adhesion evaluated by the sexual cross-cut method is a peeling area per unit area of less than 5%, which is very excellent. It is preferably less than 2%. Specifically, it demonstrates in the evaluation of an Example. [Examples]

Hereinafter, the present invention will be further described in detail based on production examples and examples. In the production examples and examples, parts and % represent parts by weight and % by weight, respectively. The chemicals used are as described below. <tetracarboxylic dianhydride (b1)> 3,3',4,4'-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Co., Ltd., trade name BPDA) 9,9-double (3,4-di Carboxyphenyl) sebacic anhydride (manufactured by JFE Chemical Co., Ltd., trade name: BPAF) 1,2,3,4-butane tetracarboxylic dianhydride (manufactured by Nippon Chemical and Chemical Co., Ltd., trade name: Likahi Rikacid BT-100) 1,2,4,5-benzenetetracarboxylic dianhydride (manufactured by Daicel), trade name: pyromellitic dianhydride, PMDA) phthalic anhydride (made by Wako Pure Chemical Industries, Ltd.) <Compound (b2)> Pentaerythritol triacrylate (1) (Manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30, also included as a vice Pentaerythritol tetraacrylate of the product) Pentaerythritol triacrylate (2) (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMM-3LM-N, also contains pentaerythritol tetraacrylate as a by-product) Dipentaerythritol pentaacrylate Ester (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: A-9570W, also contains dipentaerythritol hexaacrylate as a by-product) 2-Hydroxyethyl ester (manufactured by Japan Catalyst Co., Ltd., HEA) <Polymerization inhibitor> Methyl hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) <Catalyst> 1,8-diazabicyclo[5.4. 0]-7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) <epoxy group-containing compound (b3)> glycidyl methacrylate (Manufactured by Japan Dow Chemical Co., Ltd., GMA) 4-Hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd., trade name: 4-hydroxybutyl acrylate glycidyl ether) Biphenyl shrinkage Glycerol ether (made by Sanguang Co., Ltd., trade name: OPP-G)

<Method for Measuring Acid Value> According to the potential difference titration method of JIS K 0070, the measured acid value (mgKOH/g) was converted into a solid content.

<Synthesis Example of Compound (A1)> (Synthesis Example 1) 80.0 parts of 3,3',4,4'-biphenyl was placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. Tetracarboxylic dianhydride, 250.0 parts of pentaerythritol triacrylate (1) having a hydroxyl value of 122 mgKOH/g, 0.24 parts of methyl hydroquinone, and 217.8 parts of cyclohexanone were heated to 60 °C. Then, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the infrared (IR) measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peaks around 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 94 mgKOH/g. Next, 140.0 parts of biphenyl glycidyl ether and 91.0 parts of cyclohexanone were added to the solution, and then 2.65 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours to carry out a reaction. While continuing the reaction, the acid value of the reactant was periodically measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the ratio of the reactant containing the compound (A) in the solid content of the obtained resin varnish was 79%. Further, the reactant containing the compound (A) means a high molecular weight reactant containing a by-product of a plurality of hydroxyl groups in the compound (b2) in addition to the compound (A). The ratio of the reactant containing the compound (A) is calculated from the final acid value of the resin varnish. The rest indicates a compound having no hydroxyl group or an unreacted raw material in the compound (b2) used in the reaction. The same applies to the following Synthesis Example 2 to Synthesis Example 11.

(Synthesis Example 2) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 80.0 parts of 1,2,3,4-butanetetracarboxylic dianhydride and 402.0 parts of hydroxyl value were charged. It was 113 mg KOH/g of pentaerythritol triacrylate (2), 0.33 part of methyl hydroquinone, and 318.0 parts of cyclohexanone, and the temperature was raised to 60 °C. Then, 2.41 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 95 mgKOH/g. Next, 182.9 parts of biphenyl glycidyl ether and 118.0 parts of cyclohexanone were added to the solution, and then 3.88 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reactant was periodically measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the reactant containing the compound (A) in the obtained resin varnish solid content was 73%.

(Synthesis Example 3) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 80.0 parts of 1,2,4,5-benzenetetracarboxylic dianhydride and 364.9 parts of a hydroxyl value were charged. 113 mg KOH/g of pentaerythritol triacrylate (2), 0.31 part of methyl hydroquinone, and 294.1 parts of cyclohexanone were heated to 60 °C. Then, 2.22 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 93 mgKOH/g. Next, 166.0 parts of biphenyl glycidyl ether and 107.1 parts of cyclohexanone were added to the solution, and then 3.58 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours, and cooled to room. The reaction is terminated. While continuing the reaction, the acid value of the reactant was periodically measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the reactant containing the compound (A) in the obtained resin varnish solid content was 74%.

(Synthesis Example 4) 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 359.0 parts were placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. Dipentaerythritol pentaacrylate having a hydroxyl value of 85 mgKOH/g, 0.29 parts of methyl hydroquinone, and 290.1 parts of cyclohexanone were heated to 60 °C. Then, 2.19 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 74 mgKOH/g. Then, 123.1 parts of biphenyl glycidyl ether and 78.5 parts of cyclohexanone were added, and then 3.53 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours, and cooled to room temperature to terminate the reaction. . While continuing the reaction, the acid value of the reactant was periodically measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the reactant containing the compound (A) in the solid content of the obtained resin varnish was 83%.

(Synthesis Example 5) 80.0 parts of 9,9-bis(3,4-dicarboxyphenyl)sebacic anhydride and 160.2 parts were placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. The pentaerythritol triacrylate (1) having a hydroxyl value of 122 mgKOH/g, 0.16 parts of methyl hydroquinone, and 158.8 parts of cyclohexanone were heated to 60 °C. Then, 1.20 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 82 mgKOH/g. Then, 79.0 parts of biphenyl glycidyl ether and 50.7 parts of cyclohexanone were added, and then 1.93 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours, and the reaction was continuously measured while continuing the reaction. When the acid value of the reactant is 5.0 mgKOH/g or less, the reaction is stopped by cooling to room temperature. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the reactant containing the compound (A) in the solid content of the obtained resin varnish was 79%.

(Synthesis Example 6) 80.0 parts of 9,9-bis(3,4-dicarboxyphenyl)sebacic anhydride and 160.2 parts were placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. The pentaerythritol triacrylate (1) having a hydroxyl value of 122 mgKOH/g, 0.16 parts of methyl hydroquinone, and 158.8 parts of cyclohexanone were heated to 60 °C. Then, 1.20 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 82 mgKOH/g. Then, 50.3 parts of glycidyl methacrylate and 31.6 parts of cyclohexanone were added, and then 1.94 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours while continuing the reaction while periodically. The acid value of the reactant was measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the reactant containing the compound (A) in the solid content of the obtained resin varnish was 75%.

(Synthesis Example 7) 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 250.0 parts were placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. Pentaerythritol triacrylate (1) having a hydroxyl value of 122 mgKOH/g, 0.24 parts of methyl hydroquinone, and 217.8 parts of cyclohexanone were heated to 60 °C. Then, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 94 mgKOH/g. Then, 78.3 parts of glycidyl methacrylate and 54.0 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours while continuing the reaction while periodically. The acid value of the reactant was measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the reactant containing the compound (A) in the solid content of the obtained resin varnish was 76%.

(Synthesis Example 8) 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 359.0 parts were placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. Dipentaerythritol pentaacrylate having a hydroxyl value of 85 mgKOH/g, 0.29 parts of methyl hydroquinone, and 290.1 parts of cyclohexanone were heated to 60 °C. Then, 2.19 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 74 mgKOH/g. Then, 78.3 parts of glycidyl methacrylate and 48.7 parts of cyclohexanone were added, and then 3.53 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours while continuing the reaction while periodically. The acid value of the reactant was measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the reactant containing the compound (A) in the solid content of the obtained resin varnish was 69%.

(Synthesis Example 9) 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 63.1 parts were placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. The hydroxyl value was 483 mgKOH/g of 2-hydroxyethyl acrylate, 0.11 part of methyl hydroquinone, and 94.6 parts of cyclohexanone, and the temperature was raised to 60 °C. Then, 0.72 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 215 mgKOH/g. Then, 123.1 parts of biphenyl glycidyl ether and 80.9 parts of cyclohexanone were added, and then 1.15 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours, and the reaction was continuously measured while continuing the reaction. When the acid value of the reactant is 5.0 mgKOH/g or less, the reaction is stopped by cooling to room temperature. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the reactant containing the compound (A) in the solid content of the obtained resin varnish was 89%.

(Synthesis Example 10) 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 63.1 parts were placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. The hydroxyl value was 483 mgKOH/g of 2-hydroxyethyl acrylate, 0.11 part of methyl hydroquinone, and 94.6 parts of cyclohexanone, and the temperature was raised to 60 °C. Then, 0.72 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 215 mgKOH/g. Then, 108.8 parts of 4-hydroxybutyl acrylate glycidyl ether and 71.4 parts of cyclohexanone were added, and then 1.15 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours while continuing the reaction. The acid value of the reactant was periodically measured. When the acid value was 5.0 mgKOH/g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g. Therefore, the reactant containing the compound (A) in the solid content of the obtained resin varnish was 89%. (Synthesis Example 11) 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 250.0 parts were placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. Pentaerythritol triacrylate (1) having a hydroxyl value of 122 mgKOH/g, 0.24 parts of methyl hydroquinone, and 217.8 parts of cyclohexanone were heated to 60 °C. Then, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 94 mgKOH/g. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 94 mgKOH/g. Therefore, the reactant containing the compound (A) in the solid content of the obtained resin varnish was 72%.

(Synthesis Example 12) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 80.0 parts of 1,2,3,4-butanetetracarboxylic dianhydride and 402.0 parts of hydroxyl value were charged. It was 113 mg KOH/g of pentaerythritol triacrylate (2), 0.34 part of methyl hydroquinone, and 203.8 parts of cyclohexanone, and the temperature was raised to 60 °C. Then, 1.75 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 95 mgKOH/g. Then, 116.4 parts of glycidyl methacrylate and 188.5 parts of cyclohexanone were added, and then 3.88 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours while continuing the reaction while periodically. The acid value of the reactant was measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g, so that the reactant in the solid content of the obtained resin varnish was 71%. Further, the reactant does not contain the compound (A). The same applies to Synthesis Example 13 and Synthesis Example 14 below.

(Synthesis Example 13) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 80.0 parts of 1,2,4,5-benzenetetracarboxylic dianhydride and 364.9 parts of a hydroxyl value were charged. 113 mg KOH/g of pentaerythritol triacrylate (2), 0.31 part of methyl hydroquinone, and 293.9 parts of cyclohexanone were heated to 60 °C. Then, 2.22 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 93 mgKOH/g. Then, 105.6 parts of glycidyl methacrylate and 66.9 parts of cyclohexanone were added, and then 3.58 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours while continuing the reaction while periodically. The acid value of the reactant was measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g, so that the reactant in the solid content of the obtained resin varnish was 71%.

(Synthesis Example 14) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer, 80.0 parts of 1,2,3,4-butanetetracarboxylic dianhydride and 533.3 parts of a hydroxyl value were charged. The temperature was raised to 60 ° C at 85 mg KOH/g dipentaerythritol pentaacrylate, 0.37 parts methyl hydroquinone, and 405.5 parts cyclohexanone. Then, 3.07 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst was added, and the mixture was stirred at 90 ° C for 8 hours. In the IR measurement of the reactant, it was confirmed that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was stopped to stop the reaction. The acid value of the reactant was measured at this time point and found to be 75 mgKOH/g. Then, 116.4 parts of glycidyl methacrylate and 72.6 parts of cyclohexanone were added, and then 4.93 parts of dimethylbenzylamine as a catalyst was added, and the mixture was stirred at 100 ° C for 6 hours while continuing the reaction while periodically. The acid value of the reactant was measured. When the acid value was 5.0 mgKOH/g or less, the reaction was cooled to room temperature to stop the reaction. The obtained resin varnish was light yellow transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH/g, so that the reactant in the solid content of the obtained resin varnish was 68%.

A summary of the synthesis and an overview of the reactants obtained are shown in Table 1. The abbreviations described in the table indicate the product names of the compounds.

[Table 1] Table 1.

(Preparation of metal oxide composition) The resin varnish containing the compound (A) produced by the above-mentioned synthesis example was used, and the metal oxide was dispersed according to the formulation (parts) shown in Table 2 to prepare a dispersed metal oxide. Metal oxide composition of matter. Further, a resin varnish was used as a producer in the synthesis example. The dispersion method was predispersed (using zirconia beads (0.5 mm) as a medium, dispersed by a paint shaker for 1 hour), and officially dispersed (using zirconia beads (0.1 mm) as a medium, using Shou Industrial ( The production of the disperser UAM-015 to disperse) is carried out in two stages.

[Table 2] Table 2.

The abbreviation in Table 2 is shown below. TiO ₂ : "MT-05" manufactured by Tayca Co., Ltd. (average primary particle diameter: 10 nm) ZrO ₂ : "PCS-60" manufactured by Nippon Electric Co., Ltd. (average primary particle diameter: 20 nm) BaTiO ₃ : "KZM-20" manufactured by 堺Chemical Industries Co., Ltd. (average primary particle size: 20 nm) ZnO: "FINEX-50" manufactured by 堺Chemical Industries Co., Ltd. (on average Particle size: 20 nm) SiO ₂ : "AEROSIL 50" manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 50 nm) Al ₂ O ₃ : Japan Airo "Aluminium Oxide C" (average primary particle size: 13 nm) manufactured by Nippon Aerosil Co., Ltd. MEK: methyl ethyl ketone Methobuta: 3-methoxy-1-butanol

<D50 Particle Size> The D50 particle diameter of the obtained metal oxide composition was measured using "Nnotrac UPA" manufactured by Nikkiso Co., Ltd. Practically, it must be below 200 nm.

<Preparation and Evaluation of Curable Resin Composition and Laminate: Examples 1 to 33 and Comparative Examples 1 to 7 (Example 1) A compound having an anthracene structure and two propylene groups ( A9,9-bis[4-(2-acryloxyethoxy)phenyl]anthracene (trade name: "NK Ester A-BPEF", manufactured by Shin-Nakamura Chemical Co., Ltd.), and Pentaerythritol tetraacrylate (trade name: "Aronix M450", manufactured by Toagosei Co., Ltd.) having a compound (X) having three or more (meth) acrylonitrile groups, to be (A): (X) = 30 parts: 70 parts of the mixture were mixed, and 5 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals) and propylene glycol monomethyl ether as a photopolymerization initiator were mixed to obtain a solid content. 40% of a curable resin composition (also referred to as a coating composition or a coating liquid). The composition was applied to a 125 μm thick adhesive polyethylene terephthalate (PET) film by a bar coater so that the film thickness after drying became 1.5 μm. After "Lumirror UH13" manufactured by Toray Co., Ltd., a high-pressure mercury lamp was used to irradiate ultraviolet rays of 400 mJ/cm ² to form a resin layer. Then, the high-pressure mercury lamp was used to irradiate the ultraviolet rays of 2000 mJ/cm ² once to three times. On the resin layer as the active energy ray-cured film obtained by the sputtering method, the thickness of the ITO film as the transparent conductive film is 30 nm, and only the transparent conductive film is patterned (etched). It is formed into a stripe shape to obtain a laminate.

(Example 2) The same as Example 1 except that the ratio of NK ester (NK Ester) A-BPEF (A) to pentaerythritol tetraacrylate (X) was changed to (A): (X) = 50:50. The way to get the laminate.

(Example 3) The same as Example 1 except that the ratio of NK ester (NK Ester) A-BPEF (A) to pentaerythritol tetraacrylate (X) was changed to (A): (X) = 70:30. The way to get the laminate.

(Example 4) The same as Example 1 except that the ratio of NK ester (NK Ester) A-BPEF (A) to pentaerythritol tetraacrylate (X) was changed to (A): (X) = 100:0. The way to get the laminate.

(Example 5) Except that NK ester (NK Ester) A-BPEF (A) and pentaerythritol tetraacrylate (X), and zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to (A): (X): the particle component of the metal oxide = 10:40:50, the same as in the first embodiment The way to get the laminate.

(Example 6) Except that NK ester (NK Ester) A-BPEF (A) and pentaerythritol tetraacrylate (X), and zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to (A): (X): the particle component of the metal oxide = 25:25:50, the same as in the first embodiment The way to get the laminate.

(Example 7) Except that NK ester (NK Ester) A-BPEF (A) and pentaerythritol tetraacrylate (X), and zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to (A): (X): the particle content of the metal oxide = 35:15:50, the same as in the first embodiment The way to get the laminate.

(Example 8) Except that NK ester (NK Ester) A-BPEF (A) and pentaerythritol tetraacrylate (X), and zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to (A): (X): the particle content of the metal oxide = 50:0:50, the same as in the first embodiment The way to get the laminate.

(Example 9) Synthesis Example 1 which is a compound (A) having a biphenyl structure and two or more (meth) acryl fluorenyl groups, and a compound (X) having three or more (meth) acryl fluorenyl groups Pentaerythritol tetraacrylate (trade name: "Aronix M450", manufactured by Toagosei Co., Ltd.), mixed in such a manner that the reaction product containing the compound (A) of Synthesis Example 1: (X) = 30:70 Further, 5 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals) and propylene glycol monomethyl ether as a photopolymerization initiator were mixed to obtain a curable composition adjusted to have a solid content of 40% (also referred to as a hardening composition). It is a coating composition or coating liquid). The composition was applied to a 125 μm-thick adhesive PET film (Toray Miller) by a bar coater so that the film thickness after drying became 1.5 μm. After (Lumirror) UH13"), ultraviolet rays of 400 mJ/cm ² were irradiated with a high pressure mercury lamp to form a resin layer. Then, ultraviolet rays of 2000 mJ/cm ² were irradiated once to three times with a high pressure mercury lamp. On the resin layer as the active energy ray-cured film, the thickness of the ITO film as the transparent conductive film is 30 nm, and the transparent conductive film is patterned (etched). It is formed into a stripe shape to obtain a laminate.

(Example 10) The ratio of the reaction product containing the compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X) was changed to the reaction product containing the compound (A) of Synthesis Example 1: (X) = 50: A laminate was obtained in the same manner as in Example 9 except for 50.

(Example 11) The ratio of the reaction product containing the compound (A) of Synthesis Example 1 and the pentaerythritol tetraacrylate (X) was changed to the reaction product containing the compound (A) of Synthesis Example 1: (X) = 70: A laminate was obtained in the same manner as in Example 9 except for 30.

(Example 12) The reaction product containing the compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 1: (X): particle composition of the metal oxide = 10:40:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 13) The reaction product containing the compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 1: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 14) Except that the reactant containing the compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 1: (X): particle composition of the metal oxide = 35:15:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 15) Except that the reactant containing the compound (A) of Synthesis Example 2 and pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 2: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 16) Except that the reactant containing the compound (A) of Synthesis Example 3 and pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 3: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 17) The reaction product containing the compound (A) of Synthesis Example 4 and the pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 4: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 18) The reaction product containing the compound (A) of Synthesis Example 5 and the pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 5: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 19) Except that the reactant containing the compound (A) of Synthesis Example 6 and pentaerythritol tetraacrylate (X), and the particle concentration of the metal oxide of 30% by weight and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 6: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 20) The reaction product containing the compound (A) of Synthesis Example 7 and pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 7: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 21) Except that the reactant containing the compound (A) of Synthesis Example 8 and pentaerythritol tetraacrylate (X), and the particle concentration of the metal oxide of 30% by weight and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 8: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 22) Except that the reactant containing the compound (A) of Synthesis Example 9 and pentaerythritol tetraacrylate (X), and the particle concentration of the metal oxide of 30% by weight and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 9: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 23) Except that the reactant containing the compound (A) of Synthesis Example 10 and pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 10: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 24) Except that the reactant containing the compound (A) of Synthesis Example 11 and pentaerythritol tetraacrylate (X), and the zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to the reaction product containing the compound (A) of Synthesis Example 11: (X): particle composition of the metal oxide = 25:25:50 A laminate was obtained in the same manner as in Example 9 except for the same.

(Example 25) The reaction product of the compound (A) of Synthesis Example 1 and the pentaerythritol tetraacrylate (X), and the metal oxide composition (1) containing the synthesis example (1) as a metal oxide, The laminate was obtained in the same manner as in Example 9 except that the reactant of the compound (A) of Synthesis Example 1 was changed: (X): the particle component of the metal oxide = 40:11:49.

(Example 26) The reaction product of the compound (A) of Synthesis Example 1 and the pentaerythritol tetraacrylate (X), and the metal oxide composition (2) containing the synthesis example (1) as a metal oxide, The laminate was obtained in the same manner as in Example 25 except that the reactant of the compound (A) of the synthesis example 1 was changed: (X): the particle component of the metal oxide = 40:11:49.

(Example 27) Except that the reactant containing the compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), and the metal oxide composition (3) containing the synthesis example (1) as a metal oxide, The laminate was obtained in the same manner as in Example 25 except that the reactant of the compound (A) of the synthesis example 1 was changed: (X): the particle component of the metal oxide = 40:11:49.

(Example 28) In addition to the reaction product containing the compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), and the metal oxide composition (4) containing the synthesis example (1) as a metal oxide, The laminate was obtained in the same manner as in Example 25 except that the reactant of the compound (A) of the synthesis example 1 was changed: (X): the particle component of the metal oxide = 40:11:49.

(Example 29) The reaction product of the compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), and the metal oxide composition (5) containing the synthesis example (1) as a metal oxide, The laminate was obtained in the same manner as in Example 25 except that the reactant of the compound (A) of the synthesis example 1 was changed: (X): the particle component of the metal oxide = 40:11:49.

(Example 30) The reaction product of the compound (A) of Synthesis Example 1 and the pentaerythritol tetraacrylate (X), and the metal oxide composition (6) containing the synthesis example (1) as a metal oxide, The laminate was obtained in the same manner as in Example 25 except that the reactant of the compound (A) of the synthesis example 1 was changed: (X): the particle component of the metal oxide = 40:11:49.

(Example 31) The reaction product of the compound (A) of Synthesis Example 1 and the pentaerythritol tetraacrylate (X), and the metal oxide composition (7) containing the synthesis example (7) as a metal oxide, The laminate was obtained in the same manner as in Example 25 except that the reactant of the compound (A) of Synthesis Example 7 was changed: (X): the particle component of the metal oxide = 40:11:49.

(Example 32) A reactant containing the compound (A), pentaerythritol IV, in addition to the NK ester (NK Ester) A-BPEF and the metal oxide composition (1) containing the synthesis example (1) as a metal oxide The layered body was obtained in the same manner as in Example 25 except that the acrylate (X) was changed to (A): (X): the particle component of the metal oxide = 47:4:49.

(Example 33) A reactant containing the compound (A), pentaerythritol IV, in addition to the NK ester (NK Ester) A-BPEF and the metal oxide composition (7) containing the synthesis example (7) as a metal oxide The layered body was obtained in the same manner as in Example 25 except that the acrylate (X) was changed to (A): (X): the particle component of the metal oxide = 46:5:49.

(Comparative Example 1) The same as Example 1 except that the ratio of NK ester (NK Ester) A-BPEF (A) to pentaerythritol tetraacrylate (X) was changed to (A): (X) = 0:100. The way to get the laminate.

(Comparative Example 2) Except that NK ester (NK Ester) A-BPEF (A) and pentaerythritol tetraacrylate (X), and zirconia having a particle concentration of 30 wt% as a metal oxide and having a particle diameter of 15 nm were dispersed. The product (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to (A): (X): the particle content of the metal oxide was 0:50:50, and the same as in the first embodiment. The way to get the laminate.

(Comparative Example 3) except that 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene having no (meth)acryl fluorenyl group and pentaerythritol tetraacrylate (X), and oxidation as a metal A zirconia dispersion having a particle concentration of 30% by weight and a particle diameter of 15 nm (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to 9,9-bis [4-(2- A layered body was obtained in the same manner as in Example 1 except that the particle component of the metal oxide = 25:25:50 was used for the hydroxyethoxy)phenyl]anthracene: (X).

(Comparative Example 4) except that ethoxylated o-phenylphenol acrylate having one (meth)acrylinyl group and pentaerythritol tetraacrylate (X), and a particle concentration of the metal oxide were 30% by weight, A zirconia dispersion having a particle size of 15 nm (trade name: "ZR-010", manufactured by Solar Co., Ltd.), changed to ethoxylated o-phenylphenol acrylate: (X): particles of metal oxide A laminate was obtained in the same manner as in Example 1 except that the composition = 25:25:50.

(Comparative Example 5) A reaction product containing the synthesis example (12) having no fluorene structure and/or a biphenyl structure, and pentaerythritol tetraacrylate (X), and a particle concentration of the metal oxide of 30% by weight, granules The zirconia dispersion having a diameter of 15 nm (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to (X): the particle content of the metal oxide = 50:50, and Example 1 The laminate is obtained in the same manner.

(Comparative Example 6) A reaction product containing the synthesis example (13) having no fluorene structure and/or a biphenyl structure, and pentaerythritol tetraacrylate (X), and a particle concentration of the metal oxide as 30% by weight, granules The zirconia dispersion having a diameter of 15 nm (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to (X): the particle content of the metal oxide = 50:50, and Example 1 The laminate is obtained in the same manner.

(Comparative Example 7) A reaction product containing the synthesis example (14) having no fluorene structure and/or a biphenyl structure, and pentaerythritol tetraacrylate (X), and a particle concentration of the metal oxide as 30% by weight, granules The zirconia dispersion having a diameter of 15 nm (trade name: "ZR-010", manufactured by Solar Co., Ltd.) was changed to (X): the particle content of the metal oxide = 50:50, and Example 1 The laminate is obtained in the same manner.

(Evaluation method) The adhesion was evaluated before laminating the transparent conductive film and after laminating the transparent conductive film. Regarding transparency and scratch resistance, evaluation was performed before laminating a transparent conductive film. The evaluation results are shown in Tables 3 and 4.

The abbreviations in Tables 3 and 4 are shown below. In addition, the unit of the amount of preparation described in the table is a part. Photopolymerization initiator: "Irgacure 184" manufactured by Ciba Specialty Chemicals (Solvent): PGME (propylene glycol monomethyl ether) [Table 3] Table 3

[Table 4] Table 4

(1) Adhesion (before lamination of transparent conductive film) Resistance was evaluated by an adhesive cross-cut method in accordance with JIS K5600-5-6. The results were classified into the following 0 to 5. In practice, it must be Category 0 or Category 1. 0: The edge of the slit is completely smooth and there is no peeling in any of the lattice eyes. 1: The layered body at the intersection of the slits has a small peeling, and there is less than 5% peeling per unit area. 2: The laminate is peeled off along the edge of the slit and/or at the intersection. There is 5% or more and less than 15% peeling per unit area. 3: The laminate body partially or comprehensively produces large peeling along the edge of the slit, and/or many portions of the lattice eye are partially or completely peeled off. There is more than 15% and less than 35% peeling per unit area. 4: The laminate body partially or comprehensively produces large peeling along the edge of the slit, and/or the lattice eyes of several portions are partially or comprehensively peeled off. There is less than 35% peeling per unit area. 5: More than 35% of the peeling per unit area.

(2) Adhesiveness (after lamination of a transparent conductive film) Resistance was evaluated by an adhesive cross-cut method in accordance with JIS K5600-5-6. As a method of evaluation, the test results were classified into the following 0 to 5. The adhesion of the substrate thus evaluated to the resin layer and the transparent conductive film must be practically classified into Category 0 or Category 1. Here, the peeling of the base material and the resin layer can be confirmed by visually confirming the laminated body or measuring the film thickness. 0: The edge of the slit is completely smooth and there is no peeling in any of the lattice eyes. 1: The laminate of the intersection of the slits has a small peeling. Less than 5% peeling per unit area. 2: The laminate is peeled off along the edge of the slit and/or at the intersection. There is 5% or more and less than 15% peeling per unit area. 3: The laminate body partially or comprehensively produces large peeling along the edge of the slit, and/or many portions of the lattice eye are partially or completely peeled off. There is more than 15% and less than 35% peeling per unit area. 4: The laminate body partially or comprehensively produces large peeling along the edge of the slit, and/or the lattice eyes of several portions are partially or comprehensively peeled off. There is less than 35% peeling per unit area. 5: More than 35% of the peeling per unit area.

(3) Transparency (haze value) The haze (haze value) of the laminate having the substrate and the resin layer before laminating the transparent conductive film was measured using a haze meter. Practically, the haze value must be 1.5% or less.

(4) Scratch resistance (hard-coating property) The laminated body which has the base material and the resin layer before laminating the transparent conductive film was set on the Gakushin-type Rubbing Tester test machine, and No.0000 of steel wool was used. It was tempered 10 times with a load of 250 g. For the taken-out laminate, the injury was judged based on the visual evaluation of the following five stages. The larger the value, the better the scratch resistance of the laminate. 5: Completely free of scars. 4: With a small amount of scars. 3: With a flaw, but the substrate is not visible. 2: With a scar, a part of the hardened film peeled off. 1: The cured film peeled off and the substrate was exposed.

From the results of Tables 3 and 4, it was found that the laminates of Examples 1 to 33 were excellent in transparency and adhesion balance. In addition, even if a metal oxide is contained in the resin layer as the active energy ray-cured film, the transparency and the adhesion are excellent and the balance is excellent.

On the other hand, the adhesion between the polyester base material of Comparative Example (1) to Comparative Example (7) containing no compound (A) and the resin layer as the active energy ray-curing film, and the resin as the active energy ray-curing film The adhesion between the layer and the transparent conductive film is insufficient.

no

Claims (9)

A laminate comprising a resin layer obtained by curing an active energy ray-curable composition containing a compound (A) having a fluorene structure and/or a biphenyl group on a substrate as a polyester film. The structure and the two or more (meth)acrylonitrile groups, and the laminate further has a transparent conductive film. The laminate according to claim 1, wherein the resin layer is a layer obtained by hardening a composition further comprising a compound having three or more (meth) acrylonitrile groups ( X) (except in the case of the compound (A)). The laminate according to claim 2, wherein the compound (A) having a fluorene structure and/or a biphenyl structure and two or more (meth) acryl fluorenyl groups has three or more ( The content of the compound (A) is from 10% by weight to 90% by weight based on 100% by weight of the total of the solid components of the methyl (meth) fluorenyl group compound (X) (excluding the case of the compound (A)). The laminate according to any one of claims 1 to 3, wherein the compound (A) is a compound (A1) represented by the following formula (1), and the formula (1): (In the formula (1), at least one of R ₁ and R ₃ is a tetravalent or monovalent organic residue shown below, and R ₂ represents a monovalent organic residue having a (meth) acrylonitrile group) . The laminate according to any one of claims 1 to 3, wherein the compound (A) is a compound (A2) represented by the following formula (2), and the formula (2): R ₅ -OR ₄ -OR ₅ (In the formula (2), R ₄ is a divalent organic residue shown below, and R ₅ represents a monovalent organic residue having a (meth) acrylonitrile group) . The laminate according to any one of claims 1 to 5, wherein, in the case of irradiating an active energy ray having an integrated light amount of 2000 mJ/cm ² or more, the use is in accordance with Japanese Industrial Standard K5600-5- The adhesion between the substrate and the resin layer measured by the adhesion cross-cut method of 6 is less than 5% of the peeling area per unit area. The laminate according to any one of claims 1 to 6, wherein the composition further comprises a metal oxide. The laminate according to claim 7, wherein the metal oxide comprises titanium and/or zirconium atoms. A method for producing a laminate comprising: coating a compound (A) comprising a fluorene structure and/or a biphenyl structure and two or more (meth) acryl fluorenyl groups on a substrate as a polyester film The active energy ray-curable composition, the step of irradiating the active energy ray to harden it to form a resin layer, and the step of forming a transparent conductive film.