JP2017037830A - Laminate having transparent conductive film and production method of laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film having hard coat property, transparency and enough adhesiveness to endure severe irradiation with active energy rays in the production of a transparent conductive film.SOLUTION: A laminate is provided, which has a resin layer formed by curing an active energy ray-curable composition comprising a compound (A) having a fluorene structure and two or more (meth)acryloyl groups and a metal oxide containing a titanium and/or zirconium atom on a substrate that is a polyester film, and further has a transparent conductive film.SELECTED DRAWING: None

Description

  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 production method for forming the laminate.

Conventionally, a transparent conductive laminate in which a transparent conductive film is provided on a substrate such as polyester has been used for touch panel applications and the like. As the transparent conductive film, a thin film of metal oxide such as indium tin oxide (ITO) is generally used, and is laminated on the base material by sputtering or vacuum deposition.
As an operation method of the touch panel, a resistance film type is mainstream, but in recent years, a capacitance type has been rapidly expanded. A laminate having transparent conductivity used for a resistive film type touch panel is generally composed of a transparent conductive film that is not patterned. On the other hand, a transparent conductive laminate in which patterned transparent conductive films are laminated is generally used for the capacitive touch panel.

The transparent conductive laminate used for the capacitive touch panel is usually patterned with a transparent conductive film by photolithography etching or the like, and the pattern portion and the non-pattern portion of the transparent conductive film are planarly viewed. Exists.
A capacitive touch panel using such a transparent conductive layered laminate having a transparent conductive film has a problem with a so-called “bone-viewing” raw material in which the pattern portion of the transparent conductive film is visible. This degrades the quality of the display device.
For example, Patent Documents 1 and 2 propose to suppress the appearance of a transparent conductive film pattern.

JP 2011-84075 A Patent No. 5110226

In recent years, depending on the use of the laminate, it is multilayered on one or both sides of the substrate, 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 techniques of Patent Document 1 and Patent Document 2, although the effect of suppressing the bone appearance of the transparent conductive film pattern is seen, when the resin layer receives a large amount of active energy rays, the adhesion with the base material decreases. There was a problem such as. In addition, in order to ensure the adhesion between the base material and the resin layer, there is a problem that the layer configuration of the laminate is limited when trying to design the layer configuration so that the accumulated amount of active energy rays does not become large. It was.
Therefore, an object of the present invention is to provide a laminate having transparency and adhesiveness that can withstand irradiation of a large amount of active energy rays and a transparent conductivity in producing a laminate having transparent conductivity.

  The present invention cures an active energy ray-curable composition containing a compound (A) having a fluorene structure and / or a biphenyl structure and two or more (meth) acryloyl groups on a substrate that is a polyester film. The present invention relates to a laminate having a resin layer and a transparent conductive film.

Further, in the present invention, the resin layer is a layer obtained by curing a composition containing a compound (X) having three or more (meth) acryloyl groups (excluding the case where it is a compound (A)). It is related with the said laminated body.

The present invention also relates to a compound (A) having a fluorene structure and / or a biphenyl structure, and two or more (meth) acryloyl groups, and a compound (X) having three or more (meth) acryloyl groups (wherein It is related with the said laminated body whose content of a compound (A) is 10 to 90 weight% in the total of 100 weight% of solid content of the compound (A) except the case.

Moreover, this invention relates to the said laminated body whose said compound (A) is a compound (A1) represented by following General formula (1).
General formula (1):

(In General Formula (1), at least one of R ₁ and R ₃ is a tetravalent or monovalent organic residue shown below,
R ₂ represents a monovalent organic residue having a (meth) acryloyl group. )

Moreover, this invention relates to the said laminated body whose said compound (A) is a compound (A2) represented by following General formula (2).
General formula (2):
R ₅ —O—R ₄ —O—R ₅

(In the general formula (2), R ₄ is a divalent organic residue shown below,
R ₅ represents a monovalent organic residue having a (meth) acryloyl group. )

Moreover, this invention is the adhesiveness of the said base material measured by the adhesive crosscut method by JISK5600-5-6 at the time of irradiating the active energy ray more than 2000 mJ / cm < ² > of integrated light quantity. However, it is related with the said laminated body whose peeling area per unit area is less than 5%.

Moreover, this invention relates to the said laminated body in which the said composition contains a metal oxide further.
In addition, the present invention relates to the laminate, wherein the metal oxide includes titanium and / or zirconium atoms.

An active energy ray-curable composition containing a compound (A) having a fluorene structure and / or a biphenyl structure and two or more (meth) acryloyl groups is applied onto a substrate that is a polyester film, and an active energy ray Irradiating and curing to form a resin layer;
It is related with the manufacturing method of a laminated body including the process of forming a transparent conductive film.

  According to the present invention, it is possible to provide a laminate having transparency and adhesiveness capable of withstanding a large amount of active energy ray irradiation and transparent conductivity.

  The laminated body of this invention is provided in order of the resin layer which is an active energy ray cured film, and a transparent conductive film on the one surface or both surfaces on a base film.

  Hereinafter, each component which comprises the laminated body which has the base material which is the polyester film of this invention, the resin layer formed by hardening | curing an active energy ray curable composition, and a transparent conductive film is demonstrated 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 1.62 to 1.69, more preferably in the range of 1.63 to 1.68, and particularly preferably in the range of 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 made of an organic or inorganic substance on its surface, and specific examples thereof include an easy-adhesion layer for increasing the adhesion to other layers.

As a commercially available polyester film with an easy-adhesion layer,
Toray Industries, Inc .: Lumirror series, Toyobo Co., Ltd .: Cosmo Shine series. Particularly, Toray's UML13 and U48 series, which are highly transparent and used for optical applications, are preferable.

<Resin layer>
The resin layer of the present invention is a layer formed 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) acryloyl groups.

The compound (A) only needs to have one or more fluorene structures and / or biphenyl structures and two or more (meth) acryloyl groups in the structure, and the compound (A) has adhesion to the polyester film. Excellent.

Preferable specific examples of compound (A) also include compound (A1) represented by the following general formula (1). Since compound (A1) is excellent in hard coat properties, it can be suitably used.

General formula (1):



In general 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,
R ₂ represents a monovalent organic residue having a (meth) acryloyl group.

In the general formula (1), R ₁ is not particularly limited as long as it has a fluorene structure or a biphenyl structure, and preferred specific examples include the following tetravalent organic residues. Preferably, it is a residue having a biphenyl structure.

In the general formula (1), when R ₃ has a fluorene structure or a biphenyl structure, R ₁ may not have a fluorene structure or a biphenyl structure. Although it does not specifically limit as such, The tetravalent organic residue shown below is mentioned as a suitable specific example. A residue having an aromatic ring is preferred.

In the general formula (1), R ₃ is not particularly limited as long as it has a fluorene structure or a biphenyl structure, but preferred specific examples include the following monovalent organic residues.

In the general formula (1), when R ₁ has a fluorene structure or a biphenyl structure, R ₃ may not have a fluorene structure or a biphenyl structure. Although it does not specifically limit as such, A hydrogen atom or the monovalent organic residue shown below is mentioned.

In the general formula (1), R ₂ is not particularly limited as long as it has a (meth) acryloyl group, but preferred specific examples include the following monovalent organic residues.

It is preferable that the compound (A1) represented by the general formula (1) has two or more fluorene structures and / or biphenyl structures because of excellent adhesion to the substrate, and further R ₁ and R ₃
It is preferable that both have a fluorene structure or a biphenyl structure.

The number of (meth) acryloyl groups in compound (A) needs to be two or more. When it is 2 or less, the adhesiveness between the obtained active energy ray cured film and the base material which is a polyester film is lowered. Furthermore, since the hard coat property of the resin layer is excellent, the number of (meth) acryloyl groups is preferably 3 or more, and more preferably 6 or more.

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

  The tetracarboxylic dianhydride (b1) is not particularly limited as long as it has a fluorene structure or a biphenyl structure, and preferred examples include 3,3 ′, 4,4′-biphenyl having a biphenyl skeleton. Examples thereof include tetracarboxylic dianhydride and 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride having a fluorene skeleton, and preferably have a biphenyl structure. When 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. Although it does not specifically limit as such, As a suitable specific example, 1,2,4,5-benzenetetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride are mentioned. Preferably, it has an aromatic ring.

  Among these tetracarboxylic dianhydrides, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride can have both hard coat properties of the cured film and good dispersibility of the metal oxide. Is particularly preferred.

The compound (b2) is preferably pentaerythritol triacrylate and dipentaerythritol pentaacrylate from the viewpoints of photocurability and hard coat properties.
Specific commercial products of pentaerythritol triacrylate and dipentaerythritol pentaacrylate include Biscoat # 300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.), and PETIA (Daicel UCB ( Co., Ltd.), Aronix M305 (manufactured by Toagosei Co., Ltd.), NK ester A-TMM-3LMN (manufactured by Shin-Nakamura Chemical Co., Ltd.), light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.), SR- 444 (manufactured by Sartomer), light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), Aronix M402 (manufactured by Toagosei Co., Ltd.), and the like.

  These commercial products contain about 5 to 15% by weight of pentaerythritol diacrylate and dipentaerythritol tetraacrylate each having two hydroxyl groups as subcomponents. Therefore, in the reaction of tetracarboxylic dianhydride (b1) with pentaerythritol triacrylate and dipentaerythritol pentaacrylate, in addition to the compound (A1) represented by the general formula (1), a reaction product derived from subcomponents Further, a resin having a higher molecular weight is also generated.

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

The compound (b3) can be further reacted without purifying the reaction product containing the compound (A1-1) in which R ₃ is a hydrogen atom obtained by the above reaction.

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

  These reactions may be carried out without solvent or in a solvent inert to the reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene and toluene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; diethyl ether, tetrahydrofuran or Ether solvents such as dioxane; Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazo Examples include polar solvents such as lysinone. Two or more of these solvents may be used in combination.

  When adding a solvent, it is preferable to perform a curing treatment after volatilizing the solvent. The solvent is not particularly limited, and various known organic solvents can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-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, 2-ethoxyethyl acetate, butyl acetate , Isoamyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, and methyl pyrrolidone. These organic solvents may be used in combination of two or more.

Preferable specific examples of compound (A) also include compound (A2) represented by the following general formula (2).
General formula (2):
R ₅ —O—R ₄ —O—R ₅

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

In the general formula (2), R ₄ is not particularly limited as long as it has a fluorene structure or a biphenyl structure, but preferred specific examples include divalent organic residues shown below. Preferably, it is a residue having a fluorene structure.

In the general formula (2), R ₅ is not particularly limited as long as it has a (meth) acryloyl group, but preferred specific examples include the following monovalent organic residues.

Examples of the compound (A2) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. Moreover, as a commercial item, NK ester A-BPEF by Shin-Nakamura Chemical Co., Ltd., Ogsol EA series by Osaka Gas Chemical Co., Ltd., etc. can be used.

The active energy ray-curable composition can further contain a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization of a (meth) acryloyl group for forming an active energy ray cured film by photoexcitation. For example, a monocarbonyl compound or a dicarbonyl compound An acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl compound, or the like can be used.

  Specifically, as the monocarbonyl compound, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl -Ethanone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4) , 7,10,13-pentaoxotridecyl) benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethyl-1-propanamine Hydrochloride, 4-benzoyl-N, N-dimethyl-N-2- (1-oxo-2-propenyloxy) Til) metaammonium oxalate, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3 4-dimethyl-9-oxo-9H thioxanthone-2-yloxy-N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline, and the like.

Examples of dicarbonyl compounds include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.
Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropan-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-morpholinopropan-1-one, 2-benzyl-2-dimethyla Mino-1- (4-morpholinophenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino -Propanonyl) -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 normal butyl ether.
Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide, and the like.

Examples of aminocarbonyl compounds include methyl-4- (dimethoxyamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate, and isoamyl-4- (dimethylamino) benzoate. 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis (4-diethylaminobenzal) cyclopenta Non etc. are mentioned.
Commercially available photopolymerization initiators include Irgacure 184, 651, 500, 907, 127, 369, 784, 2959, manufactured by Ciba Specialty Chemicals Co., Ltd., Lucilin TPO manufactured by BASF, Esacure One manufactured by Nippon Sibel Hegner, Inc. can give.

The photopolymerization initiator is not limited to the above compound, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization by ultraviolet rays. These photopolymerization initiators may be used alone or in combination of two or more.
The amount of the photopolymerization initiator used is not particularly limited, but the total amount of the active energy ray-curable compound including the compound (A) (in the case where a photocurable compound other than the compound (A) is included, the compound (A) And the total amount of photocurable compounds other than the compound (A)) are preferably used within a range of 1 to 20 parts by weight per 100 parts by weight.
A known organic amine or the like can be added as a sensitizer.
Furthermore, in addition to the radical polymerization initiator, a cationic polymerization initiator may be used in combination.

The active energy ray-curable composition can further contain a compound (X) having three or more (meth) acryloyl groups (except when it is a compound (A)). Compound (X) can further improve the hard coat property of the resin layer.
As the compound (X), poly (meth) acrylates such as polyurethane poly (meth) acrylate and polyepoxypoly (meth) acrylate, and polyfunctional acrylates are preferably used from the viewpoint of coating strength and scratch resistance. be able to.
Polyepoxy poly (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid and converting the functional group to a (meth) acryloyl group, and (meth) acrylic to a bisphenol A type epoxy resin. There are acid addition products, (meth) acrylic acid addition products to novolac type epoxy resins, and the like.

  Polyurethane poly (meth) acrylate is, for example, one obtained by reacting diisocyanate with (meth) acrylate having a hydroxyl group, or isocyanate group-containing urethane obtained by reacting polyol and polyisocyanate under the condition of excess isocyanate group. Some are obtained by reacting a prepolymer with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.

  Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexanetriol, trimellilol propane, polytetra Examples include methylene glycol and a condensation polymer of adipic acid and ethylene glycol.

Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like.
Examples of the (meth) acrylates having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and (meth) acryloyl isocyanate.

The following can be illustrated as a commercial item of a photocurable compound.
Toa Gosei Co., Ltd .: Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060,
Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400
Kayaku Sartomer Co., Ltd .: SR-295,
Daicel UCB Co., Ltd .: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602,
Shin Nakamura Chemical Co., Ltd .: NK Ester A-TMMT, NK Oligo EA-1020, 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,
Manufactured by BASF: LaromerEA81,
Sannopco: Photomer 3016,
Arakawa Chemical Industries, Ltd .: beam set 371, beam set 575, beam set 577, beam set 700, beam set 710;
Manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, 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,
Nippon 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,
Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A, Light acrylate DPE-6A, UA-306H, UA-306T, UA-306I,
Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330.

The above compound (X) having three or more (meth) acryloyl groups may be used alone or in combination.
Further, in general, pentaerythritol triacrylate and dipentaerythritol pentaacrylate that can be used as the compound (b2) include pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate having no hydroxyl group. Therefore, when pentaerythritol triacrylate and dipentaerythritol pentaacrylate are used for the compound (b2), pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate contained in these contribute to the improvement of the hard coat property as the compound (X). .

  Compound (A) having a fluorene structure and / or biphenyl structure, and two or more (meth) acryloyl groups, and compound (X) having three or more (meth) acryloyl groups (provided that the compound (A)) The content of the compound (A) is preferably from 10 to 90% by weight, more preferably from 20 to 80% by weight, in a total of 100% by weight of the solid content of (except the case). It is because it is excellent in the adhesiveness of a polyester base material and a resin layer, and hard-coat property as it is in the said range.

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

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

When a metal oxide is included, the content thereof is preferably 10 to 80% by weight, more preferably 30 to 60% by weight, based on the solid content of the curable composition.
As the metal oxide, one prepared in advance as a dispersion containing the compound (A) can be used. A dispersion using the compound (A1) is preferable.

Next, the manufacturing method of the resin layer formed by hardening | curing an active energy ray curable composition is demonstrated.
The method for producing the resin layer includes, for example, applying the active energy ray-curable resin composition to a substrate that is a polyester film, and irradiating the active energy ray to form the active energy ray-curable composition on the substrate. Curing.
More specifically, after applying the resin composition to a base material that is a polyester film, the film thickness after drying is preferably 0.02 to 30 μm, more preferably 0.02 to 20 μm, It can be formed by curing treatment.

As a coating method, a known method can be used. For example, a method using a lot or a wire bar, or various coating methods such as microgravure, gravure, die, curtain, lip, slot or spin can be used. it can.
The curing treatment can be performed by irradiating active energy rays such as ultraviolet rays, electron beams, visible rays having a wavelength of 400 to 500 nm, using a known technique. 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 as a source (light source) of ultraviolet rays and visible light having a wavelength of 400 to 500 nm. As the electron beam source, a thermionic emission gun, an electrolytic emission gun, or the like can be used.

The active energy dose to be irradiated is preferably in the range of 50 to 1000 mJ / cm ² from the viewpoint of easy management in the process.
These active energy rays can be used in combination with heat treatment by infrared rays, far infrared rays, hot air, high frequency heating or the like.

The cured film may be formed by applying an active energy ray-curable composition to a substrate and naturally or forcibly drying it, followed by curing treatment, or after coating and curing treatment. Alternatively, forced drying may be performed, but it is more preferable to perform the curing treatment after natural or forced drying.
In particular, in the case of curing with an electron beam, it is more preferable to carry out the curing treatment after natural or forced drying in order to prevent the inhibition of curing by water or the decrease in strength of the coating film due to the remaining organic solvent.
The timing of the curing treatment may be simultaneous with coating or after coating.

Since the obtained cured film is excellent in transparency and adhesion, it can be suitably used as an optical material.
The thickness of the cured film is preferably 0.02 to 30 μm.
Furthermore, 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 cured film of the present invention can further contain various additives within a range not impairing the object and effects of the present invention. Specifically, photocurable compounds other than compound (A) and compound (X), polymerization inhibitors, photosensitizers, leveling agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, UV absorbers , Infrared absorbers, antioxidants, silane coupling agents, conductive polymers, conductive surfactants, inorganic fillers, pigments, dyes and the like.

<Transparent conductive film>
As a material of the transparent conductive film, a known material used for an electrode of a touch panel can be used. Examples thereof include metal oxides such as tin oxide, indium oxide, antimony oxide, zinc oxide, ITO (indium tin oxide), and ATO (antimony tin oxide). Among these, ITO is preferably used.

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 from the viewpoint of ensuring good conductivity with a surface resistance value of 10 ³ Ω / □ or less, for example. On the other hand, if the thickness of the transparent conductive film becomes too large, there may be a problem that the transparency is 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 40 nm or less. preferable.

  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, more preferably 1.90 or more. The upper limit is preferably 2.20 or less, and more preferably 2.10 or less.

  It does not specifically limit as a formation method of a transparent conductive film, A conventionally well-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, the transparent conductive film formed as described above is patterned. Patterning can form various patterns according to the use to which a transparent conductive film is applied. Note that the pattern portion and the non-pattern portion are formed by patterning the transparent conductive film. Examples of the shape of the pattern portion include a stripe shape and a lattice shape.

  The patterning of the transparent conductive film is generally performed by etching. For example, a transparent conductive film is patterned by forming a patterned etching resist film on the transparent conductive film by a photolithography method, a laser exposure method, or a printing method and then performing an etching process.

  A conventionally well-known thing is used as an etching liquid. For example, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid and phosphoric acid, organic acids such as acetic acid, and mixtures thereof, and aqueous solutions thereof are used.

The laminated body of this invention has a base material which is a polyester film, a resin layer which is an active energy ray cured film, and a transparent conductive film, and the base material and the resin layer should just be adjacent. The other layer configuration is arbitrary, and a film or an adhesive layer having a different refractive index can be provided on one side of the base material or the resin layer as necessary.

Some preferred structural examples of the laminate of the present invention are listed below, but the present invention is not limited thereto. In the following configuration example, the transparent conductive film is a patterned transparent conductive film. Other layers other than the transparent conductive film are not patterned.
(I) Base material / 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 / base material / resin layer / transparent conductive film (VI) resin layer // base material / resin layer / transparent conductive film where (M) is a film or adhesive having a different refractive index Any one of the layers is included.

  Films having different refractive indexes have functions other than the functions of the resin layer of the present invention. The formation method is not particularly limited, and it is formed by a known method. For example, dry coating methods such as vapor deposition and sputtering, methods using lots and wire bars, and wet coating methods such as microgravure, gravure, die, curtain, lip, slot, and spin can be used. There is no limitation on the material to be used, and if necessary, one or more kinds of functions such as an information recording function, an antiglare function, a Newton ring prevention function, an adhesive function, a specific wavelength blocking function, and a color tone correction function can be imparted to the laminate. Any material that can be used can be used.

The laminated body of the present invention is irradiated with active energy rays when the resin layer or an arbitrary layer is cured during production or when the transparent conductive film is patterned. Even if the total amount of active energy rays irradiated to the resin layer in this production process is 2000 mJ / cm ² or more, the adhesion between the base material made of polyester and the resin layer made of the active energy ray cured film is excellent. The integrated light amount includes the integrated light amount at the time of initial curing for forming a resin layer that is an active energy ray cured film.

[Adhesion]
Adhesiveness of a laminate having a substrate which is a polyester film of the present invention, a resin layer which is an active energy ray cured film, and a transparent conductive film is evaluated by an adhesive crosscut method according to JIS K5600-5-6. The adhesion is very excellent with an isolated area per unit area of less than 5%. Preferably it is less than 2%.
Details will be described in the evaluation of examples.

Hereinafter, the present invention will be described in more detail based on production examples and examples. In Production Examples and Examples, parts and% represent parts by weight and% by weight, respectively.
The chemicals used are as follows. <Tetracarboxylic dianhydride (b1)>
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation, trade name BPDA)
9,9-bis (3,4-dicarboxyphenyl) fluorenedioic anhydride (manufactured by JFE Chemical Co., Ltd., trade name: BPAF)
1,2,3,4-butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid BT-100)
1,2,4,5-benzenetetracarboxylic dianhydride (trade name: pyromellitic dianhydride, PMDA, manufactured by Daicel Corporation)
Phthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)
<Compound (b2)>
Pentaerythritol triacrylate (1) (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30, including pentaerythritol tetraacrylate as a by-product)
Pentaerythritol triacrylate (2) (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMM-3LM-N, including by-product pentaerythritol tetraacrylate) dipentaerythritol pentaacrylate (Shin-Nakamura Chemical Industry ( Co., Ltd., trade name: A-9570W, including dipentaerythritol hexaacrylate as a by-product)
2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd., HEA)
<Polymerization inhibitor>
Methylhydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.)
<Catalyst>
1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.)
<Epoxy group-containing compound (b3)>
Glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd., GMA)
4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd., trade name: 4 hydroxybutyl acrylate glycidyl ether)
Biphenyl glycidyl ether (manufactured by Sanko Co., Ltd., trade name: OPP-G)

<Method for measuring acid value>
Based on the potentiometric titration method of JIS K 0070, the measured acid value (mgKOH / g) was converted to solid content.

<Synthesis Example of Compound (A1)>
(Synthesis Example 1)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pentavalent hydroxyl group 122 mgKOH / g penta 250.0 parts of erythritol triacrylate (1), 0.24 parts of methylhydroquinone and 217.8 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this time, the acid value of the reaction product was measured and found to be 94 mgKOH / g. Subsequently, 140.0 parts of biphenyl glycidyl ether and 91.0 parts of cyclohexanone were added to this solution, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours to be reacted. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish is light yellow and transparent, has a solid content of 60%, and the final acid value is 3.0 mgKOH / g. Therefore, it contains the compound (A) in the solid content of the obtained resin varnish. The percentage of reactant is 79%.
The reactant containing the compound (A) represents a high molecular weight reactant derived from a byproduct containing a plurality of hydroxyl groups in the compound (b2) in addition to the compound (A). The ratio of the reaction product containing the compound (A) was calculated from the final acid value of the resin varnish. The remainder represents a compound having no hydroxyl group or an unreacted raw material in the compound (b2) used for the reaction. The same applies to the following synthesis 2 to 11.

(Synthesis Example 2)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, pentaerythritol tris with 80.0 parts 1,2,3,4-butanetetracarboxylic dianhydride and hydroxyl value 113 mgKOH / g Acrylate (2) 402.0 parts, methylhydroquinone 0.33 part, cyclohexanone 318.0 parts were charged, and the temperature was raised to 60 ° C. Next, 2.41 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this time, the acid value of the reaction product was measured and found to be 95 mgKOH / g.
Subsequently, 182.9 parts of biphenyl glycidyl ether and 118.0 parts of cyclohexanone were added to this solution, and then 3.88 parts of dimethylbenzylamine was added as a catalyst, followed by stirring at 100 ° C. for 6 hours. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction product containing the compound (A) in the obtained resin varnish solid content Is 73%.

(Synthesis Example 3)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 parts of 1,2,4,5-benzenetetracarboxylic dianhydride and pentaerythritol tris having a hydroxyl value of 113 mgKOH / g Acrylic (2) 364.9 parts, methylhydroquinone 0.31 part, cyclohexanone 294.1 parts were charged, and the temperature was raised to 60 ° C. Next, 2.22 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. When the acid value of the reaction product was measured at this time, it was 93 mgKOH / g.
Subsequently, 166.0 parts of biphenyl glycidyl ether and 107.1 parts of cyclohexanone were added to this solution, and then 3.58 parts of dimethylbenzylamine was added as a catalyst, stirred at 100 ° C. for 6 hours, and cooled to room temperature. The reaction was terminated. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction product containing the compound (A) in the obtained resin varnish solid content Is 74%.

(Synthesis Example 4)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and a hydroxyl value of 85 mgKOH / g The mixture was charged with 359.0 parts of pentaerythritol pentaacrylate, 0.29 parts of methylhydroquinone and 290.1 parts of cyclohexanone and heated to 60 ° C. Next, 2.19 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured and found to be 74 mgKOH / g.
Thereafter, 123.1 parts of biphenyl glycidyl ether and 78.5 parts of cyclohexanone were added, then 3.53 parts of dimethylbenzylamine was added as a catalyst, stirred at 100 ° C. for 6 hours, and cooled to room temperature to complete the reaction. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish was light yellow and transparent, had a solid content of 60%, and the final acid value was 3.0 mgKOH / g. The reaction product containing the compound (A) in the solid content of the resin varnish obtained Is 83%.

(Synthesis Example 5)
In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer, 90.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, a hydroxyl value of 122 mgKOH / g 160.2 parts of pentaerythritol triacrylate (1), 0.16 parts of methylhydroquinone, and 158.8 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 1.20 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured and found to be 82 mgKOH / g.
Thereafter, 79.0 parts of biphenyl glycidyl ether and 50.7 parts of cyclohexanone were added, and then 1.93 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours. The acid value was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction containing the compound (A) in the solid content of the obtained resin varnish. The thing is 79%.

(Synthesis Example 6)
In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer, 90.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, a hydroxyl value of 122 mgKOH / g 160.2 parts of pentaerythritol triacrylate (1), 0.16 parts of methylhydroquinone, and 158.8 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 1.20 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured and found to be 82 mgKOH / g. Thereafter, 50.3 parts of methacryl glycidyl ether and 31.6 parts of cyclohexanone were added, and then 1.94 parts of dimethylbenzylamine was added as a catalyst and stirred at 100 ° C. for 6 hours. The acid value was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction containing the compound (A) in the solid content of the obtained resin varnish. The thing is 75%.

(Synthesis Example 7)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pentavalent hydroxyl group 122 mgKOH / g penta 250.0 parts of erythritol triacrylate (1), 0.24 parts of methylhydroquinone and 217.8 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this time, the acid value of the reaction product was measured and found to be 94 mgKOH / g.
Thereafter, 78.3 parts of methacryl glycidyl ether and 54.0 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, followed by stirring at 100 ° C. for 6 hours. The acid value was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction containing the compound (A) in the solid content of the obtained resin varnish. The thing is 76%.

(Synthesis Example 8)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and a hydroxyl value of 85 mgKOH / g The mixture was charged with 359.0 parts of pentaerythritol pentaacrylate, 0.29 parts of methylhydroquinone and 290.1 parts of cyclohexanone and heated to 60 ° C. Next, 2.19 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured and found to be 74 mgKOH / g.
Thereafter, 78.3 parts of methacryl glycidyl ether and 48.7 parts of cyclohexanone were added, and then 3.53 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours. The acid value was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction containing the compound (A) in the solid content of the obtained resin varnish. The thing is 69%.

(Synthesis Example 9)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 of hydroxyl value 483 mgKOH / g -63.1 parts of hydroxyethyl acrylate, 0.11 part of methylhydroquinone and 94.6 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 0.72 part of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this time, the acid value of the reaction product was measured and found to be 215 mgKOH / g.
Thereafter, 123.1 parts of biphenyl glycidyl ether and 80.9 parts of cyclohexanone were added, and then 1.15 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours. The acid value was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction containing the compound (A) in the solid content of the obtained resin varnish. The thing is 89%.

(Synthesis Example 10)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 of hydroxyl value 483 mgKOH / g -63.1 parts of hydroxyethyl acrylate, 0.11 part of methylhydroquinone and 94.6 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 0.72 part of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this time, the acid value of the reaction product was measured and found to be 215 mgKOH / g.
Thereafter, 108.8 parts of 4-hydroxybutyl acrylate glycidyl ether and 71.4 parts of cyclohexanone were added, and then 1.15 parts of dimethylbenzylamine was added as a catalyst. The mixture was stirred at 100 ° C. for 6 hours, and the reaction was continued periodically. The acid value of the reaction product was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction containing the compound (A) in the solid content of the obtained resin varnish. The thing is 89%.
(Synthesis Example 11)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pentavalent hydroxyl group 122 mgKOH / g penta 250.0 parts of erythritol triacrylate (1), 0.24 parts of methylhydroquinone and 217.8 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this time, the acid value of the reaction product was measured and found to be 94 mgKOH / g. Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 94 mg KOH / g, the reaction product containing the compound (A) in the solid content of the obtained resin varnish was 72%.

(Synthesis Example 12)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, pentaerythritol tris with 80.0 parts 1,2,3,4-butanetetracarboxylic dianhydride and hydroxyl value 113 mgKOH / g Acrylate (2) 402.0 parts, methylhydroquinone 0.34 parts, cyclohexanone 203.8 parts were charged, and the temperature was raised to 60 ° C. Next, 1.75 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this time, the acid value of the reaction product was measured and found to be 95 mgKOH / g.
Thereafter, 116.4 parts of methacryl glycidyl ether and 188.5 parts of cyclohexanone were added, and then 3.88 parts of dimethylbenzylamine was added as a catalyst and stirred at 100 ° C. for 6 hours. The acid value was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g. Therefore, the reaction product in the solid content of the obtained resin varnish is 71%. . The reaction product does not contain the compound (A). The same applies to Synthesis Examples 13 and 14 below.

(Synthesis Example 13)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 parts of 1,2,4,5-benzenetetracarboxylic dianhydride and pentaerythritol tris having a hydroxyl value of 113 mgKOH / g Acrylic (2) 364.9 parts, methylhydroquinone 0.31 part and cyclohexanone 293.9 parts were charged, and the temperature was raised to 60 ° C. Next, 2.22 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. When the acid value of the reaction product was measured at this time, it was 93 mgKOH / g.
Thereafter, 105.6 parts of methacryl glycidyl ether and 66.9 parts of cyclohexanone were added, and then 3.58 parts of dimethylbenzylamine was added as a catalyst, followed by stirring at 100 ° C. for 6 hours. The acid value was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g. Therefore, the reaction product in the solid content of the obtained resin varnish is 71%. .

(Synthesis Example 14)
Dipentaerythritol with 80.0 parts 1,2,3,4-butanetetracarboxylic dianhydride and hydroxyl value 85 mgKOH / g in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer The mixture was charged with 533.3 parts of pentaacrylate, 0.37 parts of methylhydroquinone and 405.5 parts of cyclohexanone and heated to 60 ° C. Next, 3.07 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780 cm ⁻¹ and 1850 cm ^−1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured and found to be 75 mgKOH / g.
Thereafter, 116.4 parts of methacryl glycidyl ether and 72.6 parts of cyclohexanone were added, and then 4.93 parts of dimethylbenzylamine was added as a catalyst, followed by stirring at 100 ° C. for 6 hours. The acid value was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g. Therefore, the reaction product in the solid content of the obtained resin varnish was 68%. .

Table 1 summarizes the synthesis and outlines the reactants obtained. Abbreviations in the table indicate product names of the compounds.

(Creation of metal oxide composition)
Using the resin varnish containing the compound (A) prepared according to the above synthesis example, the metal oxide was dispersed by mixing (parts) shown in Table 2 to prepare a metal oxide composition in which the metal oxide was dispersed. .
In addition, what was created in the said synthesis example was used for the resin varnish.
Dispersion methods are pre-dispersion (using zirconia beads (0.5 mm) as a medium and dispersing for 1 hour with a paint shaker) and main dispersion (using zirconia beads (0.1 mm) as a medium). (Dispersion with machine UAM-015).

Abbreviations in Table 2 are shown below.
TiO ₂ : “MT-05” (average primary particle size: 10 nm) manufactured by Teika Co., Ltd.
ZrO ₂ : “PCS-60” manufactured by Nippon Electric Works Co., Ltd. (average primary particle size: 20 nm)
BaTiO ₃ : “KZM-20” manufactured by Sakai Chemical Industry Co., Ltd. (average primary particle size: 20 nm)
ZnO: “FINEX-50” manufactured by Sakai Chemical Industry Co., Ltd. (average primary particle size: 20 nm)
SiO ₂ : “AEROSIL50” manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 50 nm)
Al ₂ O ₅ : “Aluminium Oxide C” manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 13 nm)
MEK: methyl ethyl ketone methobuta: 3-methoxy-1-butanol

<D50 particle size>
The D50 particle size of the obtained metal oxide composition was measured using “Nanotrack UPA” manufactured by Nikkiso Co., Ltd. Practically, it must be 200 nm or less.

<Production and Evaluation of Curable Resin Composition and Laminate: Examples 1-33, Comparative Examples 1-7>
Example 1
As a compound (A) having a fluorene structure and two acryloyl groups, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (trade name: “NK Ester A-BPEF”, Shin-Nakamura Chemical Co., Ltd. As a compound (X) having three or more (meth) acryloyl groups, and pentaerythritol tetraacrylate (trade name: “Aronix M450” manufactured by Toagosei Co., Ltd.), (A): (X) = 30 parts : Curable resin composition (mixed to 70 parts, and further mixed with 5 parts Irgacure 184 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator and 40% solid content by mixing with propylene glycol monomethyl ether ( Also referred to as a coating composition or coating solution).
This composition was coated on a 125 μm thick easy-adhesive PET film (“Lumirror UH13” manufactured by Toray Industries, Inc.) with a bar coater so that the film thickness after drying was 1.5 μm, and then high-pressure mercury. The resin layer was formed by irradiating ultraviolet rays of 400 mJ / cm ^{2 with} a lamp. Thereafter, ultraviolet rays of 2000 mJ / cm ² were irradiated once to three times with a high-pressure mercury lamp.
On the obtained resin layer, which is a cured active energy ray film, a transparent conductive film is laminated by sputtering so that the thickness of the ITO film is 30 nm, and then only the transparent conductive film is patterned into a stripe pattern (etching process). Thus, a laminate was obtained.

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

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

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

(Example 5)
In addition to NK ester A-BPEF (A) and pentaerythritol tetraacrylate (X), a zirconia dispersion having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide (trade name: “ZR-010”, manufactured by Solar Corporation ) Was changed to (A) :( X): metal oxide particle content = 10: 40: 50 to obtain a laminate in the same manner as in Example 1.

(Example 6)
In addition to NK ester A-BPEF (A) and pentaerythritol tetraacrylate (X), a zirconia dispersion having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide (trade name: “ZR-010”, manufactured by Solar Corporation ) Was changed to (A) :( X): metal oxide particle content = 25: 25: 50 to obtain a laminate in the same manner as in Example 1.

(Example 7)
In addition to NK ester A-BPEF (A) and pentaerythritol tetraacrylate (X), a zirconia dispersion having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide (trade name: “ZR-010”, manufactured by Solar Corporation ) Was changed to (A) :( X): metal oxide particle content = 35: 15: 50 to obtain a laminate in the same manner as in Example 1.

(Example 8)
In addition to NK ester A-BPEF (A) and pentaerythritol tetraacrylate (X), a zirconia dispersion having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide (trade name: “ZR-010”, manufactured by Solar Corporation ) Was changed to (A) :( X): metal oxide particle content = 0: 50: 50 to obtain a laminate in the same manner as in Example 1.

Example 9
As compound (A) having a biphenyl structure and two or more (meth) acryloyl groups, pentaerythritol tetraacrylate (trade name: “Product”: Compound 1 and compound (X) having three or more (meth) acryloyl groups Aronix M450 (manufactured by Toa Gosei Co., Ltd.) and a reaction product containing the compound (A) of Synthesis Example 1: (X) = 30: 70, and Irgacure 184 (Ciba Specialty Chemicals) as a photopolymerization initiator. (Product) 5 parts of propylene glycol monomethyl ether were mixed to obtain a curable composition (also referred to as a coating composition or a coating solution) adjusted to a solid content of 40%.
This composition was coated on a 125 μm thick easy-adhesive PET film (“Lumirror UH13” manufactured by Toray Industries, Inc.) with a bar coater so that the film thickness after drying was 1.5 μm, and then high-pressure mercury. The resin layer was formed by irradiating ultraviolet rays of 400 mJ / cm ^{2 with} a lamp. Thereafter, ultraviolet rays of 2000 mJ / cm ² were irradiated 1 to 3 times with a high-pressure mercury lamp.
On the obtained resin layer, which is a cured active energy ray film, a transparent conductive film is laminated by sputtering so that the thickness of the ITO film is 30 nm, and then only the transparent conductive film is patterned into a stripe pattern (etching process). Thus, a laminate was obtained.

(Example 10)
Except that the ratio of the reactant containing the compound (A) of Synthesis Example 1 and the pentaerythritol tetraacrylate (X) is changed to the reactant containing the compound (A) of Synthesis Example 2: (X) = 50: 50 In the same manner as in Example 9, a laminate was obtained.

(Example 11)
Except that the ratio of the reactant containing the compound (A) of Synthesis Example 1 and the pentaerythritol tetraacrylate (X) was changed to the reactant containing the compound (A) of Synthesis Example 1: (X) = 70: 30 In the same manner as in Example 9, a laminate was obtained.

(Example 12)
In addition to the reaction product containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30% by weight and a particle size of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) in Synthesis Example 1 is changed to (X): metal oxide particle content = 10: 40: 50. Got the body.

(Example 13)
In addition to the reaction product containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30% by weight and a particle size of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 14)
In addition to the reaction product containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30% by weight and a particle size of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) in Synthesis Example 1 was changed to (X): metal oxide particle content = 35: 15: 50. Got the body.

(Example 15)
In addition to the reactant containing compound (A) of Synthesis Example 2 and pentaerythritol tetraacrylate (X), a zirconia dispersion having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide (trade name: “ZR-010”) Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 16)
In addition to the reactant containing compound (A) of Synthesis Example 3 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 17)
In addition to the reactant containing compound (A) of Synthesis Example 4 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 18)
In addition to the reactant containing compound (A) of Synthesis Example 5 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 19)
In addition to the reactant containing the compound (A) of Synthesis Example 6 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 20)
In addition to the reactant containing compound (A) of Synthesis Example 7 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30 wt% and a particle diameter of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 21)
In addition to the reactant containing compound (A) of Synthesis Example 8 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30 wt% and a particle diameter of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 22)
In addition to the reactant containing compound (A) of Synthesis Example 9 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 23)
In addition to the reactant containing compound (A) of Synthesis Example 10 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 24)
In addition to the reactant containing compound (A) of Synthesis Example 11 and pentaerythritol tetraacrylate (X), a zirconia dispersion (trade name: “ZR-010”) having a particle concentration of 30 wt% and a particle diameter of 15 nm as a metal oxide. Laminated by the same method as in Example 9 except that the reaction product containing the compound (A) of Synthesis Example 1 is changed to (X): metal oxide particle content = 25: 25: 50. Got the body.

(Example 25)
In addition to the reactant containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), the metal oxide composition (1) containing Synthesis Example (1) as a metal oxide is converted to the compound of Synthesis Example 1 A reaction product containing (A): (X): A layered product was obtained in the same manner as in Example 9 except that the metal oxide particle content was changed to 40:11:49.

(Example 26)
In addition to the reactant containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), the metal oxide composition (2) containing Synthesis Example (1) as a metal oxide is converted to the compound of Synthesis Example 1 Reactant containing (A): (X): Laminate was obtained in the same manner as in Example 25 except that the metal oxide particle content was changed to 40:11:49.

(Example 27)
In addition to the reactant containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), the metal oxide composition (3) containing Synthesis Example (1) as a metal oxide is converted to the compound of Synthesis Example 1 Reactant containing (A): (X): Laminate was obtained in the same manner as in Example 25 except that the metal oxide particle content was changed to 40:11:49.

(Example 28)
In addition to the reactant containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), the metal oxide composition (4) containing Synthesis Example (1) as a metal oxide is converted to the compound of Synthesis Example 1 Reactant containing (A): (X): Laminate was obtained in the same manner as in Example 25 except that the metal oxide particle content was changed to 40:11:49.

(Example 29)
In addition to the reactant containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), the metal oxide composition (5) containing Synthesis Example (1) as a metal oxide is converted to the compound of Synthesis Example 1 Reactant containing (A): (X): Laminate was obtained in the same manner as in Example 25 except that the metal oxide particle content was changed to 40:11:49.

(Example 30)
In addition to the reactant containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), the metal oxide composition (6) containing Synthesis Example (1) as a metal oxide is converted to the compound of Synthesis Example 1 Reactant containing (A): (X): Laminate was obtained in the same manner as in Example 25 except that the metal oxide particle content was changed to 40:11:49.

(Example 31)
In addition to the reactant containing compound (A) of Synthesis Example 1 and pentaerythritol tetraacrylate (X), a metal oxide composition (7) containing Synthesis Example (6) as a metal oxide was converted to a compound of Synthesis Example 6. Reactant containing (A): (X): Laminate was obtained in the same manner as in Example 25 except that the metal oxide particle content was changed to 40:11:49.

(Example 32)
A reactant containing pentaerythritol tetraacrylate (X), NK ester A-BPEF and compound (A) in metal oxide composition (1) containing synthesis example (1) as a metal oxide, (A) :( X): A laminate was obtained in the same manner as in Example 25 except that the metal oxide particle content was changed to 47: 4: 49.

(Example 33)
A reaction product containing compound (A) in metal oxide composition (7) containing synthesis example (6) as NK ester A-BPEF and metal oxide, pentaerythritol tetraacrylate (X), (A) :( X): A laminate was obtained in the same manner as in Example 25 except that the metal oxide particle content was changed to 46: 5: 49.

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

(Comparative Example 2)
In addition to NK ester A-BPEF (A) and pentaerythritol tetraacrylate (X), a zirconia dispersion having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide (trade name: “ZR-010”, manufactured by Solar Corporation ) Was changed to (A) :( X): metal oxide particle content = 50: 0: 50 to obtain a laminate in the same manner as in Example 1.

(Comparative Example 3)
In addition to 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and pentaerythritol tetraacrylate (X) having no (meth) acryloyl group, a particle concentration of 30% by weight as a metal oxide, particle size A 15-nm zirconia dispersion (trade name: “ZR-010”, manufactured by Solar Co., Ltd.), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene: (X): metal oxide particle content = A laminate was obtained in the same manner as in Example 1 except that the ratio was changed to 25:25:50.

(Comparative Example 4)
In addition to ethoxylated o-phenylphenol acrylate having one (meth) acryloyl group and pentaerythritol tetraacrylate (X), a zirconia dispersion having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide (trade name: “ ZR-010 "(manufactured by Solar Corporation) was changed to ethoxylated o-phenylphenol acrylate: (X): metal oxide particle content = 25: 25: 50 in the same manner as in Example 1 to obtain a laminate. Got.

(Comparative Example 5)
In addition to the reactant containing the synthesis example (12) having no fluorene structure and / or biphenyl structure and pentaerythritol tetraacrylate (X), a zirconia dispersion having a particle concentration of 30 wt% and a particle diameter of 15 nm as a metal oxide ( A laminate was obtained in the same manner as in Example 1 except that the product name: “ZR-010” (manufactured by Solar Co., Ltd.) was changed to (X): metal oxide particle content = 50: 50.

(Comparative Example 6)
In addition to the reactant including Synthesis Example (13) having no fluorene structure and / or biphenyl structure and pentaerythritol tetraacrylate (X), a zirconia dispersion having a particle concentration of 30% by weight and a particle diameter of 15 nm as a metal oxide ( A laminate was obtained in the same manner as in Example 1 except that the product name: “ZR-010” (manufactured by Solar Co., Ltd.) was changed to (X): metal oxide particle content = 50: 50.

(Comparative Example 7)
In addition to the reactant including the synthesis example (14) having no fluorene structure and / or biphenyl structure and pentaerythritol tetraacrylate (X), a zirconia dispersion (particle size: 30% by weight, particle size: 15 nm) A laminate was obtained in the same manner as in Example 1 except that the product name: “ZR-010” (manufactured by Solar Co., Ltd.) was changed to (X): metal oxide particle content = 50: 50.

(Evaluation method)
The adhesion was evaluated before and after laminating the transparent conductive film.
The transparency and scratch resistance were evaluated before laminating the transparent conductive film. The evaluation results are shown in Table 3 and Table 4.

The abbreviations in Table 3 and Table 4 are shown below. In addition, the unit of the compounding quantity described in the table is part.
Photopolymerization initiator: “Irgacure 184” manufactured by Ciba Specialty Chemicals
Solvent: PGME (propylene glycol monomethyl ether)

(1) Adhesiveness (before transparent conductive film lamination)
In accordance with JIS K5600-5-6, resistance was evaluated by an adhesive cross-cut method. The result was classified into the following 0-5. Practically, it is necessary to be in class 0 or class 1.
0: The edge of the cut is completely smooth and there is no peeling of any lattice eye 1: Small peeling of the laminate at the intersection of the cut. Peel off less than 5% per unit area 2: The laminate is peeled along the edges of the cut and / or at the intersection. 5% or more and less than 15% peeling 3 per unit area 3: Laminate partially or completely peeled along the edge of the cut, and / or various parts of the eyes partially or completely It is peeled off. Separation of 15% or more and less than 35% per unit area 4: The laminate is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely removed It is peeling off. Less than 35% peeling per unit area 5: More than 35% peeling per unit area.

(2) Adhesion (after transparent conductive film lamination)
In accordance with JIS K5600-5-6, resistance was evaluated by an adhesive cross-cut method.
As an evaluation method, the test results were classified into the following 0 to 5. Practically, the adhesion between the base material, the resin layer, and the transparent conductive film to be evaluated needs to be class 0 or class 1. Here, it can confirm that it is peeling with a base material and a resin layer by visually confirming a laminated body or measuring a film thickness.
0: The edge of the cut is completely smooth and there is no peeling of any lattice eye 1: Small peeling of the laminate at the intersection of the cut. Peel off less than 5% per unit area 2: The laminate is peeled along the edges of the cut and / or at the intersection. 5% or more and less than 15% peeling 3 per unit area 3: Laminate partially or completely peeled along the edge of the cut, and / or various parts of the eyes partially or completely It is peeled off. Separation of 15% or more and less than 35% per unit area 4: The laminate is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely removed It is peeling off. Less than 35% peeling per unit area 5: More than 35% peeling per unit area.

(3) Transparency (Haze value)
The turbidity (Haze value) of the laminate having the base material and the resin layer before laminating the transparent conductive film was measured using a Haze meter. Practically, the Haze value needs to be 1.5% or less.

(4) Scratch resistance (hard coat property)
The laminated body having the base material and the resin layer before laminating the transparent conductive film was set on a Gakushin tester, and was shook 10 times with a load of 250 g using steel wool No. 0000. About the taken-out laminated body, the degree of damage was judged according to the following five-step visual evaluation. It shows that the abrasion resistance of a laminated body is so favorable that a numerical value is large.
5: No scratches 4: Slightly scratches 3: Scratches are attached, but the substrate is not visible 2: Scratches are present, and part of the cured film is peeled off 1: The cured film is peeled off The base material is bare

  From the results in Table 3 and Table 4, it was found that the Examples 1 to 33 laminates were excellent in balance between transparency and adhesion. Moreover, even if a metal oxide is contained in the resin layer which is an active energy ray cured film, the transparency and the adhesion are excellent in a good balance.

  On the other hand, Comparative Example (1) to Comparative Example (7) containing no compound (A) are the adhesiveness between the polyester substrate and the resin layer which is an active energy ray cured film and the resin which is an active energy ray cured film. The adhesion between the layer and the transparent conductive film was insufficient.

Claims (7)

A metal oxide containing a compound (A) having a fluorene structure and two or more (meth) acryloyl groups, and at least one atom selected from the group consisting of titanium, zirconium, and aluminum on a base material that is a polyester film The laminated body which has a resin layer formed by hardening | curing the active energy ray curable composition containing these, and also has a transparent conductive film. The said resin layer is a layer formed by hardening | curing the composition containing the compound (X) (However, the case where it is a compound (A)) which has a 3 or more (meth) acryloyl group further. The laminated body as described in. Compound (A) having a fluorene structure and two or more (meth) acryloyl groups, and a compound (X) having three or more (meth) acryloyl groups (except in the case of compound (A)) The laminate according to claim 2, wherein the content of the compound (A) is 10 to 90% by weight in a total of 100% by weight. The said compound (A) is a compound (A1) represented by following General formula (1), The laminated body of any one of Claims 1-3.
General formula (1):



(In General Formula (1), R ₁ is a tetravalent organic residue shown below, R ₃ represents either a hydrogen atom or a monovalent organic residue shown below,
R ₂ represents a monovalent organic residue having a (meth) acryloyl group. )



The said compound (A) is a compound (A2) represented by following General formula (2), The laminated body of any one of Claims 1-3.
General formula (2):
R ₅ —O—R ₄ —O—R ₅

(In the general formula (2), R ₄ is a divalent organic residue shown below,
R ₅ represents a monovalent organic residue having a (meth) acryloyl group. )

The adhesiveness between the base material and the resin layer measured by the adhesive cross-cut method according to JIS K5600-5-6 when irradiated with an active energy ray having an integrated light quantity of 2000 mJ / cm ² or more is determined per unit area. The laminate according to any one of claims 1 to 5, wherein the peeled area is less than 5%. An active energy ray-curable composition containing a compound (A) having a fluorene structure and two or more (meth) acryloyl groups is applied onto a substrate that is a polyester film, and cured by irradiation with active energy rays. Forming a resin layer;
The manufacturing method of a laminated body including the process of forming a transparent conductive film.