JP2016175959A - Active energy ray-polymerizable resin composition and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an active energy ray-polymerizable resin composition excellent in adhesiveness, processability, moisture heat resistance and the like and suitable to be used as a coating agent or an adhesive in a field of optics; and a laminate having excellent adhesiveness between a substrate and a resin layer formed of the above resin composition, punching processability and moisture heat resistance, causing no problem in yellowing for use, and particularly having a transparent film such as a prism sheet and an optical film as a substrate.SOLUTION: An active energy ray-polymerizable composition is provided, comprising an α,β-ethylenically unsaturated double bond group-containing compound (A), an active energy ray polymerization initiator (B), and a compound (C) having a molecular weight of 30 to 1000 and containing at least one hydroxyl group. The active energy ray-polymerizable composition contains 0.01 to 10 parts by mass of the compound (C) having a molecular weight of 30 to 1000 and at least one hydroxyl group, with respect to 100 parts by mass of the active energy ray-polymerizable composition.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray polymerizable resin composition and a laminate using the resin composition. In particular, the present invention relates to a resin composition and a laminate that are suitable for use in optical elements.

In addition to various characteristics such as fast polymerization rate, good workability due to the absence of solvent, energy saving of extremely low energy requirements, active energy ray polymerization technology has recently reduced environmental pollution due to environmental pollution problems. Therefore, the field of use is expanding in the fields of building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical devices, displays, and the like.

These contain a resin that can be polymerized with active energy rays and a monomer having an α, β-ethylenically unsaturated double bond group, and the monomer also functions as a solvent. There is an advantage that the solvent does not volatilize sometimes. And as this resin having active energy ray polymerizability, α, β-ethylenically unsaturated double bond group at the molecular terminal of low molecular weight polyester resin, polyurethane resin, polyepoxy resin, polyacrylic resin, etc. And oligomers having an α, β-ethylenically unsaturated double bond group are used. (Patent Document 1)

  On the other hand, in recent years, the development and generalization of information communication devices including displays has been remarkable, and in the field of display devices, further improvements in the performance and productivity of materials such as coating agents, adhesives, and sealing agents are required. . And various embodiment which uses the said active energy ray polymeric resin composition as a material of a display apparatus is proposed.

  In display devices, various films are usually used depending on the application, such as an antireflection film for preventing reflection from an external light source, and a protective film (protection film) for preventing scratches on the surface of the display device. ing. For example, a polarizing plate or a retardation film is laminated as a liquid crystal cell member constituting a liquid crystal display (LCD). Such a film is attached to an adherend via an adhesive and is used in a display device as a laminate for an optical element, and an active energy ray polymerizable composition is used as an adhesive as one form. .

  However, while the conventional active energy ray polymerizable resin composition has advantages such as a high polymerization rate, the polymer tends to have difficulty in obtaining sufficient transparency required for optical applications. In addition, when a laminated body for an optical element is produced using the above resin composition, the dimensional change characteristics of the material of each layer in the laminated body are different. (Also called curl) tends to occur. Patent Document 2 discloses an ultraviolet curable composition using polyester acrylate and a conjugated diene polymer and having low transparency and small volume shrinkage. However, the composition using the polyester acrylate cannot satisfy the adhesion and heat and humidity resistance of the coat layer.

  Furthermore, in the field of display devices, a backlight system that illuminates a liquid crystal layer from the back surface is widespread. Typically, a backlight unit such as an edge light type or a direct type is provided on the lower surface side of the liquid crystal layer. Equipped. Such an edge light type backlight unit basically includes a linear lamp serving as a light source, a rectangular plate-shaped light guide plate arranged so that an end thereof is along the lamp, and a surface side of the light guide plate. And a prism sheet disposed on the surface side of the sheet. In recent years, light-emitting diodes (LEDs) that excel in color reproducibility and power saving are often used as light sources instead of cathode-ray tubes (CCFLs). There is a growing demand for sex.

  Recently, as the needs for thinning of these display devices and miniaturization of images have increased, the resin for optical films such as prism sheets, Fresnel lenses and lenticular lenses having the fine optical structure used for these displays has been developed. High refractive index resins have been developed and are becoming thinner. However, the reduction in thickness makes the film strength weak and makes it difficult to increase the size. In order to solve this problem, a method of reinforcing the optical film with a transparent film imparting rigidity has been proposed. As an adhesive for adhering these films in the method, a resin composition comprising a thermoplastic resin and a polyisocyanate, a thermoplastic resin and an acrylate ester compound, and a polyisocyanate and a polyester is disclosed (for example, Here, Patent Document 3), a method of using an active energy ray-polymerizable resin composition such as ultraviolet rays in order to increase the curing rate has been studied. However, when these active energy ray polymerizable resin compositions are used as an adhesive, there are cases where sufficient adhesive force and adhesion cannot be obtained due to moisture absorption or distortion due to temperature change.

  As described above, in the field of display devices, development of an active energy ray-polymerizable resin composition that is excellent in various properties required for optical applications in addition to conventional advantages is desired. More specifically, it is an active energy ray-polymerizable resin composition that can be suitably used as a coating agent or an adhesive that constitutes a laminate for an optical element, substantially containing no organic solvent, and having adhesion and In addition to excellent transparency, there is a demand for a resin composition that has good durability under harsher environments under high humidity and high temperature.

JP 2013-140365 A JP 2003-192745 A JP-A-10-158349

  In view of the above situation, an object of the present invention is to provide an active energy ray-polymerizable resin composition that is excellent in adhesion, workability, heat-and-moisture resistance, and can be suitably used as a coating agent or an adhesive in the optical field. To do. In addition, the present invention is excellent in adhesion between the base material and the resin layer comprising the above resin composition, punching workability and heat-and-moisture resistance, and has a problem of yellowing in use, particularly a transparent body such as a prism sheet or an optical film. It aims at providing the laminated body which uses a film as a base material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the following active energy ray-polymerizable resin composition can achieve the above target, and have completed the present invention.

  That is, the present invention relates to an α, β-ethylenically unsaturated double bond group-containing compound (A), an active energy ray polymerization initiator (B), and a compound containing at least one hydroxyl group having a molecular weight of 30 to 1000 ( An active energy ray polymerizable composition containing C) (excluding the α, β-ethylenically unsaturated double bond group-containing compound (A) and the active energy ray polymerization initiator (B)), Active energy ray-polymerizable, characterized by containing 0.01 to 10 parts by mass of a compound (C) containing at least one hydroxyl group having a molecular weight of 30 to 1000 with respect to 100 parts by mass of the active energy ray-polymerizable composition. Relates to the composition.

  Further, the present invention provides the above activity, wherein the α, β-ethylenically unsaturated double bond group-containing compound (A) comprises a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound (A-1). The present invention relates to an energy beam polymerizable composition.

  In the present invention, the α, β-ethylenically unsaturated double bond group-containing compound (A) includes an α, β-ethylenically unsaturated double bond group-containing compound (A-2) having a ring structure. It is related with the said active energy ray polymeric resin composition.

  Moreover, this invention relates to the said active energy ray polymeric composition in which an (alpha), (beta) -ethylenically unsaturated double bond group containing compound (A) contains the oligomer (A-3) of mass mean molecular weight 300-30000.

  Moreover, this invention relates to the said active energy ray polymeric composition which contains 0.05-20 mass% of active energy ray polymerization initiators (B) in the active energy ray polymeric composition whole quantity.

  Moreover, this invention relates to the laminated body formed by laminating | stacking the layer which consists of said active energy ray polymeric composition on the single side | surface or both surfaces of a base material (F).

  In the present invention, the substrate (F) is a polyacetylcellulose film, polynorbornene film, polypropylene film, polyacryl film, polycarbonate film, polyester film, polyvinyl alcohol film or polyimide film. The present invention relates to a certain laminated body.

  According to the present invention, it is possible to provide an active energy ray polymerizable resin composition and a laminate excellent in adhesion, workability, heat-and-moisture resistance, and the like. As a result, a coating agent, an adhesive, and a laminate that can be suitably used in the optical field can be provided.

Hereinafter, embodiments of the present invention will be described.
<Active energy ray polymerizable resin composition>
The active energy ray-polymerizable resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) comprises an α, β-ethylenically unsaturated double bond group-containing compound (A) and an active energy ray. Polymerization initiator (B), compound (C) containing at least one hydroxyl group having a molecular weight of 30 to 1000 (provided that α, β-ethylenically unsaturated double bond group-containing compound (A) and active energy ray polymerization are initiated) Active energy ray-polymerizable composition containing an agent (B)), and a compound containing at least one hydroxyl group having a molecular weight of 30 to 1000 with respect to 100 parts by mass of the active energy ray-polymerizable composition ( An active energy ray-polymerizable composition containing 0.01 to 10 parts by mass of C).
It is.

Here, the “active energy ray” means an energy ray in a broad sense that can provide energy necessary for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams, and radiation. . The active energy ray-polymerizable resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) undergoes a polymerization reaction upon irradiation with the active energy ray to form a cured product. Although it does not specifically limit, In one Embodiment of this invention, it is preferable that the said active energy ray is a light ray containing an ultraviolet-ray.
In addition, in this specification, when expressed as “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyloxy and / or methacryloyloxy”, and “allyl and / or Or "methallyl".

Hereinafter, the constituent components of the resin composition will be specifically described.
<Α, β-ethylenically unsaturated double bond group-containing compound (A)>
The α, β-ethylenically unsaturated double bond group-containing compound (A) is not particularly limited as long as it is a compound containing one or more α, β-unsaturated double bond groups. Α, β-ethylenically unsaturated double bond group-containing compound (A-1) having a hydroxyl group, α, β-ethylenically unsaturated double bond group-containing compound (A-2) having a cyclic structure, weight average molecular weight It is preferable to contain one or more compounds selected from the group consisting of 300 to 30,000 oligomers (A-3).

  The hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound (A-1) (hereinafter referred to as compound (A-1)) will be described. By containing the compound (A-1), compatibility with the compound (C) containing at least one hydroxyl group having a molecular weight of 30 to 1000 (hereinafter referred to as compound (C)) can be improved. Moreover, by having a hydroxyl group, a hydrogen bond between the compound (C) and the active energy ray-curable resin composition can be improved in cohesive strength and crosslinking degree, and at least one of the base materials (F) This is effective for improving heat resistance, moist heat resistance, and thermal dimensional stability as a laminate having the resin layer made of the active energy ray polymerizable resin composition provided on the main surface of the resin. Moreover, there exists an effect which forms a hydrogen bond with the surface functional group of a base material (F), and improves adhesiveness.

  The compound (A-1) is not particularly limited as long as it has a hydroxyl group in its structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, (meth) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, (meth) acrylic acid 10-hydroxydecyl, (meta ) 12-hydroxylauryl acrylate, ethyl (meth) acrylate Fatty acid esters such as α- (hydroxymethyl), monofunctional (meth) acrylic acid glycerol, (meth) acrylic acid glycidyl laurate, (meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate (Meth) acrylic acid ester or (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound Or a hydroxyl group such as an alkylene oxide-added (meth) acrylic acid ester in which an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide is repeatedly added to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound. Contained Aliphatic (meth) acrylate;

  For example, repeated addition of hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, or alkylene oxide such as ethylene oxide or propylene oxide Hydroxyl group-containing aliphatic vinyl ethers such as alkylene oxide addition vinyl ethers having a hydroxyl group at the terminal end;

  For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide Hydroxyl group-containing aliphatic (meth) allyl alcohols such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal of repeating addition of Or (meth) allyl ethers;

For example, α, β-ethylenically unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;
For example, N-hydroxyethyl (meth) acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as “N-hydroxyethyl (meth) acrylamide”. The same applies below. ], Hydroxyl-containing (meth) acrylamides such as N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide;

  For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid 2-hydroxy- 3-phenoxymethyl, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, (meth) 2-hydroxy-3-phenoxydecyl acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, 2- (4-benzoyl-3-hydroxy) (meth) acrylate Phenoxy) Cyclic groups other than ethyl and hydroxyl groups and heterocycles Having concrete (meth) acrylic acid esters;

  For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone [2-hydroxy-4- {2-acryloyloxy} ethoxybenzophenone and 2-hydroxy-4- {2-methacryloyloxy} ethoxybenzophenone Are also expressed as “2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone”. The same applies below. ], 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- Hydroxyl-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy -3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-ben Hydroxyl group-containing benzotriazole-based triazole (meth) acrylic acid esters;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- Meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S- Hydroxyl-containing triazines such as triazine and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine (meta ) Acrylic esters;

Examples thereof include monomers having a hydroxyl group and an ethenyl group such as vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.
As the compound (A-1), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane from the viewpoint of adhesion to the substrate. Α, β-ethylenically unsaturated double bond group-containing compounds having 2 to 18 carbon atoms, such as dimethanol mono (meth) acrylic acid ester, 1 to 2 mol of ε-caprolactone and 2-hydroxyethyl (meth) acrylate Particularly preferred.

  The α, β-ethylenically unsaturated double bond group-containing compound (A-2) (hereinafter referred to as compound (A-2)) having a cyclic structure will be described. First, the compound (A-2) does not include the compound (A-1). An α, β-ethylenically unsaturated double bond group-containing compound having a cyclic structure includes an α, β-ethylenically unsaturated double bond group-containing compound having a ring structure containing no hetero atom in the molecule (A-2 -1) (hereinafter referred to as Compound (A-2-1))) and an α, β-ethylenically unsaturated double bond group-containing compound (A-2-2) having a ring structure containing a hetero atom in the molecule (Hereinafter referred to as compound (A-2-2)), and (A-2-1) is preferred in terms of heat-resistant yellowing. By containing a compound (A-2), there exists an effect which improves durability, such as heat resistance or heat-and-moisture resistance.

The compound (A-2-1) is not particularly limited as long as it has a ring structure other than a heterocyclic ring in its structure. For example, cyclohexyl (meth) acrylate, 1-methyl (meth) acrylate 1-cyclopentyl, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, 1-methyl-1-cyclohexyl (meth) acrylate, 1- (meth) acrylic acid 1- Ethyl-1-cyclohexyl, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate, benzyl (meth) acrylate, iso-bornyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid 2-phenoxyethyl, (meth) acrylic acid 2-oxo-1 2-phenylethyl, 2-oxo-1,2-diphenylethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, ( 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate , (Meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid 2-ethyladamantyl-2-yl, (meth) acrylic acid 2-n-propyladamantyl-2-yl, 2-isopropyladamantyl-2-yl (meth) acrylate (Meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl, (meth) acrylic acid 1- (adamantan-1-yl) -1-ethyl, (meth) acrylic acid 1- (adamantane-1 -Yl) -1-methylpropyl, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1 .0 ^3,7] non-2-yl, (meth) acrylic acid 5-oxo-4-oxa - tricyclo [5.2.1.0 ^{3, 8]} dec-2-yl, (meth) acrylic acid Dihydro-α-terpinyl, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [ 3.3.1] Oct-2-yl, 2 -(Meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2 -(Meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) acrylic (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o-2-propenylphenyl, (meth ) (Meth) acrylic acid cyclic esters such as cyclohexyl glycidyl ether and (meth) acrylic acid phenyl glycidyl ether;

  For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (Meth) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3- ( Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meth) acrylamides containing cyclic structures such as (meth) acrylamide

  For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Carboxylic acids such as cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid and the like, and carboxylic acids containing alicyclic and aromatic rings containing aromatic groups and aromatic rings, and acid anhydrides thereof Kind;

  For example, (meth) acrylic acid cyclic esters containing a sulfonyl group, such as (meth) acrylic acid sulfophenoxyethyl, (meth) acrylic acid sulfocyclohexyl, (meth) acrylic acid sulfobenzyl;

  For example, (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate, phenyl-2- ( Metal salts and ammonium salts of (meth) acrylic acid cyclic esters containing a sulfonyl group such as (meth) acryloyloxyethyl phosphate;

  For example, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meth) acrylic acid 1 , 3-adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, di (meth) acrylate di Cyclopentenyl, dicyclopentenyloxyethyl di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxy) di (meth) acrylate Propyl) benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) Tetraethylene oxide adduct of lopan, tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, tetraethylene oxide of di (meth) acrylic acid-4,4′-sulfonyldiphenol Adduct, Tetraethylene oxide adduct of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, Tetra of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) methane Ethylene oxide adduct, di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (meta ) Tetraethylene oxide adduct of acrylic acid-2,2-bis (hydroxyphenyl) propane-dicap Bifunctional (meth) acrylic acid cyclic esters such as lolactonate, tetraethylene oxide adduct of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane-dicaprolactonate;

  For example, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 1-allyladamantane, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinyl Cyclic compounds containing alkenyl groups such as benzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid, cyclohexyl vinyl ether, cyclohexylmaleimide, vinylcyclohexene monooxirane ;

  For example, vinyl benzoylformate, vinyl benzoyl acetate, vinyl benzoylpropionate, vinyl benzoylbutyrate, vinyl benzoylvalerate, vinyl benzoylhexanoate, vinyl benzoyldodecanoate, 1-naphthoylvinyl acetate, 1-naphthoylpropionate, 1- Naphthoyl vinyl butyrate, 1-naphthoyl vinyl valerate, 1-naphtho vinyl hexanoate, 2-naphtho vinyl acetate, 2-naphtho vinyl propionate, 2-naphtho vinyl butyrate, 2-naphtho vinyl butyrate, 2- Vinyl naphthoyl hexanoate, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotine Vinyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl Vinyl acetate, vinyl 2-furoylpropionate, vinyl 2-furoylbutyrate, vinyl 2-furoylvalerate, vinyl 2-furoylhexanoate, vinyl 2-furoyldecanoate, vinyl 2-furoyldodecanoate, 3-furoyl Vinyl acetate, vinyl 3-furoylpropionate, vinyl 3-furoylbutyrate, vinyl 3-furoylvalerate, vinyl 3-furoylhexanoate, vinyl 3-furoyldecanoate, vinyl 3-furoyldodecanoate, vinyl anthraniloyl acetate , Vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, 4- (2-t-ethoxycarbonylethyl) Aromatic vinyl compounds having an acyl group, such as oxy) styrene, 4- (2-t-butoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylpropyloxy) styrene;

  For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoylpropionate (meth) allyl, benzoylbutyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexane Acid (meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoyl Aromatic (meth) allyl having an acyl group such as hexanoic acid (meth) allyl Ethylenically unsaturated cyclic monomers containing carbonyl groups of compounds, and the like;

  For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( Aromatic vinyl monomers such as 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

  Hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate, 4 -Octadecyl vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenylbenzoic acid Decyl, 4-isopropenyl benzoate dodecyl, 4-isopropenyl benzoate tetradecyl, 4-isopropenyl benzoate hexadecyl, 4-isopropenyl benzoate octadecyl, 4-isopropenyl benzoate eicosyl, 4-isopropenyl benzoate docosyl, etc. Head of Vinyl benzoate ester or isopropenyl benzoic acid ester monomers having alkyl group;

  For example, tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether , N-pentyltetra (ethylene oxide) vinyl phenyl ether, tetra (propylene oxide) vinyl phenyl ether, methyl tetra (propylene oxide) vinyl phenyl ether, ethyl tetra (propylene oxide) vinyl phenyl ether, propoxy tetra (propylene oxide) vinyl phenyl ether N-butyltetra (propylene oxide) vinyl phenyl ether, n Pentaxytetra (propylene oxide) vinyl phenyl ether, poly (ethylene oxide) vinyl phenyl ether, methyl poly (ethylene oxide) vinyl phenyl ether, ethyl poly (ethylene oxide) vinyl phenyl ether, poly (propylene oxide) vinyl phenyl ether, methyl poly (propene Oxide) vinyl phenyl ether, ethyl poly (propylene oxide) ethenyl phenyl ether, poly (ethylene oxide) vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene oxide) ethenyl benzyl ether, poly (propylene oxide) vinyl Benzyl ether, methyl vinyl poly (propylene oxide) vinyl benzyl Ether, ethyl poly (propylene oxide) vinyl benzyl ether, poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether Vinyl phenyl ether monomers having a long-chain polyalkylene oxide moiety such as methyl poly (propylene oxide) vinyl phenyl ethyl ether, ethyl poly (propylene oxide) vinyl phenyl ethyl ether;

  For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether Type monomers;

  For example, poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (propylene oxide) isopropenyl phenyl ether, methyl poly (propylene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethylene oxide) isopropenyl benzyl ether, methyl poly (ethylene oxide) isopropenyl benzyl ether, ethyl poly (ethylene oxide) isopropenyl benzyl ether, poly (propylene oxide) isopropenyl benzyl Ether, methyl poly (propylene oxide) Isopropenyl-based monomers having a polyalkylene oxide moiety, such as propenyl benzyl ether;

  For example, mono-long chain alkyl ester cyclic monomers of dicarboxylic acid such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

For example, monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate;
Polyalkylene oxides such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl polyvinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropylenylbenzoate poly (propylene oxide) Vinyl benzoate or isopropenyl benzoate monomers having a moiety;

  For example, alkenyl group-containing cyclic sulfonic acids such as styrenesulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid;

For example, ammonium styrene sulfonate, monomethyl ammonium styrene sulfonate, dimethyl ammonium styrene sulfonate, trimethyl ammonium styrene sulfonate, tetramethyl ammonium styrene sulfonate, ethyl ammonium styrene sulfonate, diethyl ammonium styrene sulfonate, triethyl styrene sulfonate Styrenesulfonic acid such as ammonium, tetraethylammonium styrenesulfonate, propylammonium styrenesulfonate, dipropylammonium styrenesulfonate, tripropylammonium styrenesulfonate, butylammonium styrenesulfonate, pentylammonium styrenesulfonate or hexylammonium styrenesulfonate Ammonium salts of
Metal salts of styrene sulfonic acid such as sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, magnesium styrene sulfonate, zinc styrene sulfonate, iron styrene sulfonate;
Metal salts and ammonium salts of alkenyl group-containing vinyloxybenzenesulfonic acid such as ammonium vinyloxybenzenesulfonate, sodium vinyloxybenzenesulfonate, potassium vinyloxybenzenesulfonate, etc .;
2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonate sodium, 2-methyl-2-propenyloxybenzenesulfonate potassium and the like 2-methyl-2-propenyloxybenzenesulfonate Examples include acid metal salts and ammonium salts.

  In addition, for example, o-di (meth) allylbisphenol A, hydrogenated bisphenol A in which an aromatic ring structure is hydrogenated, and the like have an α, β-unsaturated double bond group, compound (A-2-1) )include. These may use only 1 type or may use multiple types together.

  As the compound (A-2-1), in terms of durability such as heat resistance and water resistance, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, iso-bornyl acrylate, acrylic Particularly preferred are dicyclopentanyl acid, dicyclopentanyl diacrylate, dicyclopentenyl acrylate, dicyclopentenyl diacrylate, and 2-ethyladamantyl-2-yl acrylate.

  The compound (A-2-2) is not particularly limited as long as it has a heterocyclic structure in its structure. For example, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) Heterocyclic (meth) acrylic acid esters containing nitrogen atoms such as acrylate, 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate;

  For example, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 2 -Vinyl-2-imidazoline, 4,5-dihydro-2-vinyl-1H-imidazole, 2-vinyl-1H-imidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl-1H-pyrazole 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 1-vinylindazole 1-vinylquinoline, 1-vinylisoxaline, 1-vinylquinazoline, 1-vinylcinnoline, Nilcarbazole, 1,1′-divinyl-2,2′-bi (1H-imidazole), N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, Vinyl group-containing compounds having a nitrogen atom-containing heterocycle such as 1-vinyl-2 (1H) -pyridinethione;

  For example, 1- (meth) allyl-1H-imidazole, 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazol-3-ium, 1- ( (Meth) allyl-3-ethyl-1H-imidazol-3-ium, 5-bromo-1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 1- (meth) allyl-5,5- Diethylpyrimidine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5-triazine-2-amine, 2-vinyl Piperazine, 4-vinylpiperazine, 1-benzyl-2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 2-vinylpyridine, -Vinylpyridine, 4-vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3- Vinylpyrazine, 2-vinylpyrimidine, 2-vinylpyridazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl-1,3,5-dimethyl-2,4-diamine, 3 -Vinyl group-containing compounds having a nitrogen atom-containing six-membered ring such as vinyl-1,2,4,5-tetrazine;

  For example, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl-1H-benzimidazole, 2-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquinoline, 2-vinyliso Xaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 1- (meth) allyl-1H-benzimidazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meta ) Nitrogen atoms such as allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline Containing heteropolycyclic vinyl group-containing compounds;

  For example, 1-methyl-4,5-divinyl-1H-imidazole, 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine, 2,6-divinylpyridine and the like containing nitrogen atoms Compounds having a ring structure and two or more vinyl groups;

  For example, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5- (1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5-isopropylpyrimidine, 2- (Meth) allylpyridine-containing compounds having a nitrogen atom-containing heterocyclic structure, such as (meth) allylpyridine, 4- (meth) allylpyridine, 3,6-dihydro-3- (meth) allylpyridine;

  For example, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meth) allylindazole, 3-phenyl-4- (meth) allylisoquinoline, 9- (meth) allyl (Meth) allyl group-containing compounds having a heteropolycyclic structure containing a nitrogen atom, such as -9H-carbazole;

  For example, imide (meth) acrylate, 2- (4-oxazolin-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone Heterocyclic structures containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification (Meth) acrylic acid esters having;

  For example, 4-acryloylmorpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2 -Heterocyclic acrylamides such as (ylmethoxymethyl) (meth) acrylamide;

  For example, maleimide derivatives having both nitrogen and oxygen atoms such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

  For example, 2-vinyl oxazole, 2-phenyl-4-vinyl oxazole, 2-phenyl-5-vinyl oxazole, 5-ethoxy-2-vinyl oxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5 -It has a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, 2-vinylbenzoxazole Vinyl group-containing compounds;

  For example, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ( (Meth) acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran -4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2- Dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxoteto Hydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 , 3-Dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, and the like. ;

  For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

  For example, 2-vinylthiazol, 4-methyl-5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzo Examples include ethenyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom such as thiazole, and these may be used alone or in combination.

Compound (A-2-2) is glycidyl acrylate, glycidyl methacrylate, methacrylic acid (3,4-epoxycyclohexyl) from the viewpoint of compatibility with compound (C) and durability such as heat resistance and water resistance. ) Methyl, tetrahydrofurfuryl acrylate, 4-acryloylmorpholine, 1-vinylimidazole, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, di (meth) acrylic acid ethoxylated isocyanuric acid, Tri (meth) acrylic acid ethoxylated isocyanuric acid is particularly preferred.

  The oligomer (A-3) having a weight average molecular weight of 300 to 30,000 (hereinafter referred to as oligomer (A-3)) will be described. First, the oligomer (A-3) does not include the compounds (A-1) and (A-2) and the compound (A-4) described later. The oligomer (A-3) is at least selected from the group consisting of a polyester oligomer (A-3-1), a polyurethane oligomer (A-3-2), and a polyepoxy oligomer (A-3-3). One or more kinds of oligomers are preferable, and can be used without any particular limitation. By containing the oligomer (A-3), the cohesive force of the active energy ray-curable resin composition can be improved, and the active energy ray polymerization provided on at least one main surface of the base material (F). As a laminate having a resin layer made of a conductive resin composition, the present invention is effective for improving heat resistance, moist heat resistance, and thermal dimensional stability. Moreover, there exists an effect which improves the adhesiveness of a base material (F).

  As the polyester-based oligomer (A-3-1), the terminal of the polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol on the main chain skeleton or a hydroxyl group in the polyester chain and (meth) acrylic acid, maleic acid, etc. A compound obtained by esterification with an α, β-ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule, or a carboxyl group in the terminal or polyester chain of (meth) It is a compound obtained by esterification with the aforementioned compound (X) such as 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth) acrylate. In addition, a polyester oligomer obtained from an acid anhydride, glycidyl (meth) acrylate, and a compound having at least one hydroxyl group can also be used as the polyester oligomer (A-3-1).

  Examples of the polybasic acid include aliphatic, alicyclic, and aromatic acids, and each can be used without any particular limitation. More specifically, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, and dodecanedioic acid. Examples thereof include acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used. Derivatives of succinic anhydride (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl anhydride Succinic acid, etc.), glutaric anhydride derivatives (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc. ), Maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecyl Maleic anhydride, 2,3-dichloromaleic anhydride, phenyl maleic anhydride Phosphate, also anhydride derivative of 2,3-diphenyl maleic anhydride, etc.) and the like can be used. .

  More specifically, as the alicyclic polybasic acid, for example, as the alicyclic dicarboxylic acid, for example, dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclopropane-1α, 2β-dicarboxylic acid , Cyclopropane-1β, 2α-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, cyclobutane-1α, 2β-dicarboxylic acid, cyclobutane-1α, 3β-dicarboxylic acid, cyclobutane-1α, 3α-dicarboxylic acid, (1R) -Cyclopentane-1β, 2α-dicarboxylic acid, trans-cyclopentane-1,3-dicarboxylic acid, (1β, 2β) -cyclopentane-1,3-dicarboxylic acid, (1β, 3β) -cyclopentane-1, 3-dicarboxylic acid, (1S, 2S) -1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, , 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Saturated cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid, 1-cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid Acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene- 1,3-dicarboxylic acid, 2,5-hexadiene-1α, 4α-dicar Unsaturated double bond in such phosphate rings include one or two unsaturated alicyclic dicarboxylic acid having, like these alicyclic dicarboxylic acids and anhydrides thereof can be used.

  In addition, derivatives of hexahydrophthalic anhydride ((3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), tetrahydrophthalic anhydride derivatives (1,2,3,6-tetrahydrophthalic anhydride, 3 -Methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) The hydrogenated phthalic anhydride derivative can also be used as an alicyclic dicarboxylic acid anhydride.

  More specifically, examples of the aromatic polybasic acid include, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, 2 , 2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindanedicarboxylic acid 1,2-azulene dicarboxylic acid, 1,3-azulene dicarboxylic acid, 4,5-azulene dicarboxylic acid, (−)-1,3-acenaphthene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,5- Anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracenedical Acids, 1,2-phenanthrene dicarboxylic acids, 4,5-phenanthrene dicarboxylic acids, aromatic dicarboxylic acids such as 3,9-perylene dicarboxylic acid, and aromatic dicarboxylic acids such as phthalic anhydride and 4-methylphthalic anhydride An anhydride is mentioned, These aromatic dicarboxylic acid and its anhydride etc. can be utilized.

  Furthermore, chlorendic anhydride, het anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3 , 6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used as the polybasic acid.

  Polyhydric alcohols include relatively low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500 and relatively high molecular weight polyols having a number average molecular weight (Mn) of 500 to 30,000. Each can be used without any particular limitation.

  More specific examples of relatively low molecular weight polyols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2, 4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (Addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol, Aliphatic or cycloaliphatic diols such as octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, dimer diol;

  1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4, 4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4′-isopropylidenephenol, addition-type bisphenol obtained by adding alkylene oxide to bisphenol Aromatic diols and the like.

Examples of the raw material bisphenol of addition-type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.
More specific examples of the relatively high molecular weight polyols include high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. The high molecular weight polycarbonate polyol is obtained by reacting the above-mentioned relatively low molecular weight diol with a carbonate or phosgene.

As a commercial item of the said high molecular weight polyester polyol, the Byron series by Toyobo Co., Ltd., the Kuraray polyol P series by Kuraray, and the Kyowapol series by Kyowa Hakko Chemical Co., Ltd. are mentioned, for example.
As a commercial product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd. can be used.
Examples of commercially available high molecular weight polycarbonate polyols include Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray polyol PMHC series, and Kuraray polyol C series manufactured by Kuraray.

Examples of commercially available high molecular weight polyurethane polyols include Byron UR series manufactured by Toyobo Co., Ltd., Takelac E158 (hydroxyl value = 20, acid value <3) manufactured by Mitsui Chemicals Polyurethane, Takelac E551T (hydroxyl value = 30, Acid value <3), Takelac Y2789 (hydroxyl value = 10, acid value <2) and the like.
In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly (β-methyl-γ-valerolactone) diol, and polyvalerolactone diol can also be used as the high molecular weight polyol. Included in polyols.

  The polyurethane oligomer (A-3-2) is a compound obtained by reacting a compound having at least one isocyanate group with the compound (X), or a compound having at least one isocyanate group and the above-mentioned many compounds. Obtained by reacting a compound obtained by reacting the compound (X) with a urethane prepolymer having a terminal isocyanate group obtained by reacting a monohydric alcohol with a compound having at least one isocyanate group and a polyhydric alcohol. A compound obtained by reacting the compound (X) with a urethane prepolymer having a terminal isocyanate group obtained by reacting a urethane prepolymer having a terminal isocyanate group with a compound having at least one amino group. is there. Moreover, what contains the urea bond group obtained by making an isocyanate group and an amino group react is also included in a polyurethane-type oligomer (A-3-2).

  Examples of the compound having at least one isocyanate group include monofunctional polyisocyanates and polyfunctional isocyanates, and aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, etc., respectively. Can be mentioned. More specifically, as monofunctional polyisocyanate, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl Isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methyl Benzyl isocyanate, (S)-(−)-α-methylbenzyl isocyan Nate, (R)-(-)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p- And toluenesulfonyl isocyanate.

  Among polyfunctional isocyanates, as aromatic polyisocyanate, more specifically, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4, Examples thereof include 4′-diphenyl ether diisocyanate and 4,4 ′, 4 ″ -triphenylmethane triisocyanate.

Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

  In addition, a 2-methylpentane-2,4-diol adduct of the above polyisocyanate, a trimer having an isocyanurate ring, etc. can be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

More specifically, as amines having an amino group, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2 , 4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethyl Propylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, (di 2-hydroxypropyl ethylene) diamine, aliphatic such as piperazine polyamine;
Cycloaliphatic polyamines such as isophoronediamine and dicyclohexylmethane-4,4′-diamine;
Phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-bis- ( Aromatic diamines such as sec-butyl) diphenylmethane can be used.

  The polyepoxy oligomer (A-3-3) is a compound having a glycidyl group and an α, β-unsaturated double bond group having one or more carboxyl groups in the molecule such as (meth) acrylic acid and maleic acid. This is a compound obtained by reaction with a contained compound, and representative examples include bisphenol type, epoxidized oil type, phenol novolac type, and alicyclic type. As the bisphenol type polyepoxy oligomer, α, β-unsaturation having one or more carboxyl groups in the molecule such as bisphenol type diglycidyl ether obtained by reacting bisphenols and epichlorohydrin and (meth) acrylic acid It is obtained by reacting with a double bond group-containing compound.

  Epoxidized oil Polyepoxy oligomer includes epoxidized oil such as soybean oil and α, β-unsaturated double bond having one or more carboxyl groups in the molecule such as (meth) acrylic acid and maleic acid. Those obtained by reaction with a group-containing compound can be used. The novolak type polyepoxy oligomer is obtained by a reaction between a novolak type epoxy resin and an α, β-unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule such as (meth) acrylic acid. Things can be used. As an alicyclic polyepoxy oligomer, a reaction between an alicyclic epoxy resin and an α, β-unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule such as (meth) acrylic acid. The synthesized one can be used.

  The mass average molecular weight (hereinafter referred to as Mw) of the oligomer (A-3) having at least one α, β-unsaturated double bond group in the molecule is compatible with the polymerized coating film and good durability. It is necessary to be in the range of 300 to 30,000 in terms of (heat resistance, moist heat resistance) and aggregation density. Furthermore, Mw is more preferably in the range of 400 to 20,000. When the Mw of the oligomer (A-3) exceeds 30,000, the fluidity is lowered and the compatibility with the compound (A-4) other than the oligomer (A-3) is also lowered. When the coating property of the adhesive is reduced or the active energy ray polymerizable adhesive is used, the durability such as the adhesiveness of the polymer coating may be reduced, or the coating may be whitened. When the Mw of (A-3) is less than 300, after the active energy ray polymerizable adhesive is applied to and laminated on the various base materials (F), the active energy ray polymerizable adhesive layer undergoes cohesive failure. It may be easier.

  Regarding the α, β-ethylenically unsaturated double bond group-containing compound (A) contained in the active energy ray-polymerizable adhesive of the present invention, the aforementioned compound (A-1), compound (A-2), and oligomer In addition to (A-3), there is a limit to using other α, β-ethylenically unsaturated double bond group-containing compound (A-4) (hereinafter referred to as compound (A-4)) as necessary. Absent.

  Examples of the other α, β-ethylenically unsaturated double bond group-containing compound (A-4) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, ( 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n (meth) acrylate -Amyl, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, (meta ) N-nonyl acrylate, (meth) acrylic iso-nonyl, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic acid o (Meth) acrylic acid alkyl esters such as kutadecyl, lauryl (meth) acrylate, stearyl (meth) acrylate;

For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2- (2-propenyloxy) ethyl, (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, (Meth) acrylic acid esters further containing an unsaturated group such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;
For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

  For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meth) acrylic acid 2- (ethoxyca (Rubonyloxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) 2- (Butoxycarbonyloxy) ethyl acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxy) (meth) acrylate Aliphatic (meth) acrylic acid esters having one carbonyl group such as carbonyloxy) butyl;

  For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

  For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

  For example, sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-sulfobutyl (meth) acrylate, (meth) 4-sulfobutyl acrylate, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulfolauryl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters containing a sulfonyl group such as sulfostearyl acrylate;

  For example, metal salts and ammonium of (meth) acrylic acid esters containing sulfonyl groups such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate salt;

  For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, phenyl-2- (meth) acryloyloxyethyl phosphate, (meth) acrylic acid Phosphonic acid group-containing (meth) acrylic acid esters such as acid phosphooxyethylene oxide (ethylene oxide addition moles: 4 to 10) and (meth) acrylic acid acid phosphooxypropylene oxide (propylene oxide addition moles: 4 to 10) Kind;

  For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

  For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate, hydroxypivalylhydroxypivalate hydroxypivalate dicaprolactonate, 1,6-hexane di (meth) acrylate Gio Di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol di, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7 -Heptanediol, di (meth) acrylic acid 1,8-octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol di, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) 1,2-dodecanediol acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, di (meth) acrylate 1,16-hexadecanediol acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1 di (meth) acrylate , 5-pentanediol, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, di (meth) 2,2-diethyl-1,3-propanediol acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, di (meth) 2-ethyl-1,3-hexanediol acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl di (meth) acrylate -1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di ( 2-methyl-2-propyl-1,3-propanediol (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl di (meth) acrylate 1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1, di (meth) acrylate 3-hexanediol, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, di ( Bifunctional (meth) acrylic acid esters such as 2,4-diethyl-1,5-pentanediol (meth) acrylate and 1,1,1-trishydroxymethylethane di (meth) acrylate;

  For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Trifunctional (meth) acrylic esters such as pentaerythritol tri (meth) acrylate;

For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters such as real sharp emission oxide;
For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acid, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;
For example, ethyl vinyl ether, 1-propyl vinyl ether, 2-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, n-hexyl, 2-ethylhexyl vinyl ether, n -Aliphatic vinyl ethers such as octyl vinyl ether, iso-octyl vinyl ether, n-nonyl vinyl ether, iso-nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether;

For example, fluorine-containing ethenyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;
For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing α, β-unsaturated double bond group-containing compounds such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;
For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleami , Fumaramide, mesaconamide, citraconic amide, itaconic amide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N Aliphatic (meth) acrylamides such as' -dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

  For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- 2-methoxyethyl (meth) acrylamide, N- (oxetane-2-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N, N-di (methoxymethyl) (Meth) acrylamides containing N-alkoxy groups such as (meth) acrylamide and N, N-di (ethoxymethyl) (meth) acrylamide;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;
For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itacononitrile, 2-propenenitrile, 2-methacrylic acid (meth) acrylate, etc. β-unsaturated double bond group-containing compounds;

For example, saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate, (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of acids;
For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

  For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

For example, vinyl esters such as vinyl chloride, vinylidene chloride and allyl chloride;
For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;
For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

  For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, and the like. In particular, it is not limited to these. These may use only 1 type or may use multiple types together.

  As said other (alpha), (beta) -ethylenically unsaturated double bond group containing compound ((A-4)), the compound which has a (meth) acryloyl group from a reactive viewpoint is preferable, and also active energy ray polymeric adhesion | attachment As an agent, it is preferable that bifunctional or more (meth) acrylic acid ester is included from a viewpoint of an active energy ray polymerization rate.

As a preferred ratio of the components constituting the α, β-ethylenically unsaturated double bond group-containing compound (A), α, β-ethylenically unsaturated double bond group-containing compound (A) and active energy ray polymerization described later When the total amount of the initiator (B) in the active energy ray polymerizable adhesive is 100 parts by mass, the compound (A-1) is 1 to 70 parts by mass, and the compound (A-2) is 1 to 70 parts by mass. The oligomer (A-3) is preferably 1 to 50 parts by mass, and the other α, β-ethylenically unsaturated double bond group-containing compound (A-4) is preferably 50 parts by mass or less.
When the amount of the compound (A-1) is less than 1 part by mass, not only the compatibility with the compound (C) is lowered, but also the adhesion with the substrate (F) described later is lowered. When there are more compounds (A-1) than 70 mass parts, since water resistance is inferior, it is unpreferable. When the compound (A-2) is less than 1 part by mass, the heat resistance and moist heat resistance of the coating film are lowered. When there are more compounds (A-2) than 70 mass parts, the softness | flexibility of a coating film will be lost and it will become weak, and since adhesiveness with the below-mentioned base material (F) falls, it is unpreferable. When the amount of the compound (A-3) is less than 1 part by mass, durability such as adhesiveness of the polymer coating film is lowered, which is not preferable. Moreover, when there are more compounds (A-3) than 50 mass parts, when it is set as an active energy ray polymerizable adhesive, since fluidity | liquidity will fall, the applicability | paintability of an active energy ray polymerizable adhesive will fall. It is not preferable.

  The active energy ray polymerization initiator (B) may be any compound that generates radicals upon irradiation with active energy rays, and a compound arbitrarily selected from known compounds can be used. In this invention, it is necessary to contain 0.05-20 mass% of active energy ray polymerization initiators (B) in the active energy ray polymerizable composition whole quantity. If it is less than 0.05 parts by mass, the α, β-ethylenically unsaturated double bond group-containing compound (A) cannot be sufficiently cured. When the amount exceeds 20 parts by mass, the α, β-ethylenically unsaturated double bond group-containing compound (A) is relatively reduced, so that the cured coating film cannot obtain sufficient performance.

  Specific examples include the following. 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl Dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-thioxanthone, camphorquinone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like.

Moreover, as a commercial item, the following is mentioned, for example. Irgacure 184,907,651,1700,1800,819,369, 261 (BASF), DAROCUR-TPO (BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), Darocur-1173 (Merck), Ezacure KIP150, and TZT (Nihon Shibel Hegner), Kayacure BMS, Kayacure DMBI (Nippon Kayaku) and the like.
Moreover, the photoinitiator which has at least 1 (meth) acryloyl group in a molecule | numerator can also be used.

Furthermore, sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), Rp-2074 Photoacid generators exemplified by iodonium salts (made by Rhodia Japan) and the like can also be used. Use is preferable because crosslinking proceeds and an adhesive layer having excellent durability against heat and humidity is formed.
In the present invention, as the component (B), the above-mentioned compounds can be used alone or in combination of two or more.

  Furthermore, in order to improve the performance of the active energy ray polymerization initiator (B), an active energy ray sensitizer may be used in combination. Representative examples of the active energy ray sensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles or other nitrogen-containing compounds. Of these, anthracene or benzophenone, thioxanthone or perylene, phenothiazine, and rose bengal are preferably used.

  Compound (C) containing at least one hydroxyl group having a molecular weight of 30 to 1000 (excluding α, β-ethylenically unsaturated double bond group-containing compound (A) and active energy ray polymerization initiator (B)) explain.

  In the present invention, the compound (C)) is a monomer of a compound having one or more hydroxyl groups in the molecule and not having an α, β-unsaturated double bond group. The compound (C) is not particularly limited as long as it is a compound having one or more hydroxyl groups in the molecule and having no α, β-unsaturated double bond group. The hydroxyl group in the compound (C) is preferable from the viewpoint of improving the reaction rate and suppressing polymerization curing shrinkage. Moreover, by having a hydroxyl group, a hydrogen bond with the compound (A) containing a hydroxyl group works, and the cohesive force and the degree of crosslinking of the active energy ray-curable resin composition can be improved. Although it does not specifically limit as compound (C) which shows an effect in heat resistance, heat-and-moisture resistance, and thermal dimensional stability improvement, As a specific example, the following compounds are mentioned.

  The compound (C) having one or more hydroxyl groups in the molecule and having no α, β-unsaturated double bond group has one or more hydroxyl groups in its structure, and α, β-unsaturated. There is no particular limitation as long as it does not have a saturated double bond group, for example, monoalkyl ethers such as alkanol, polyoxyalkylene glycol monoalkyl ether, and alkylene glycol;

  For example, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,3-heptanetriol, 2,6-dimethyl-1,2,6-hexanetriol, 1,2,3- Hexanetriol, 1,2,3-butanetriol, 3-methyl-1,3,5-pentanetriol, 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol, 1,3-cyclopentanediol, trans-1,2-cyclooctanediol, 1,16-hexadecanediol, 1,3-propanediol, 1,4-butane Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanedio Polyalcohols and polyalkylene glycols such as Le;

  For example, ethylene glycol, glycerol, glycolic acid, glyoxylic acid, isopropyl alcohol, propylene glycol, diethylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, glycerol, 1,4-hexanediol, 1,4-hexane Polyfunctional alcohols such as dimethanol;

  For example, polyethers such as alkoxylated trimethylolpropane, ethoxylated or propoxylated polyether compounds, polyethylene glycol-200 or -600, polyglycerol;

  For example, polyesters such as adipic acid, dimer acid, hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid;

  For example, aromatic hydroxyls such as benzyl alcohol, bisphenol A, bisphenol S, ethoxylated bisphenol A, ethoxylated bisphenol S;

  The compound (C) preferably has a weight average molecular weight of 30 to 1,000. Furthermore, the weight average molecular weight is particularly preferably 50 to 300. In terms of molecular weight, adhesion, heat resistance, and thermal dimensional stability, ethylene glycol, glycerin, glycolic acid, glyoxylic acid, methyl alcohol, ethyl alcohol, isopropyl alcohol, propylene glycol, diethylene glycol, benzyl alcohol, trimethylolpropane, penta Erythritol and the like are preferable. Moreover, it is preferable to have two or more hydroxyl groups in the molecule from the viewpoint of adhesion, heat resistance, and thermal number method stability, and ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol are particularly preferable.

  The active energy ray polymerizable composition of the present invention contains an α, β-ethylenically unsaturated double bond group-containing compound (A), an active energy ray polymerization initiator (B), and a compound (C). The compound (C) is included as an essential component in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the active energy ray polymerizable composition (excluding the compound (C)). By including the compound (C), curability, adhesion to the substrate (F) described later, heat resistance, thermal dimensional stability, and the like are improved. These effects are considered to be because the cohesive force is increased by the formation of hydrogen bonds between the compound (C) and the reaction product after curing. Furthermore, it is considered that there is an effect of forming a hydrogen bond with the compound (C), the base material (F) and the active energy ray polymerizable composition, and improving cohesion and adhesion to the base material.

  With respect to 100 parts by mass of the active energy ray polymerizable composition (excluding the compound (C)), the compound (C) is 0.01 parts by mass or less, and the above effect is not observed and the amount is 10 parts by mass or more. Because the water resistance is poor, or the crosslinking degree and molecular weight of the cured product after reaction due to the chain transfer effect in radical polymerization, the cohesive force is lowered and the adhesion, heat resistance, and thermal dimensional stability are reduced. It is not preferable. Further, from the viewpoint of curability and adhesion to the substrate (F) described later, the compound (C) is 0.3 with respect to 100 parts by mass of the active energy ray polymerizable composition (excluding the compound (C)). It is preferable that it is -7 mass parts, More preferably, it is 0.5-5 mass parts.

  The active energy ray-polymerizable resin composition of the present invention has an active energy ray polymerization initiator (B) that is not soluble in the active energy ray-polymerizable resin composition or has a high viscosity. A small amount of an organic solvent may be contained to dissolve the linear polymerization initiator (B). The content of the organic solvent in the active energy ray polymerizable resin composition is within 5% by mass. The organic solvent that can be used is not particularly limited, but specifically, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbons An organic solvent such as a system solvent can be further added to adjust the viscosity of the active energy ray polymerizable resin composition, or the active energy ray polymerizable resin composition can be heated to lower the viscosity.

  In the active energy ray polymerizable resin composition of the present invention, additives other than the above-described components can be appropriately blended as long as the effects of the present invention are not impaired. For example, blending organic or inorganic fillers from the viewpoints of polymerization cure shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. it can. As such a filler, polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, and the like can be used, and the shape is not particularly limited, such as particles and fibers. In addition, when blending the above polymers, flexibility imparting agents, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy imparting agents, dispersion stabilizers, fluidity imparting agents, dissipators. It is also possible to dissolve, semi-dissolve, or micro-disperse in the active energy ray-polymerizable resin composition as a polymer blend or a polymer alloy, not as a filler, such as a foaming agent.

The active energy ray-polymerizable resin composition of the present invention can be used in any form of liquid, paste, and film, but is preferably liquid from the viewpoint of ease of use.
The active energy ray polymerizable resin composition in the present invention has a viscosity of 1 to 1500 mPa · s when the film thickness of the active energy ray polymerizable resin composition layer is 0.1 to 6 μm depending on the intended use. Is important, preferably 10 to 1300 mPa · s, and more preferably 20 to 1000 mPa · s. When the viscosity is higher than 1500 mPa · s, when the base material (F) is coated, a thin film coating of 0.1 to 6 μm cannot be performed, and optical characteristics such as transmittance are deteriorated. On the other hand, when the viscosity is lower than 1 mPa · s, it becomes difficult to control the film thickness of the active energy ray polymerizable resin composition layer.

  Moreover, when the film thickness of the active energy ray polymerizable resin composition layer is 6 to 300 μm depending on the intended use, it is important that the viscosity is 1500 to 100,000 mPa · s, preferably 3,000 to More preferably, it is 50,000 mPa · s.

Next, the coating process of the active energy ray polymerizable resin composition will be described.
The resin composition of the present invention is preferably used for a coating agent or an adhesive. Typically, the resin composition is applied to one side or both sides of a substrate by an appropriate method according to a conventional method, and then polymerized and cured to form a resin layer. Therefore, one Embodiment of this invention is related with the laminated body which has the below-mentioned base material (F) and the resin layer which consists of a resin composition provided in the at least one surface of this base material (F). In this embodiment, the film thickness of the resin layer is set according to the use of the laminate.

  For example, when using the said resin composition for the use of the laminated bodies for optical elements, such as the below-mentioned hard coat film or a prism sheet, the said resin composition is thin-film coated. The thickness of the resin layer formed by coating is preferably from 0.1 to 6 μm, and more preferably from 0.1 to 3 μm. By setting the thickness of the resin layer to 0.1 μm or more, it is easy to obtain sufficient adhesion or adhesive force when the resin composition is used as a coating agent or an adhesive. On the other hand, when the thickness of the resin layer exceeds 6 μm, there is often no change in properties such as adhesion or adhesive strength.

  Moreover, when using the said resin composition for the use of laminated bodies for optical elements, such as a decorative film (it means the filling sheet for touchscreens), the said resin composition is thick-film-coated. The thickness of the resin layer formed by coating is preferably 6 to 300 μm, and more preferably 20 μm to 250 μm. By making the thickness of the resin layer 6 μm or more, it is easy to obtain sufficient stress relaxation properties and creep characteristics in addition to the filling function of the touch panel when the resin composition is used as a coating agent or an adhesive. is there. On the other hand, by setting the thickness of the resin composition layer to 300 μm or less, it is easy to suppress a decrease in coating properties such as streaking.

  There is no restriction | limiting in particular in the coating method of the said resin composition. For example, various well-known methods such as Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, micro gravure coater, lip coater, comma coater, curtain coater, knife coater, reverse coater, spin coater, etc. Can be applied. Moreover, it can select without particular restriction | limiting also about forms, such as thin film coating or thick film coating.

  The resin composition of the present invention can be applied onto a substrate by a known and usual method, and then has an α, β-unsaturated bonding group by irradiating the formed coating layer with active energy rays. The polymerization reaction of the compound proceeds to form a cured product. In one embodiment of the present invention, it is preferable that the active energy ray is mainly composed of light energy in the wavelength range of 150 to 550 nm including ultraviolet rays. Suitable light sources for providing such light energy include, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, LED lamps, xenon lamps, and metal halide lamps. Is mentioned. In addition, in another embodiment of the present invention, a laser beam, an X-ray, an electron beam, or the like can be used as an active energy ray for exposure.

The irradiation intensity of the active energy ray is preferably 0.1 to 500 mW / cm ² . When the light irradiation intensity is less than 0.1 mW / cm ² , it takes a long time for curing, and when it exceeds 500 mW / cm ² , the substrate may be deteriorated in various substrates due to heat radiated from the lamp. This is not preferable. The integrated dose expressed as the product of the irradiation intensity and the irradiation time is preferably 0.1 to 5,000 mJ / cm ² . When the total irradiation amount is less than 0.1 mJ / cm ^2, requiring a long time for polymerization and curing, since the larger 5,000 mJ / cm ^2, the irradiation time is very long, poor productivity, which is not preferable. A typical active energy ray polymerizable resin composition generally requires an integrated dose of 1,000 mJ / cm ² or more. However, the above resin composition according to the present invention is favorably polymerized even at a low integrated dose of less than 1,000 mJ / cm ² .

  In the laminate of the present invention, the resin layer on the substrate is formed by polymerization and curing of the resin composition by irradiation with active energy rays, and has a glass transition temperature of approximately −80 ° C. to 150 ° C. ( Hereinafter referred to as Tg). From the viewpoint of punching workability and bendability of the laminate, the Tg of the resin layer is more preferably in the range of −40 to 120 ° C., and further preferably in the range of 0 to 120 ° C.

Here, the laminated body characterized by laminating | stacking on the single side | surface of a base material (F) or both surfaces using an active energy ray polymeric resin composition is demonstrated generally.
The polymerization reaction by the active energy ray of the active energy ray-polymerizable resin composition of the present invention is positioned on at least one surface of the transparent film that is a film-like substrate and the transparent film among the above-described substrates (F). The active energy ray polymerizable resin composition layer is preferably used for forming a laminate.
In the present invention, a laminate of transparent films can be obtained as follows.

  The resin composition of the present invention is applied to one side of a transparent film that is a film-like substrate, another transparent film is laminated on the surface of the resin composition layer, and the resin composition is further applied to one side or both sides of the laminate. The laminate can be obtained by coating and further laminating on another transparent film, glass, or transparent molded body.

  The active energy ray polymerization reaction of the resin composition of the present invention used as a coating agent proceeds by irradiating an active energy ray at the time of coating the resin composition on one side or both sides. It is preferable to proceed the polymerization reaction. Under the present circumstances, the said base material (F) may be a timber, a metal plate, a plastic plate, a film-like base material, a glass plate, a paper processed product, etc., and these can be especially used without a restriction | limiting.

  The active energy ray polymerization reaction of the resin composition of the present invention used as an adhesive proceeds when the resin composition is applied or laminated, and further after irradiation with active energy rays. It is preferable to advance the polymerization reaction by irradiating active energy rays later. At this time, the base material (F) needs to be made of a material that easily transmits the active energy rays in order to advance the polymerization reaction by irradiation with the active energy rays. In particular, it is preferable to use a transparent film (H) or a transparent glass plate as the substrate (F). However, if a transparent film or a transparent glass plate is used as one substrate, the other substrate is difficult to transmit active energy rays, such as wood, metal plates, plastic plates, paper processed products, etc. The base material which consists of can also be used. In this case, the resin composition can be polymerized and cured by irradiating active energy rays from the transparent film (H) or the transparent glass plate side.

  The transparent film of this invention can be used for optical films, such as information communication apparatuses, such as a display and a touch panel.

  In the laminated body of this invention, it is preferable to use a film-form base material as a base material (F). Specific examples of the film-like substrate include cellophane, various plastic films, and paper. Of these, the use of various transparent plastic films is preferred. Moreover, as a film-like base material, as long as the film is transparent, it may have a single layer structure, or may have a multilayer structure formed by laminating a plurality of base materials. Even if it has a film, it can be used conveniently. When constituting the laminate of the present invention, it is preferable to form a resin layer comprising the resin composition of the present invention on at least one surface of a transparent film.

  Hereinafter, more specific embodiments of the laminate of the present invention will be described by taking as an example the case where a transparent film (H) is used as a substrate. That is, the following description relates to a laminate having a resin layer, such as a coat layer or an adhesive layer, formed of the resin composition of the present invention on at least one main surface of a transparent film.

  A laminate constituted by using the resin composition of the present invention as a coating agent is typically a sheet-like film having a structure of transparent film / coat layer or coat layer / transparent film / coat layer. . Such a laminate can be obtained by applying a resin composition to at least one main surface of the transparent film (H), polymerizing and curing the resin composition, and forming a coat layer.

  On the other hand, a laminate constituted by using the resin composition of the present invention as an adhesive is typically transparent film / adhesive layer / transparent film, or transparent film / adhesive layer / transparent film / adhesive layer / transparent film. The sheet-like multilayer film obtained by laminating a plurality of transparent films. In another embodiment, the laminate is a sheet-like multilayer film such as transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film, and other optical members such as glass or optical molded bodies. It may have a fixed configuration. The laminate can be obtained by curing the adhesive layer by polymerizing and curing the approximate resin composition from one side or both sides of the film with active energy rays.

  When the resin composition is used as a coating agent or an adhesive, the polymerization and curing of the resin composition is carried out by applying active energy rays to the coating layer at the time of coating the resin composition, at the time of laminating or after laminating the film-like substrate. It is implemented by irradiating. Although it does not specifically limit, it is preferable that the said irradiation is implemented after lamination | stacking, such as a film-form base material.

  As described above, when the transparent film (H) is used as the substrate (F), the laminate can be suitably used for optical applications. From the viewpoint of obtaining good optical properties, the transparent film (H) used in the laminate is, for example, heat excellent in optical properties such as transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropic properties. It is preferable that it is various transparent films (H) comprised from a plastic resin. Such various transparent films (H) are also referred to as various plastic films or plastic sheets. Specific examples include, for example, polyvinyl alcohol films, polytriacetyl cellulose films, polyolefin films such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymers, polyester films such as polyethylene terephthalate and polybutylene terephthalate, Examples include polycarbonate films, polynorbornene films, polyarylate films, polyacrylic films, polyphenylene sulfide films, polystyrene films, polyvinyl films, polyamide films, polyimide films, and polyoxirane films.

  In the laminate of the present invention, when a multilayer film is formed by laminating a plurality of transparent films (H), the transparent films (H) to be used may be the same or different. For example, a polyacrylic film may be laminated on a polycycloolefin film via an adhesive layer.

  The thickness of the transparent film (H) can be appropriately determined, but is generally 1 to 500 μm and preferably 1 to 300 μm from the viewpoints of workability such as strength or handleability and thin layer properties. 5 to 200 μm is more preferable. In the optical application, the thickness of the transparent film (H) is particularly preferably in the range of 5 to 150 μm.

  In one embodiment of the optical element laminate according to the present invention, it is preferable to use the optical film (I) mainly used in optical applications as the transparent film (H). Here, the optical film (I) is a film obtained by subjecting the transparent film (H) itself to a special treatment, such as optical functions (light transmission, light diffusion, light collection, refraction, scattering, and HAZE). A film having an optical function is called an optical film. In order to impart these optical functions, these functional materials are not only kneaded into a film or laminated by sputtering, but also an adhesive containing a functional material or a coating agent is used. In general, the contained film is laminated with an adhesive or the like to give an optical function. In addition, the optical film (I) is used alone or by laminating several kinds of optical films in multiple layers with a coating agent or an adhesive.

  Specific examples of the optical film include, for example, a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a light diffusion film, a brightness enhancement film, a prism film ( A prism sheet), a decorative film (meaning a filling sheet for a touch panel), a light guide film (also referred to as a light guide plate), and the like. The laminated optical film using the resin composition of the present invention as an adhesive is a glass plate such as a liquid crystal display device, a PDP module, a touch panel module, and an organic EL module, and a transparent film such as the above various plastic films. Furthermore, it is preferable that the resin composition of the present invention is further laminated and pasted as an adhesive and used as a laminate for optical elements.

Lamination of each optical film (reflection sheet, light guide plate, prism sheet, diffusion sheet, brightness enhancement film, 3D film, etc.) in the backlight unit using the active energy ray polymerizable resin composition as an adhesive, especially the lamination of the prism sheet. More specifically, can be obtained as follows. Hereinafter, as an example of the laminated body for an optical element, a laminate of prism sheets is given, and the embodiment of the laminated body will be described more specifically.
A prism sheet is a sheet that is used on a display and is installed on the upper surface of the light guide plate of the backlight of a liquid crystal panel to improve the brightness in the front direction. It is an optical film (I) called a lens sheet.
The above-mentioned prism sheet generally has a structure in which a prism portion (lens portion) of an acrylic resin is finely laminated on a base film of a polyester resin, and illuminance distribution, luminance distribution, and emission angle characteristics. In consideration of the above, two prism sheets are stacked (substantially orthogonal) so that the optical axes are different from each other in order to improve the front luminance. At this time, the front luminance changes depending on the prism pitch, prism depth, prism material, and optical axis angle, and is used by being laminated and fixed with an adhesive or the like. Laminated and used as a laminated body for optical elements.

  Although not particularly limited, for example, the prism sheet can be laminated as follows. Apply the active energy ray-polymerizable resin composition as an adhesive to the back side of the prism sheet (the side where the convex lens surface is not laminated) or any sheet-like optical film, and then apply the other to the formed adhesive layer. After overlapping the lens surface which is the convex part of the prism sheet, the active energy ray is irradiated from the back side of one sheet or the optical film side, and the adhesive layer that has been cured with the active energy ray is placed between both sheet-like members. Form and stack. This method irradiates active energy rays with an adhesive layer formed by using an active energy ray polymerizable resin composition as an adhesive between two optical films, so that the adhesive is polymerized and cured. Has the advantage of being less susceptible to oxygen inhibition. However, on the other hand, since the active energy rays are irradiated to the adhesive layer through the optical film, the optical film on the side irradiated with the active energy rays is easy to transmit without attenuating the active energy rays as much as possible. Is preferably used.

  As described above, as an embodiment of the optical element laminate, the prism sheet lamination has been described as an example. However, the laminate is characterized by using the resin composition of the present invention as a coating agent or adhesive for various substrates. Therefore, it is not limited to the prism sheet, and it should be easily understood that a laminated body that can be suitably used in optical applications can be configured in other embodiments using other various base materials.

  Hereinafter, specific embodiments of the present invention will be described with reference to examples. However, the present invention is not limited to the following examples. Prior to the description of the examples, a method for measuring the weight average molecular weight (Mw) will be described.

  The weight average molecular weight uses gel permeation chromatography “HLC-8220GPC” manufactured by Tosoh Corporation, and separation columns: “TSK-GEL SUPER H5000”, “TSK-GEL SUPER H4000”, “TSK-GEL” manufactured by Tosoh Corporation. The “SUPER H3000” and “TSK-GEL SUPER H2000” were connected in series, and tetrahydrofuran at a temperature of 40 ° C. was used as the mobile phase, and the polystyrene-equivalent weight average molecular weight was measured at a flow rate of 0.6 ml / min.

<Adjustment of active energy ray polymerizable resin composition>
[Composition Examples 1-41]
Formulation example after charging into a light-shielded 300 ml glass bottle substituted with oxygen concentration of 10% or less at a ratio (parts by mass) shown in Table 1 and thoroughly stirring with a disper to sufficiently deaerate. The active energy ray-polymerizable resin composition shown in FIG. In addition, the numerical value in Table 1 represents a mass part, and a blank represents 0 mass part.

  About the active energy ray polymeric resin composition of the compounding example shown in Table 1, the solution external appearance and viscosity were calculated | required according to the following method, and the result was shown in Table 2.

Abbreviations in the table are as follows.
<Compound (A-1)>
4HBA: 4-hydroxybutyl acrylate 2HEA: 2-hydroxyethyl acrylate 2HPA: 2-hydroxypropyl acrylate CHDMMA: 1,4-cyclohexanedimethanol acrylate <Compound (A-2-1)>
IBXA: Isobornyl acrylate DCPA: Dicyclopentanyl acrylate <Compound (A-2-2)>
M-315: Triacrylic acid isocyanuric acid ethylene oxide modified product (manufactured by Toagosei Co., Ltd.)
ACMO: 4-acryloylmorpholine GMA: glycidyl acrylate <compound (A-3)>
Ebecryl 810: manufactured by Daicel Cytec Co., Ltd. polyester oligomer (polyester acrylate weight average molecular weight 1000)
UV3000B: polyurethane synthetic oligomer (urethane acrylate weight average molecular weight 18000) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
Ebecry 600: Polyepoxy oligomer produced by Daicel Cytec
(Epoxy acrylate weight average molecular weight 500)
<Compound (A-4)>
nBA: butyl acrylate NPGDA: neopentyl glycol diacrylate DEAA: diethyl acrylamide <active energy ray polymerization initiator (B)>
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, DAROCUR TPO)
CPI110P: Triarylsulfonium salt type photoacid generator (manufactured by San Apro)
<Active energy ray sensitizer>
DETX-S: Nippon Kayaku Co., Ltd. thioxanthone sensitizer <compound (C)>
EtOH: ethyl alcohol (molecular weight 46)
EG: ethylene glycol (molecular weight 62)
GlY: Glycerin (molecular weight 92)
TMP: trimethylolpropane (molecular weight 134)
PETN: Pentaerythritol (molecular weight 136)
PGL10: manufactured by Daicel Corporation, polyglycerol 10 (glycerin decamer, molecular weight 759)
<Compound (C ′) containing at least one hydroxyl group having a molecular weight exceeding 1000>
PGLX: Polyglycerol 40 (glycerin 40-mer, molecular weight 2981) manufactured by Daicel Corporation

"appearance"
The appearance of the resin composition obtained in each formulation example was observed and visually evaluated.

"viscosity"
About 1.2 ml of the resin composition obtained in each blending example was measured with an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) under an atmosphere of 23 ° C., and a rotation speed of 0.5 to The solution viscosity (mPa · s) was measured at 100 rpm for 1 minute.

<Example of production of laminate A>
[Examples 1 to 34] [Comparative Examples 1 to 7]
A laminate A was prepared using the active energy ray polymerizable resin composition shown in Table 1. Two prism sheets (prism sheet made by Nippon Special Optical Resin Co., Ltd .: trade name “LPV90-1.0”, material: poly (methyl methacrylate), thickness: 2 mm), which is a polyacrylic transparent film, are prepared as a base material. did. The corona treatment was performed on the back surface (the surface having no prism) of the first prism sheet with a discharge amount of 300 W · min / m ² , and then the compositions shown in the examples and comparative examples described in Table 1 were used. Using a wire bar coater, coating was performed such that the film thickness after coating was 1 μm to form a resin layer. Next, the front surface (prism surface) of the second prism sheet is laminated so that the optical axis of the first prism sheet and the optical axis of the second prism sheet are orthogonal to each other, and the first prism sheet / resin layer / A laminate composed of the second prism sheet was obtained. Next, the four sides of the laminate were fixed to the tinplate using cellophane tape so that the front surface of the first prism sheet was in contact with the tinplate. A laminate of prism sheets fixed by irradiating ultraviolet rays with a maximum illuminance of 300 mW / cm ² and an integrated light quantity of 300 mJ / cm ² from the back side of the second prism sheet with an active energy ray irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation). A was produced.

  About the obtained laminated body A (laminated body of the fixed prism sheet), peel strength, gel fraction, punching workability, and heat-and-moisture resistance were determined according to the following methods, and the results are also shown in Table 3.

<Peel strength>
Peel strength was measured according to JIS K6854-4 Adhesive-Peel Adhesive Strength Test Method-Part 4: Floating Roller Method. That is, the obtained laminate A (fixed prism sheet laminate) was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. Using a double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.), the sample was attached on a metal plate using a laminator to obtain a laminate for measuring the fixed prism sheet laminate A and the metal plate. . The measurement laminate is cut in advance between the two prism sheets, and the measurement laminate is peeled off at a speed of 300 mm / min at 23 ° C. and a relative humidity of 50%. The peel strength was determined. The peel strength was evaluated according to the following four levels. .
(Evaluation criteria)
A: Peeling force is 5.0 (N / 25 mm) or more, peeling is impossible or prism sheet is broken. (Very good)
○: Peeling force is 1.0 (N / 25 mm) or more and less than 5.0 (N / 25 mm). (Good)
(Triangle | delta): The peeling force is 0.5 (N / 25mm) or more and less than 1.0 (N / 25mm). (Available)
X: Peeling force is less than 0.5 (N / 25 mm). (Bad)

<Gel fraction>
After coating a polynorbornene-based film (manufactured by Nippon Zeon Co., Ltd., trade name “Zeonor film (registered trademark) ZF-14, thickness: 100 μm”) with an active energy ray polymerizable resin composition using a wire bar coater. The film was coated so that the film thickness was 25 μm, and a resin layer was formed. Further, after a polynorbornene-based film is laminated on the resin layer to obtain a laminate composed of three layers, a maximum illuminance of 300 mW / cm ² and an integrated light amount of 300 mJ / cm are obtained with an active energy ray irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation). ² active energy rays were irradiated to polymerize and cure the resin layer. Thereafter, the polynorbornene-based film was peeled off to obtain a resin layer. After measuring the mass of the resin layer (referred to as “mass 1”), the resin layer was sandwiched between metal meshes (SUS316, 150 mesh) and refluxed in methyl ethyl ketone (MEK) for 3 hours. Further, it was dried at 80 ° C. for 30 minutes, and the mass of the resin layer (referred to as “mass 2”) was measured. The gel fraction was calculated from the following formula and evaluated in three stages.
Gel fraction (%) = {1- (mass 1-mass 2) / mass 1}} × 100
(Evaluation criteria)
○: Gel fraction is 90% or more (good)
Δ: Gel fraction 80% to less than 90% (can be used)
X: Gel fraction is less than 80% (defect)

<Punching workability>
Using a super straight cutter (100 mm × 100 mm) manufactured by Dumbbell, the fixed prism sheet laminate A produced in the above example was punched from the back side of the second prism sheet. About the laminated body A punched out, the distance between the prism sheet and the resin layer produced by punching was measured with a ruler, and the average value of the distance was evaluated in the following three stages.
(Evaluation criteria)
○: 0 mm, no floating, no peeling (good)
Δ: 0 to 0.5 mm (can be used)
×: Over 0.5 mm (defect)

《Moisture and heat resistance》
The fixed prism sheet laminate was cut into a size of 50 mm × 40 mm and exposed to an environment of 60 ° C.-90% RH and 85 ° C.-85% RH for 1000 hours. About the laminated body after exposure, the distance of the prism sheet and resin layer which arose by exposure was measured with the ruler, and the average value of the distance was evaluated in the following four steps.
(Evaluation criteria)
A: No peeling under conditions of 85 ° C.-85% RH. (Very good)
○: No peeling under conditions of 60 ° C. and 90% RH. (Good)
(Triangle | delta): There exists peeling of less than 0.5 mm on the conditions of 60 degreeC-90% RH. (Available)
X: There exists peeling of 0.5 mm or more on condition of 60 degreeC-90% RH. (Bad)

<Example of production of laminate B>
[Examples 35 to 87] [Comparative Examples 8 to 14]
Using the active energy ray polymerizable resin composition shown in Table 1, the following laminate B was prepared. As the transparent film, a polyacetylcellulose-based film (manufactured by Fuji Film Co., Ltd., trade name “Fujitack: 80 μm”, UV absorber-containing polytriacetylcellulose-based film) was used. After performing the corona treatment on the transparent film surface with a discharge amount of 300 W · min / m ² , the wire bar coater was prepared using the compositions shown in the examples and comparative examples described in Table 4 as the active energy ray polymerizable coating agent. Using this, coating was performed so that the film thickness after coating was 2 μm, and a resin layer was formed. The four sides of the laminate B were fixed to the tinplate with cellophane tape so that the transparent film was in contact with the tinplate. After the inside of the UV irradiation device (Toshiba Corporation high pressure mercury lamp) was replaced with dry nitrogen, a laminate B was produced by irradiating ultraviolet rays with a maximum illuminance of 300 mW / cm ^{2 with} a wavelength of 365 nm and an integrated light amount of 300 mJ / cm ² from the resin layer side. .

  About the obtained laminated body, adhesive force and wet heat resistance were calculated | required in accordance with the following method, and the result was similarly shown in Table 4.

"Adhesion"
According to JIS K5600-5-6: 1999, a cross-cut peel test was performed. The number of cells peeled in 100 cells was evaluated in four stages.
(Evaluation criteria)
A: 0 square (very good)
○: 1-10 mass (good)
△: 11-30 squares (usable)
X: 31 squares or more (defect)

《Moisture and heat resistance》
The wet heat resistance of the laminate B was evaluated based on the same method and evaluation criteria as the wet heat resistance of the laminate A.

The laminates (Examples 1 to 87) using the active energy ray polymerizable resin composition of the present invention are superior in peel strength, punching workability, heat resistance, and moist heat resistance to the laminates of Comparative Examples 1 to 16. It became clear.

Claims (7)

α, β-ethylenically unsaturated double bond group-containing compound (A), active energy ray polymerization initiator (B), and compound (C) containing at least one hydroxyl group having a molecular weight of 30 to 1,000 (provided that α , Β-ethylenically unsaturated double bond group-containing compound (A) and active energy ray polymerization initiator (B) are excluded), and an active energy ray polymerizable composition An active energy ray-polymerizable composition comprising 0.01 to 10 parts by mass of a compound (C) containing at least one hydroxyl group having a molecular weight of 30 to 1000 with respect to 100 parts by mass of the product. The α, β-ethylenically unsaturated double bond group-containing compound (A) comprises a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound (A-1). The active energy ray polymerizable composition as described. The α, β-ethylenically unsaturated double bond group-containing compound (A) comprises an α, β-ethylenically unsaturated double bond group-containing compound (A-2) having a ring structure. Item 3. The active energy ray polymerizable resin composition according to Item 1 or 2. The activity according to any one of claims 1 to 3, wherein the α, β-ethylenically unsaturated double bond group-containing compound (A) comprises an oligomer (A-3) having a mass average molecular weight of 300 to 30,000. Energy ray polymerizable composition. The active energy ray-polymerizable composition according to any one of claims 1 to 4, comprising 0.05 to 20% by mass of the active energy ray polymerization initiator (B) in the total amount of the active energy ray-polymerizable composition. . A laminate comprising a layer made of the active energy ray-polymerizable composition according to any one of claims 1 to 5 on one side or both sides of a base material (F).   The substrate (F) is a polyacetylcellulose film, polynorbornene film, polypropylene film, polyacryl film, polycarbonate film, polyester film, polyvinyl alcohol film or polyimide film. The laminate according to claim 6.