JP2017066322A - Active energy ray curable adhesive composition excellent in insulation property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable adhesive composition capable of being temporary adhered with having adhesiveness during conjugation with an adherend, capable of being adhered with the adherend by reacting by irradiation of an active energy ray, having high insulation performance with high in optical transparency and high in volume resistance even under high temperature and high humidity environment.SOLUTION: There is provided an active energy ray curable adhesive composition containing following (A) to (D) components and having water absorption percentage of a cured article after active energy ray irradiation of 1% or less and glass transition temperature of 0°C or higher. (A) component: a polymer. (B) component: a compound having one or more ethylenic unsaturated group in a molecule. (C) component: a photoinitiator and/or a sensitizer. (D) component: a thermosetting crosslinking agent.SELECTED DRAWING: None

Description

  The present invention is an active energy ray curable adhesive capable of adhering to an adherend by bonding or adhering to the adherend by crosslinking or curing by irradiation with an active energy ray. The present invention relates to a composition, an active energy ray-curable adhesive sheet produced using the composition, and a laminate produced using the composition.

The pressure-sensitive adhesive is also called a pressure-sensitive adhesive, and is a kind of adhesive having adhesiveness (also referred to as tackiness) at normal temperature. It is defined as “a substance that adheres to the body”.
Adhesives are widely used for adhesive tapes, adhesive labels, adhesive films, and the like because adherends can be bonded together in a short time.
The pressure-sensitive adhesive generally contains a polymer having a low glass transition temperature (hereinafter referred to as “Tg”) as a main component, and a small amount of a crosslinking agent is often used to improve cohesion.

  When the adhesive is to be used in applications where the adherend may be exposed to high temperatures, such as for automobiles and displays, it is necessary to increase the cohesive strength at high temperatures, so high crosslink density and Tg improvement Measures such as increasing the molecular weight are necessary. However, adhesive strength and heat resistance are generally in a trade-off relationship, and trying to improve cohesive strength at high temperatures sacrifices peel strength, so that an adhesive that balances both at a high level can be obtained. Was extremely difficult.

  From such a technical background, in order to compensate for the drawbacks of the conventional adhesive, it has the simplicity of the adhesive at the time of joining, improves the cohesive force by reacting and solidifying by irradiation of heat or active energy rays after joining, So-called “adhesives” have been proposed.

  Patent Document 1 includes a) a polymer of an unsaturated monomer having a carboxyl group, a hydroxyl group or an amino group, b) a crosslinking agent selected from an isocyanate group-containing compound, an epoxy group-containing compound or an aziridinyl group-containing compound, c) a photocurable pressure-sensitive adhesive composition having at least one (meth) acryloyl group and containing a photopolymerizable compound that does not react with a) and b) and a photosensitizer. A photocurable pressure-sensitive adhesive molded product formed into a film or the like has been proposed.

  Patent Document 2 includes a polymer (A) having any of a carboxyl group, a hydroxyl group, a glycidyl group, an isocyanate group or an amide group on a base sheet or a release sheet, and an unsaturated group capable of reacting with the functional group. An adhesive sheet provided with a pressure-sensitive adhesive layer by applying and drying a mixture containing the compound (B) and the photopolymerization initiator (C) has been proposed.

  Patent Document 3 includes (a) a polymer having a weight average molecular weight of 10,000 to 2,000,000 and a Tg of −100 ° C. to 100 ° C., (b) a monomer having one or more carbon-carbon double bonds, and (c ) Adhesive compositions for optical recording media containing an initiator have been proposed.

  However, these pressure-sensitive adhesives and adhesives cannot be increased in crosslink density after irradiation with active energy rays because the polymer itself as a main component has no photosensitivity. Sex was insufficient. Furthermore, the compositions described in Patent Documents 2 and 3 have a problem that when the adhesive sheet is stored after being produced, the adhesive sticks out of the sheet.

  Patent Document 4 discloses a urethane (meth) obtained by reacting an ethylenically unsaturated group-containing acrylic polymer (A), a polyol containing at least one (meth) acrylic polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. A curable resin composition comprising an acrylate oligomer (B), a photopolymerization initiator (C), and a crosslinking agent (D) has been proposed.

This pressure-sensitive adhesive has photosensitivity because the polymer itself as a main component contains an ethylenically unsaturated group. Therefore, there is an advantage that the crosslinking density after irradiation with active energy rays can be increased, and the heat resistance of the adhesive can be increased.
However, this pressure-sensitive adhesive has a problem that it is difficult to achieve both heat resistance and adhesion because shrinkage at the time of curing increases as the crosslinking density is increased.

  As described above, the conventional pressure-sensitive adhesive does not have a sufficient balance between adhesive strength and heat resistance, and the adhesive is insufficient in heat resistance if the polymer is non-photosensitive, and is photosensitive. Has a problem that it is difficult to achieve both heat resistance and adhesion. Furthermore, when the adhesive sheet is manufactured and stored, the adhesive agent protrudes from the substrate.

  The inventors of the present invention have adhesiveness at the time of joining with an adherend and can be temporarily attached, and can adhere strongly to the adherend by reacting with irradiation of active energy rays, particularly heat resistance and adhesion. Active energy ray containing a polymer having a maleimide group as an active energy ray-curable adhesive composition that does not have a problem of the adhesive sticking out of the base material during storage of the adhesive sheet A curable adhesive composition has been proposed (Patent Document 5).

Japanese Patent Publication No. 02-016942 JP 2006-111651 A JP 2004-303404 A JP 2005-239856 A JP 2010-261029 A

  However, in the case of producing an insulating sheet using an adhesive sheet obtained from the conventional adhesive described above, there is a problem that it cannot be used as an insulating sheet because the volume resistivity is low under high temperature and humidity conditions. . In addition, the conventional adhesives sometimes become unsuitable for optical applications because the cured product may become cloudy and the transparency may be lowered.

  The present invention can be temporarily bonded with adhesion at the time of bonding to an adherend, can be bonded to the adherend by reacting by irradiation with active energy rays, has high optical transparency and is in a high temperature and high humidity environment. It aims at providing the manufacturing method of the active material ray hardening-type adhesive composition and adhesive sheet which have insulation performance with high volume resistivity, and a laminated body obtained by using this.

As a result of intensive studies to solve the above problems, the present inventors have found that in an active energy ray-curable adhesive composition, a polymer, a compound having an ethylenically unsaturated group, a photopolymerization initiator, and / or Or it contains a sensitizer and a thermosetting crosslinking agent, and the volume resistivity becomes higher than a specific value under high temperature and high humidity conditions by setting the water absorption and Tg of the cured product after irradiation with active energy rays to a specific value. As a result, the present invention has been completed.
Hereinafter, the present invention will be described in detail.

  The active energy ray-curable adhesive composition of the present invention has tackiness when bonded to an adherend and can be temporarily bonded, and is crosslinked and cured by irradiation with active energy rays to form the adherend. The cured product film has high optical transparency and the cured product film has high insulation. Therefore, the image display device can be used for applications where insulation is required.

FIG. 1 shows an example of production of an active energy curable adhesive film or sheet (hereinafter referred to as “AE curable film”) using the composition of the present invention. FIG. 2 shows an example of laminate production using the AE curable film of the present invention. FIG. 3 shows an example of laminate production using the AE curable film of the present invention.

The present invention is a composition comprising the following components (A) to (D), wherein the cured product after irradiation with active energy rays has a water absorption of 1% or less and an active energy ray curable type having a Tg of 0 ° C. or more. The present invention relates to an adhesive composition.
(A) Component: Polymer (B) Component: Compound having one or more ethylenically unsaturated groups in the molecule (C) Component: Photopolymerization initiator and / or sensitizer (D) Component: Thermosetting type Hereinafter, the components (A) to (E), the other components, and the active energy ray-curable adhesive composition will be described.

  In the present specification, the active energy ray-curable adhesive composition is also simply referred to as “adhesive composition” or “composition”. Moreover, the crosslinked product or hardened | cured material obtained by irradiating an active energy ray to a composition is collectively called "hardened | cured material." Further, acrylate or methacrylate is represented as (meth) acrylate, acryloyl group or methacryloyl group is represented as (meth) acryloyl group, and acrylic acid or methacrylic acid is represented as (meth) acrylic acid. The description “xx to yy” represents a numerical range including xx and yy.

1. (A) component (A) component of this invention is a polymer.
The molecular weight of the component (A) is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,500,000 in terms of weight average molecular weight (hereinafter referred to as “Mw”).
In the present invention, Mn and Mw mean values obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter abbreviated as GPC) using tetrahydrofuran as a solvent based on the molecular weight of polystyrene.

As the component (A), a polymer having a Tg (glass transition temperature) of −8 to 50 ° C. is preferable, and more preferably −5 to 40 ° C. (A) By making Tg of a component -8 degreeC or more, it can be set as what is excellent in the insulation of the hardened | cured material of a composition, By making Tg 50 degrees C or less, the composition before ultraviolet curing can be obtained. It can be excellent in adhesiveness to the substrate.
In the present invention, Tg means a value measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), and a value at the glass transition temperature intermediate point (Tmg) in the ΔT-temperature curve. Means.

As the component (A), various polymers can be used.
For example, polycondensation polymers such as polyester, polyamide and alkyd resins, polyaddition polymers such as polyurethane, ene-thiol compounds, novolac resins, urea-formaldehyde resins and xylene resins, vinyl monomers and cyclic ethers, etc. And polymers obtained by copolymerizing these monomers.
Among these polymers, a copolymer obtained by copolymerizing (meth) acrylate as a vinyl monomer (hereinafter referred to as “(meth) acrylate polymer”) is an optical property, adhesiveness, It is preferable because of its excellent electrical characteristics.
Hereinafter, the (meth) acrylate polymer will be described.

1-1. As the (meth) acrylate-based polymer, various polymers can be used as long as they have (meth) acrylate as an essential constituent monomer unit.
As the (meth) acrylate polymer, a polymer obtained by copolymerizing the following monomers (b) and (c) is more preferable.
Monomer (b): a compound having a hydroxyl group or / and a carboxyl group and an ethylenically unsaturated group Monomer (c): a compound other than the monomer (b) having an ethylenically unsaturated group The monomers (b) and (c) will be described.

1-1-1. Monomer (b)
The monomer (b) is a compound having a hydroxyl group or / and a carboxyl group and an ethylenically unsaturated group. By copolymerizing the monomer (b), a hydroxyl group or a carboxyl group can be introduced into the polymer, and the adhesion of the resulting composition to the substrate can be improved.
As the monomer (b), various compounds can be used as long as they have a hydroxyl group and / or a carboxyl group, and a compound having one (meth) acryloyl group [hereinafter referred to as monofunctional (meth) acrylate]. , Vinyl compounds, vinyl esters, conjugated dienes and the like.

  Examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate; Hydroxyl-containing alicyclic alkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate; Glycerol mono (meth) acrylate, polyethylene glycol mono Polyalkylene glycol mono (meth) acrylates such as (meth) acrylate, polypropylene glycol mono (meth) acrylate and polyethylene glycol-polypropylene glycol copolymers It can be mentioned as well as allyl alcohol; over preparative; hydroxyethyl (meth) acrylamide.

  Examples of the ethylenically unsaturated compound having a carboxyl group include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid and maleic anhydride, and the like; monoethyl itaconic acid Esters, monoalkyl esters of unsaturated dicarboxylic acids such as fumaric acid monobutyl ester and maleic acid monobutyl ester; and ω-carboxypolycaprolactone (meth) acrylate, (meth) acrylic acid dimer, 2- (meth) acryloyloxy Examples thereof include carboxyl group-containing (meth) acrylates such as ethylphthalic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.

Among these, hydroxyalkyl (meth) acrylate and (meth) acrylic acid are preferable because of their high adhesive strength with the optical film.
Moreover, 1 type (s) or 2 or more types can be used for a monomer (b).

1-1-2. Monomer (c)
The monomer (c) is copolymerized for the purpose of adjusting physical properties such as Tg, adhesive strength and adhesive strength of the polymer. The monomer (c) is copolymerizable with the monomer (b). In addition to the monomer (b), various compounds can be used, and examples thereof include monofunctional (meth) acrylates, vinyl compounds, vinyl esters, conjugated dienes, and (meth) acrylamides.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl. (Meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) ) Acrylate, i-nonyl (meth) acrylate, i-myristyl (meth) acrylate, n-decyl (meth) acrylate, i-decyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate and n -Stearyl (meth) acryl Alkyl of over preparative like (meth) acrylate;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and tricyclodecane (meth) ) Alicyclic alkyl (meth) acrylates such as acrylates;
Alkoxy group content such as methoxypolyethylene glycol (meth) acrylate such as 2-methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate and methoxytriethylene glycol (meth) acrylate ( (Meth) acrylate;
Such as benzyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, alkylphenol alkylene oxide modified (meth) acrylate, p-cumylphenol alkylene oxide modified (meth) acrylate and o-phenylphenol alkylene oxide modified (meth) acrylate (Meth) acrylate having an aromatic ring (Examples of alkylene oxide include ethylene oxide and propylene oxide); and pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, tetrahydrofurfuryl ( (Meth) acrylate having a heterocyclic ring such as (meth) acrylate and N- (meth) acryloyloxyethylhexahydrophthalimide, mono [2 (Meth) acryloyloxyethyl] phosphate, mono [2- (meth) acryloyloxypropyl] phosphate, 2- (meth) acryloyloxyethyldiphenyl phosphate, mono [3-chloro-2- (meth) acryloyloxypropyl] phosphate, Mono [(meth) acryloyloxyethyl] phosphate monoethanolamine salt, mono [(meth) acryloyloxyethyl] phosphate, [mono (diethylaminoethyl (meth) acrylate) salt, mono [(meth) acryloyloxyethyl] phosphate, Examples thereof include phosphoric acid (meth) acrylates such as mono (dimethylaminoethyl (meth) acrylate] salts.

Examples of the vinyl compound include styrene, vinyl toluene, acrylonitrile, methacrylonitrile, N-vinylformamide, acryloylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactone.
Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloride, vinyl pivalate, vinyl laurate, and vinyl versatate.
Examples of the conjugated diene include butadiene, isoprene, chloroprene, and isobutylene.
Examples of (meth) acrylamide include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid, N-isopropyl (meth) acrylamide and the like.

1-1-3. (Meth) acrylate polymer production method The (meth) acrylate polymer production method is not particularly limited, and may be produced according to conventional methods such as solution polymerization, emulsion polymerization and suspension polymerization.

Examples of the method for producing by radical polymerization by a solution polymerization method include a method in which a raw material monomer to be used is dissolved in an organic solvent and heated and stirred in the presence of a thermal polymerization initiator.
Further, a chain transfer agent can be used to adjust the molecular weight of the polymer, if necessary.

Examples of the thermal polymerization initiator used include peroxides that generate radical species by heat, azo compounds, and redox initiators.
Examples of the peroxide include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide and the like. Examples of the azo compound include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, and the like. Examples of redox initiators include hydrogen peroxide-iron (II) salt, peroxodisulfate-sodium hydrogen sulfite, cumene hydroperoxide-iron (II) salt, and the like.

As organic solvents, hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane;
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxy Ethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1 Alcohol-based solvents such as methoxy-2-propanol and 1-ethoxy-2-propanol;
Tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether and bis (2-butoxyethyl) ether, polyethylene glycol bis (2 Ether solvents such as ethylhexoate);
Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di-n-propyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone and methylcyclohexanone;
Methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, acetic acid-n-butyl, acetic acid-i-butyl, acetic acid-sec-butyl, pentyl acetate And ester solvents such as isopentyl acetate;
Nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, acetonitrile, propionitrile, butyronitrile, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, 2-pyrrolidone, N-methyl And nitrogen compound solvents such as pyrrolidone and ε-caprolactam; and sulfur compound solvents such as dimethyl sulfoxide and sulfolane.

  Examples of the chain transfer agent include cyanoacetic acid; C 1-8 alkyl ester of cyanoacetic acid; bromoacetic acid; C 1-8 alkyl ester of bromoacetic acid; aromatics such as anthracene, phenanthrene, fluorene, 9-phenylfluorene Compounds: aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene; benzoquinone, 2,3,5,6-tetramethyl-p- Benzoquinone derivatives such as benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, 1,1,2,2-tetrabromoethane, tribromoethylene trichloroethylene, bromotrichloromethane, tribromomethane, 3-chloro-1- Halogenated hydrocarbons such as propene; chloral, Aldehydes such as raldehydride; alkyl mercaptans having 1 to 18 carbon atoms; aromatic mercaptans such as thiophenol and toluene mercaptan; mercaptoacetic acid; 1 to 10 alkyl esters of mercaptoacetic acid; hydroxyl having 1 to 12 carbon atoms Alkyl mercaptans; and terpenes such as vinylene and terpinolene.

The preferable copolymerization ratio of each constituent monomer unit in the (meth) acrylate polymer is as follows.
The monomer (b) is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight.
The monomer (c) is preferably 20 to 99.8% by weight, more preferably 80 to 98% by weight.
By setting the copolymerization ratio of the monomer (b) to 0.1% by weight or more, the adhesive force between the composition and the adherend can be increased, and by setting it to 30% by weight or less, the composition Can maintain the moisture resistance. Furthermore, the hardened | cured material of the composition obtained by making the copolymerization ratio of a monomer (b) into a more preferable upper limit of 10 weight% or less can have a low water absorption.
By setting the copolymerization ratio of the monomer (c) to 20% by weight or more, the adhesive force between the composition and the adherend can be increased, and by setting it to 99.8% by weight or less, the composition Adhesion and active energy ray curability can be maintained.

1-2. Polymer having an ethylenically unsaturated group As the component (A) of the present invention, a polymer having an ethylenically unsaturated group (hereinafter referred to as “component (A1)”) has a high crosslinking density after curing, It is preferable because of its excellent characteristics.
Examples of the ethylenically unsaturated group (A1) include vinyl groups, (meth) acryloyl groups, (meth) acrylamide groups, and maleimide groups. From the viewpoint of excellent curability by active energy rays, maleimide groups and (meth ) An acryloyl group is preferred.

The molecular weight of the component (A1) is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,500,000 in terms of Mw.
Further, the molecular weight of the component (A1) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000 in terms of number average molecular weight (hereinafter referred to as “Mn”).
The polydispersity of the component (A1) [hereinafter also referred to as “Mw / Mn”] is preferably 1 or more and less than 8.0, and more preferably 1 or more and 7.5 or less.
By setting the polydispersity of the component (A1) to less than 8.0, the composition before UV curing can be excellent in adhesiveness to the substrate.

  As the component (A1), a polymer having a Tg (glass transition temperature) of −8 to 50 ° C. is preferable, and a temperature of −5 to 40 ° C. is more preferable. (A) By making Tg of a component -8 degreeC or more, it can be set as what is excellent in the insulation of the hardened | cured material of a composition, By making Tg 50 degrees C or less, the composition before ultraviolet curing can be obtained. It can be excellent in adhesiveness to the substrate.

As the component (A1), various polymers can be used as long as the polymer has an ethylenically unsaturated group. Among them, a polymer having a maleimide group (A1-1) [hereinafter referred to as “(A1-1 And a polymer (A1-2) having a (meth) acryloyl group [hereinafter referred to as “component (A1-2)”].
Hereinafter, the components (A1-1) and (A1-2) will be described in detail.

1-2-1. (A1-1) Component (A1-1) The component is a polymer having a maleimide group.
Here, the maleimide group is preferably a group represented by the following general formula (1).

[However, in General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R ¹ and R ² become one. Represents a hydrocarbon group forming a 5- or 6-membered ring. ]

As the alkyl group, an alkyl group having 4 or less carbon atoms is preferable.
As the alkenyl group, an alkenyl group having 4 or less carbon atoms is preferable.
A phenyl group etc. can be mentioned as an aryl group.
Examples of the hydrocarbon group which forms a 5-membered ring or a 6-membered ring as a saturated hydrocarbon group include a group —CH ₂ CH ₂ CH ₂ — and a group —CH ₂ CH ₂ CH ₂ CH ₂ —. Examples of the unsaturated hydrocarbon group include a group —CH═CHCH ₂ —, a group —CH ₂ CH═CHCH ₂ — and the like. In the unsaturated hydrocarbon group, in order for the maleimide group to undergo a dimerization reaction, it is necessary to select a finally obtained 5-membered or 6-membered ring having no aromaticity. The hydrocarbon group is preferably a saturated hydrocarbon group.

  Preferred specific examples of the maleimide group in the general formula (1) are shown in the following formulas (3) to (8). In the formula (7), X represents a chlorine atom or a bromine atom. Moreover, Ph in Formula (8) represents a phenyl group.

As R ¹ and R ² , one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, both R ¹ and R ² are alkyl groups having 4 or less carbon atoms, and each forms one to form a carbocycle The saturated hydrocarbon group to be used is preferable from the viewpoint of excellent adhesive strength.

  Further, among these, saturated hydrocarbon groups, each of which forms a carbocyclic ring, are more preferable because they have particularly excellent adhesion and can easily control the photodimerization of maleimide groups.

  The molecular weight of the component (A1-1) is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,500,000 in terms of Mw.

Specific examples of the component (A1-1) include the following polymers.
1-1) A copolymer having an ethylenically unsaturated compound containing a maleimide group as an essential constituent monomer unit.
1-2) A polymer obtained by adding a compound having a maleimide group and an isocyanate group to a copolymer having a hydroxyl group-containing unsaturated compound as an essential constituent monomer unit.
1-3) A polymer obtained by adding a compound having a maleimide group and an epoxy group or a maleimide group and an isocyanate group to a copolymer having an ethylenically unsaturated compound containing a carboxyl group as an essential constituent monomer unit.
1-4) A polymer obtained by adding a compound having a maleimide group and a hydroxyl group to a copolymer having an ethylenically unsaturated compound containing an isocyanate group as an essential constituent monomer unit.
1-5) A polymer obtained by adding a compound having a maleimide group and a carboxyl group to a copolymer having an ethylenically unsaturated compound containing an epoxy group as an essential constituent monomer unit.
1-6) A polymer obtained by adding a compound having a maleimide group and a hydroxyl group to an acid anhydride group-containing copolymer having an ethylenically unsaturated compound containing an acid anhydride group as an essential constituent monomer unit.

As the component (A1-1), the polymer of 1-1) is preferable.
Further, the polymer of 1-1) is more preferably a polymer obtained by copolymerizing the following monomers (a) to (c) [hereinafter referred to as “polymer (A11)”].
Monomer (a): a compound having a maleimide group represented by the general formula (1) and an ethylenically unsaturated group other than the maleimide groupMonomer (b): a hydroxyl group and / or a carboxyl group, Compound / monomer (c) having an ethylenically unsaturated group: Compound other than monomers (a) and (b) having an ethylenically unsaturated group Hereinafter, the monomers (a) to (c) will be described. To do.

1-2-1 [1]. Monomer (a)
The monomer (a) is a compound having the maleimide group and an ethylenically unsaturated group other than the maleimide group. By copolymerizing the monomer (a), a maleimide group that is a photosensitive group can be introduced into the component (A1-1), and the active energy ray curability, adhesion, and elastic modulus after curing of the resulting composition can be increased. Can be improved.

The maleimide group is preferably a group represented by the above general formula (1), and preferred specific examples are also the same as described above.
Examples of the ethylenically unsaturated group other than the maleimide group include a (meth) acryloyl group, a vinyl group and a vinyl ether group, and a (meth) acryloyl group is preferable. These ethylenically unsaturated groups can be used not only alone but also in combination.

  As the monomer (a), various compounds can be used as long as the compound has an ethylenically unsaturated group other than the maleimide group and the maleimide group described above, and is represented by the following general formula (2). A compound is preferable because it is easy to produce and has excellent curability.

[However, in Formula (2), R < ¹ > and R < ² > are synonymous with the above. R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6. ]

As R ¹ and R ² , one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, both R ¹ and R ² are alkyl groups having 4 or less carbon atoms, and each forms one to form a carbocycle. A compound which is a saturated hydrocarbon group is preferable because of excellent copolymerizability, and a compound which is a saturated hydrocarbon group which forms a carbocycle by combining each of them is more preferable because there is no problem such as gelation in polymerization.
The alkylene group for R ³ may be linear or branched. More preferably, it is a C1-C6 alkylene group.

1-2-1 [2]. Monomer (b)
The monomer (b) is a compound having a hydroxyl group or / and a carboxyl group and an ethylenically unsaturated group. By copolymerizing the monomer (b), a hydroxyl group or a carboxyl group can be introduced into the polymer (A11), and the adhesion of the resulting composition to the substrate can be improved.
As the monomer (b), various compounds can be used as long as the monomer (a) is copolymerizable with the monomer (a) and has a hydroxyl group and / or a carboxyl group. Monofunctional (meth) acrylate, vinyl compound , Vinyl esters, conjugated dienes and the like, and the same compounds as described above.

Among the above-mentioned compounds, hydroxyalkyl (meth) acrylate and (meth) acrylic acid are preferable because of high adhesive strength with the optical film.
Moreover, 1 type (s) or 2 or more types can be used for a monomer (b).

1-2-1 [3]. Monomer (c)
The monomer (c) is copolymerized for the purpose of adjusting the physical properties of the polymer (A11) such as Tg, adhesive strength and adhesive strength. As the monomer (c), various compounds can be used as long as it is copolymerizable with the monomers (a) and (b), and other than the monomers (a) and (b). (Meth) acrylate, vinyl compound, vinyl ester, conjugated diene, (meth) acrylamide and the like can be mentioned, and the same compounds as mentioned above can be mentioned.
These monomers (c) can be used alone or in combination of two or more.

As the monomer (c), among those described above, it is possible to use a compound having an aromatic ring and / or alicyclic skeleton and an ethylenically unsaturated group. The obtained component (A1-1) is hydrophobic and has a Tg. Is preferable because of high.
Examples of the compound having an aromatic ring and / or alicyclic skeleton and an ethylenically unsaturated group include the above-described alicyclic alkyl (meth) acrylate and (meth) acrylate having an aromatic ring, and cyclohexyl (meth) acrylate. And isobornyl (meth) acrylate are preferred, and cyclohexyl methacrylate and isobornyl acrylate are more preferred.

1-2-1 [4]. Production Method of Polymer (A11) The production method of the polymer (A11) is not particularly limited, and may be produced according to conventional methods such as solution polymerization, emulsion polymerization and suspension polymerization.
As a specific manufacturing method, the same method as the manufacturing method of the said (meth) acrylate type polymer is mentioned.

The preferred copolymerization ratio of each constituent monomer unit in the polymer (A11) is as follows.
The monomer (a) is preferably 0.1 to 50% by weight, more preferably 1 to 10% by weight.
The monomer (b) is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight.
The monomer (c) is preferably 20 to 99.8% by weight, more preferably 80 to 98% by weight.
By making the copolymerization ratio of the monomer (a) 0.1% by weight or more, the active energy ray curability of the resulting composition can be made sufficient, and by making it 50% by weight or less. , (A1-1) can be easily produced, and the resulting composition has excellent adhesive strength and can be less colored. Furthermore, the hardened | cured material of the composition obtained by making the copolymerization ratio of a monomer (a) into a more preferable upper limit 10 weight% or less can have a low water absorption.
By setting the copolymerization ratio of the monomer (b) to 0.1% by weight or more, the adhesive force between the composition and the adherend can be increased, and by setting it to 30% by weight or less, the composition Can maintain the moisture resistance. Furthermore, the hardened | cured material of the composition obtained by making the copolymerization ratio of a monomer (b) into a more preferable upper limit of 10 weight% or less can have a low water absorption.
By setting the copolymerization ratio of the monomer (c) to 20% by weight or more, the adhesive force between the composition and the adherend can be increased, and by setting it to 99.8% by weight or less, the composition Adhesion and active energy ray curability can be maintained.

1-2-2. Component (A1-2) The component (A1-2) is a copolymer having a (meth) acryloyl group.
As the component (A1-2), various polymers can be used as long as the polymer has a (meth) acryloyl group.
As the component (A1-2), a compound (d) having a functional group of any one of a hydroxyl group, a carboxyl group, an isocyanate group, an epoxy group, and an acid anhydride group and an ethylenically unsaturated group other than a maleimide group (hereinafter, "Referred to as" monomer (d) ") and a functional group-containing polymer that is a copolymer of monomer (c)
A polymer obtained by reacting a functional group that reacts with the functional group of the monomer (d) and a compound (d ′) having a (meth) acryloyl group [hereinafter referred to as “monomer (d ′)”] It is preferable in terms of easy production.
The functional group-containing polymer may be one obtained by copolymerizing the monomer (a) in addition to the monomers (d) and (c). In this case, the obtained component (A1-2) is a copolymer having a maleimide group and a (meth) acryloyl group.
The molecular weight of the component (A1-2) is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,500,000 in terms of Mw.

1-2-2 [1]. Monomer (d)
The monomer (d) includes a functional group of any one of a hydroxyl group, a carboxylic acid, an isocyanate group, an epoxy group, and an acid anhydride group, and an ethylenically unsaturated group other than a maleimide group (hereinafter simply referred to as “ethylenically unsaturated group”). ))).
Examples of the ethylenically unsaturated group include (meth) acryloyl group, vinyl group and vinyl ether group.
Specific examples of the monomer (d) include a compound having a hydroxyl group and an ethylenically unsaturated group (hereinafter referred to as “hydroxyl group-containing unsaturated compound”), a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter, “ Carboxylic acid-containing unsaturated compound ”), an epoxy group-containing ethylenically unsaturated group compound (hereinafter referred to as“ epoxy group-containing unsaturated compound ”), an isocyanate group-containing ethylenically unsaturated group compound (hereinafter referred to as“ an unsaturated compound ”). There are compounds having an acid anhydride group and an ethylenically unsaturated group (hereinafter referred to as “an acid anhydride group-containing unsaturated compound”), and the following compounds are exemplified.

○ Hydroxyl-containing unsaturated compound The compound includes the same compounds as those exemplified as the ethylenically unsaturated compound having a hydroxyl group in the monomer (b).

○ Carboxyl group-containing unsaturated compound Examples of the compound include the same compounds as those exemplified as the ethylenically unsaturated compound having a carboxyl group in the monomer (b).

○ Epoxy group-containing unsaturated compounds Glycidyl (meth) acrylate, vinylcyclohexene oxide, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc.

○ Isocyanate group-containing unsaturated compounds 2- (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, allyl isocyanate, etc.

○ Unsaturated compounds containing acid anhydride groups <br/> Maleic anhydride, itaconic anhydride, citraconic anhydride, etc.

1-2-2 [2]. Monomer (d ′)
The monomer (d ′) is a compound having a functional group that reacts with the functional group of the monomer (d) and a (meth) acryloyl group.
In the monomer (d ′), examples of the functional group include a hydroxyl group, a carboxylic acid, an epoxy group, and an isocyanate group.

The monomer (d ′) is selected according to the functional group of the monomer (d) to be used.
For example, when the monomer (d) is a hydroxyl group-containing unsaturated compound, an isocyanate group-containing unsaturated compound is selected as the monomer (d ′),
When the monomer (d) is a carboxylic acid-containing unsaturated compound, an isocyanate group-containing unsaturated compound or an epoxy group-containing unsaturated group compound is selected as the monomer (d ′),
When the monomer (d) is an epoxy group-containing unsaturated compound, a carboxylic acid-containing unsaturated compound is selected as the monomer (d ′),
When the monomer (d) is an isocyanate group-containing unsaturated compound, a hydroxyl group-containing unsaturated compound or a carboxylic acid-containing unsaturated compound is selected as the monomer (d ′).

  As a specific example of the monomer (d ′), the same compound as the monomer (d) can be used.

1-2-2 [3]. Polymer (A1-2) Production Method Polymer (A1-2) is produced by copolymerizing monomers (c) and (d) and, if necessary, monomer (a) by a conventional method. It is obtained by reacting the functional group-containing polymer obtained in this way with another monomer (d ′) that reacts with the functional group.
The aforementioned functional group-containing polymer can be produced by a method similar to the method for producing the (meth) acrylate polymer.
Modification by the obtained functional group-containing polymer and the monomer (d) that reacts with the functional group is usually performed at normal pressure, and if necessary, using any catalyst at a temperature of 50 to 100 ° C. It is performed for about 1 to 24 hours.

In order to shorten the reaction time, a known catalyst can be used as necessary. For example, in the case of a reaction between a hydroxyl group or a carboxyl group and an isocyanate group, an organic tin compound such as dibutyltin dilaurate, triethylamine, triethanolamine, dimethylbenzylamine, trioctylamine, 1,4-diazabicyclo (2,2,2) Octane, 1,8-diazabicyclo (5,4,0) undecene-7, tertiary amine compounds such as 1,5-diazabicyclo (4,3,0) nonene-5, organic weak acid salts such as acetic acid and capric acid Quaternary amine compounds such as acetone, metal salts of acetylacetone such as nasem iron and nasem zinc, metal organic weak acid salts such as lead naphthenate and potassium acetate, and trialkylphosphine compounds such as triethylphosphine.
Moreover, if it is reaction of a carboxyl group and an epoxy group, quaternary ammonium salts, such as the above-mentioned tertiary amine compound and tetra-n-butylammonium bromide, etc. are mentioned.

The preferable copolymerization ratio and modification ratio of each constituent monomer unit in the polymer (A1-2) are as follows.
The monomer (c) is preferably 70 to 99.9% by weight, more preferably 90 to 99% by weight.
The monomer (d) is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight.
The monomer (d ′) varies depending on the copolymerization amount of the monomer (d), but when the total amount of the monomers (c) and (d) is 100% by weight, 0.1 to 40% by weight % Is preferable, and more preferably 1 to 10% by weight. It is not preferable to react the monomer (d ′) beyond the amount of copolymerization of the monomer (d) because unreacted components of the monomer (d ′) remain.
By setting the copolymerization ratio of the monomer (d) to 0.1% by weight or more, the active energy ray curability of the resulting composition can be made sufficient, and by setting it to 30% by weight or less. , (A1-2) can be easily produced, and the resulting composition can be excellent in adhesive strength. Further, by setting the modification ratio of the monomer (d ′) to 0.1% by weight or more, the active energy ray curability of the composition can be made sufficient, and by making it 40% by weight or less. The adhesiveness of the composition can be maintained.

When the functional group-containing polymer further copolymerizes the monomer (a), it is as follows.
The monomer (a) is preferably 0.1 to 50% by weight, more preferably 1 to 10% by weight.
The monomer (c) is preferably 20 to 99.8% by weight, more preferably 60 to 98% by weight.
The monomer (d) is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight.
The monomer (d ′) varies depending on the copolymerization amount of the monomer (d). 1-40 weight% is preferable, More preferably, it is 1-10 weight%.

2. Component (B) The component (B) is a compound having one or more ethylenically unsaturated groups in the molecule.
(B) A component is mix | blended in order to obtain the composition which shows more superior adhesive force and heat resistance with respect to the composition.
Examples of the ethylenically unsaturated group in component (B) include a vinyl group, a vinyl ether group, a (meth) acryloyl group, and a (meth) acrylamide group.
The component (B) is not particularly limited, and various compounds can be used.

Specific examples of the component (B) can be the same as the monomers (a) to (d).
That is, monofunctional (meth) acrylates, vinyl compounds, vinyl esters, conjugated dienes, (meth) acrylamides, and the like can be mentioned. Specific examples thereof include the same compounds as described above, and one The ethylenically unsaturated compound which has the above hydroxyl group, the ethylenically unsaturated compound which has 1 or more carboxyl group, etc. can be mentioned, As a specific example, the compound similar to the above can be mentioned.

Examples of the component (B) other than the above include compounds having two or more (meth) acryloyl groups [hereinafter referred to as “polyfunctional (meth) acrylate”].
Specific examples of the polyfunctional (meth) acrylate include butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth). ) Acrylate, neopentyl glycol hydroxypivalic acid di (meth) acrylate, neopentyl glycol caprolactone adduct hydroxypivalic acid di (meth) acrylate, neopentyl glycol alkylene oxide adduct di (meth) acrylate, alkylene oxide adduct 1 , 6-hexanediol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol (Meth) acrylates and di (meth) acrylate of polyols, such as glycerin di (meth) acrylate;
Di (meth) acrylates of polyols having alicyclic groups such as tricyclodecane dimethylol di (meth) acrylate and dicyclopentanyl di (meth) acrylate;
Di (meth) acrylates of aromatic diol alkylene oxide adducts such as di (meth) acrylate of bisphenol A alkylene oxide adduct and di (meth) acrylate of bisphenol F alkylene oxide adduct;
Trimethylolpropane tri (meth) acrylate, glycerol alkylene oxide modified poly (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol alkylene oxide adduct penta (meth) acrylate, dipentaerythritol alkylene oxide adduct tetra Di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, isocyanuric acid alkylene oxide adduct (Meth) acrylate, isocyanuric acid alkylene oxide adduct tri (meth) acrylate, isocyanate Di null acid caprolactone adduct (meth) acrylate, tri (meth) acrylate of isocyanuric acid caprolactone adduct, polyfunctional (meth) polyol di (meth) acrylates such as acrylates such as ditrimethylolpropane tetra (meth) acrylate;
And
And phosphoric acid (meth) acrylates such as di [2- (meth) acryloyloxyethyl] phosphate and tris (meth) acryloyloxyethyl phosphate.
In the above-described alkylene oxide adduct, examples of the alkylene oxide include an oxyalkylene group having 2 to 5 carbon atoms, and an ethylene oxide group and a propylene oxide group are preferable.

  Furthermore, oligomers having one or more (meth) acryloyl groups in the molecule, such as urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate, can be mentioned.

  Urethane (meth) acrylates include reactants of polyhydric alcohols, polyisocyanates and hydroxy (meth) acrylate compounds, and reactants of polyhydric isocyanates and hydroxy (meth) acrylate compounds without using polyhydric alcohols. It is done.

  Examples of the polyhydric alcohol include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by the reaction of the polyhydric alcohol and the polybasic acid, the polyhydric alcohol, the polybasic acid, and ε-caprolactone. Caprolactone polyol obtained by the above reaction, polycarbonate polyol (for example, polycarbonate polyol obtained by reaction of 1,6-hexanediol and diphenyl carbonate, etc.) and the like.

  Examples of the organic polyvalent isocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl diisocyanate.

Epoxy (meth) acrylate is a reaction product of an epoxy resin and (meth) acrylic acid.
Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and novolac type epoxy resins. Examples of the bisphenol A type epoxy resin include Epicoat 827 (trade name, the same applies hereinafter), Epicoat 828, Epicoat 1001, and Epicoat 1004 manufactured by Japan Epoxy Resin Co., Ltd., and examples of the bisphenol F type epoxy resin include Epicoat 806 and Epicoat 4004P. Etc. Examples of the novolak type epoxy resin include Epicoat 152 and Epicoat 154.

Polyester (meth) acrylate is a reaction product of polyester polyol and (meth) acrylic acid.
The polyester polyol is obtained by a reaction between a polyhydric alcohol and a polybasic acid.
Examples of the polyhydric alcohol include neopentyl glycol, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol and bis- [hydroxymethyl] -cyclohexane.
Examples of the polybasic acid include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, and tetrahydrophthalic anhydride.

As the component (B), one or more of the aforementioned compounds can be used.
As the component (B), among the compounds described above, polyfunctional (meth) acrylates are preferable in that the Tg of the cured product of the composition can be increased.
In addition, as the component (B), among the above-mentioned compounds, the cured product is excellent in hydrophobicity and has a high Tg, so that the aromatic ring and / or alicyclic skeleton and one or more ethylenic groups in the molecule are used. A compound having an unsaturated group is preferred.
Examples of the compound having an aromatic ring and / or alicyclic skeleton and one or more ethylenically unsaturated groups in the molecule include the above-described alicyclic alkyl (meth) acrylate, (meth) acrylate having an aromatic ring, aromatic Di (meth) acrylates of aliphatic diol alkylene oxide adducts, di (meth) acrylates of polyols having an alicyclic group, etc., and di (meth) acrylates of polyols having an alicyclic group Are preferred, and tricyclodecane dimethylol di (meth) acrylate is more preferred.

  The proportion of the component (B) may be appropriately set according to the purpose, but is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight with respect to 100 parts by weight of the component (A).

3. (C) Component (C) component of this invention is a photoinitiator and / or a sensitizer. By including the component (C), the cured product can be excellent in adhesive strength and heat resistance.
Usually, when the ethylenically unsaturated group of the component (A) is a vinyl group or a (meth) acryloyl group, the one that initiates photopolymerization of these groups is defined as a photopolymerization initiator, and the component (A) When the ethylenically unsaturated group is a maleimide group, a substance that promotes this photodimerization is defined as a sensitizer. However, since there are compounds having both functions, it is difficult to distinguish them. And / or sensitizer ".

As component (C), benzyldimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl] Propanone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) )] Phenyl] -2-morpholinopropan-1-one, 2- Nediru 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1 Aromatic ketone compounds such as -one, Adekaoptomer N-1414 (manufactured by Asahi Denka), phenylglyoxylic acid methyl ester, ethyl anthraquinone, phenanthrenequinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis ( Benzophenone compounds such as diethylamino) benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone ;
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6 -Acylphosphine oxide compounds such as -dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxy] -2-hydroxy Thioxanthone compounds such as propyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone, 10-butyl-2-chloroacridone;
1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1 -Oxime esters such as (O-acetyloxime);
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2 2,4,5-triarylimidazole such as 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer Dimer; and acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.
These compounds may be used alone or in combination of two or more.
Among these, 1-hydroxycyclohexyl phenyl ketone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, 2-chlorothioxanthone, 2, 4-Diethylthioxanthone, isopropylthioxanthone, and 1-chloro-4-propylthioxanthone are preferable from the viewpoints of photoreactivity, adhesive strength, heat resistance, and coloring.

(C) As a compounding ratio of a component, 0.1-10 weight part is preferable with respect to 100 weight part of solid content in a composition, More preferably, it is 0.5-5 weight part.
By setting the blending ratio of component (C) to 0.1 parts by weight or more, the composition can be cured with an appropriate amount of ultraviolet light, and the productivity can be improved. The cured product can have excellent weather resistance and transparency.

4). (D) Component In the composition of the present invention, it is preferable to add a thermosetting cross-linking agent as the (D) component because it can impart excellent storage stability and peelability to the film before curing.

  Examples of the component (D) include cross-linking agents such as polyvalent isocyanate compounds, polyvalent epoxy compounds, amino resins, and metal chelates.

  Examples of the polyvalent isocyanate compound include bifunctional isocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl diisocyanate, and the like. Terminal isocyanate urethane prepolymer obtained by reacting a bifunctional isocyanate compound and a polyol compound, trimer of bifunctional isocyanate compound, bifunctional isocyanate compound, terminal isocyanate urethane prepolymer such as phenol, oxime, etc. And a block body of a polyvalent isocyanate compound blocked with.

Examples of the polyvalent epoxy compound include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol Z type epoxy resin, and hydrogenated bisphenol type epoxy resin.
The bisphenol A type epoxy resin is commercially available, and examples thereof include Epicoat 827 (trade name, the same applies hereinafter), Epicoat 828, Epicoat 1001, Epicoat 1004, etc. manufactured by Japan Epoxy Resin Co., Ltd. And Epicoat 4004P.

  In addition to these, novolak type epoxy resins such as phenol novolak resin and cresol novolak type epoxy resin, glycidyl ether type epoxy resins such as polyalkylene polyol (neopentyl glycol, glycerol, etc.) polyglycidyl ether, tetraglycidyl diaminodiphenylmethane, triglycidyl -Glycidyl-based epoxy resins such as p-aminophenol, triglycidyl-m-aminophenol, tetraglycidyl-m-xylenediamine, glycidyl ester-based epoxy such as diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, Vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate , (3,4-epoxy-6-methylcyclohexanol methyl) cycloaliphatic type such as adipate, triglycidyl iso Woo rates, heterocyclic epoxy resins such as glycidyl glycidoxy alkyl hydantoin and the like. Furthermore, halogen compounds of these epoxy resins, polyglycidyl esters of polybasic acids or polyester polycarboxylic acids of these epoxy resins, and polyglycidyl ethers of polyester polyols.

  Examples of the amino resin include melamine resin, guanamine resin, urea resin, melamine-urea cocondensation resin, and melamine-phenol cocondensation resin.

  Examples of metal cross-linking agents include aluminum trisacetylacetonate, aluminum tri-i-propionate, aluminum tri-s-butyrate, ethylacetoacetate aluminum di-i-propylate, etc., titanium tetra-i-propyrate, titanium tetra 2-ethylhexylate, triethanolamine titanium di-i-propylate, ammonium lactate ammonium salt, tetraoctylene glycol titanate, polyalkyl titanate, polytitanium acylate (polymer of titanium tetrabutyrate, titanium oleate) Organic titanium compounds such as zirconium-s-butyrate, zirconium diethoxy-t-butyrate and the like, hafnium- - butyrate, and other organometallic compounds such as antimony butyrate, and the like.

(D) As a compounding ratio of a component, 0.01-3 weight part is preferable with respect to 100 weight part of solid content of a composition, More preferably, it is 0.01-1 weight part.
By setting the blending ratio of the component (D) within this range, the initial adhesive force of the adhesive layer of the composition does not become too low, and the storage stability can be improved.

5. Other components Although the composition of this invention contains the said (A)-(D) component as an essential component, according to the objective, another component can be mix | blended.
Preferred other components include a silane coupling agent (hereinafter referred to as “component (E)”), an organic solvent (hereinafter referred to as “component (F)”), an anti-degradation agent (hereinafter referred to as component (G)), and the like. Is mentioned.
Hereinafter, the components (E) to (G) will be described.
In addition, the compound etc. which were mentioned as another component in the postscript may be used individually, or may use 2 or more types together.

5-1. (E) Component In order to improve the adhesion to the substrate and the heat and humidity resistance, etc., the composition of the present invention preferably contains a silane coupling agent as the component (E).
A silane coupling agent is a compound having one or more alkoxysilyl groups and one or more organic functional groups in one molecule. Examples of the organic functional groups include (meth) acryloyl groups, epoxy groups, amino groups, and thiols. Group is preferred, more preferably a (meth) acryloyl group.
The blending ratio of the silane coupling agent is preferably 0.5 parts by weight or more and 5% by weight or less with respect to 100 parts by weight of the solid content of the composition from the viewpoint of improving heat and moisture resistance and reducing outgas.

5-2. Component (F) The composition of the present invention preferably contains an organic solvent as the component (F) for the purpose of improving the coating property to the substrate. As the organic solvent, the organic solvent used in the production of the component (A) may be used as it is, or may be added separately. Specific examples of the component (F) include the organic solvents used in the production of the component (A).
The proportion of the component (F) may be appropriately set, but is preferably 10 to 90% by weight, more preferably 30 to 80% by weight in 100% by weight of the composition.

5-3. (G) Component The composition of the present invention is blended with an anti-degradation agent of (G) component in order to improve storage stability and prevent deterioration (coloring, swelling, etc.) of the adhesive layer over time. It is preferable to do.
As the deterioration inhibitor, a polymerization inhibitor or / and an antioxidant, an ultraviolet absorber, and a light stabilizer can be used.

● Polymerization inhibitor or / and antioxidant As polymerization inhibitor or / and antioxidant, phenol compounds such as hydroquinone and hydroquinone monomethyl ether, hindered substances such as 2,6-di-tert-butyl-4-methylphenol Various phenolic antioxidants such as phenolic compounds and polymer phenolic compounds, hindered amines, sulfur secondary antioxidants, phosphorus secondary antioxidants, tetramethylpiperidine-1-oxyl (TEMPO), 1- Examples include oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine (TEMPOL), an aluminum-cuperone complex (cuperon Al), and the like.

UV absorbers As UV absorbers, triazine UV absorbers such as TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479 manufactured by BASF, and benzotriazole UV absorbers such as TINUVIN 900, TINUVIN 928, and TINUVIN 1130 are used. Can be mentioned.

Light Stabilizer Examples of the light stabilizer include hindered amine light stabilizers such as TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF.

  Further, as the deterioration preventing agent, the antioxidants and light stabilizers described by Zenjiro Osawa, “Deterioration and Stabilization of Polymer Materials”, CMC Co., p135-142 and p240-246 can be used.

  The total blending ratio of these deterioration inhibitors is preferably 0.001 to 3% by weight, more preferably 0.01 to 2.0% by weight, based on 100 parts by weight of the solid content of the composition.

5-4. Other components other than the above The composition of the present invention may contain other components other than the components (E) to (G) as necessary.
Specific examples include photopolymerization initiation assistants, catalysts, inorganic materials, and leveling agents.
Hereinafter, these components will be described.

Photopolymerization initiation aid In order to further increase the reactivity, the composition of the present invention can be added as a photopolymerization initiation aid.
Examples of the photopolymerization initiation assistant include aliphatic amines and aromatic amines such as diethylaminophenone, dimethylaminobenzoic acid ethyl, and dimethylaminobenzoic acid isoacyl.
The blending ratio of the photopolymerization initiation assistant is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, based on 100 parts by weight of the solid content of the composition.

-Catalyst In order to shorten the reaction time of (E) component and (A) component, a well-known catalyst can be used as needed. For example, in the case of a reaction between a hydroxyl group or a carboxyl group and an isocyanate group, an organic tin compound such as dibutyltin dilaurate, triethylamine, triethanolamine, dimethylbenzylamine, trioctylamine, 1,4-diazabicyclo (2,2,2) Octane, 1,8-diazabicyclo (5,4,0) undecene-7, tertiary amine compounds such as 1,5-diazabicyclo (4,3,0) nonene-5, organic weak acid salts such as acetic acid and capric acid Quaternary amine compounds such as acetone, metal salts of acetylacetone such as nasem iron and nasem zinc, metal organic weak acid salts such as lead naphthenate and potassium acetate, and trialkylphosphine compounds such as triethylphosphine.
Moreover, if it is reaction of a carboxyl group and an epoxy group, quaternary ammonium salts, such as the above-mentioned tertiary amine compound and tetra-n-butylammonium bromide, etc. are mentioned.

● Inorganic materials Inorganic materials can be blended for the purpose of alleviating strain at the time of curing of the composition or improving adhesive strength.
Examples of the inorganic material include colloidal silica, silica, alumina, talc, and clay.
The blending ratio of the inorganic material is preferably 0 to 50% by weight, more preferably 0 to 30% by weight, and further preferably 0 to 10% by weight with respect to 100 parts by weight of the solid content of the composition.

● Leveling agent Examples of the leveling agent include silicone compounds and fluorine compounds.
The blending ratio of the leveling agent is preferably 0.5% by weight or less with respect to 100 parts by weight of the solid content of the composition because the adverse effect on the adhesive performance is small.

6). Active energy ray-curable adhesive composition The composition of the present invention essentially comprises the components (A) to (D).
The method for producing the composition of the present invention may be in accordance with a conventional method, and is obtained by stirring and mixing the components (A) to (D), and if necessary, the components (E) to (G) and other components. Can do. If necessary, the mixing time can be shortened by heating.

Further, the composition of the present invention needs to have a water absorption of 1% or less and Tg (glass transition temperature) of 0 ° C. or more after irradiation with active energy rays.
Thereby, it is excellent in insulation reliability and can be preferably used as an insulating sheet.

The water absorption of the cured product is 1% or less, preferably 0.5% or less. If the water absorption exceeds 1%, water is absorbed during the wet heat treatment, and the volume resistivity becomes low, and the preferable volume resistivity becomes less than 1 × 10 ¹¹ Ω · cm.
In the present invention, the water absorption means a value calculated by the following equation.
Water absorption (%) = [(Wn−W1) / W1] × 100
n: Integer of 2 or more ・ W1: Weight of cured product after being heated at 50 ° C. for 24 hours or more and then cooled to 23 ° C. in a desiccator ・ W2: Ion exchange of cured product after measurement of W1 at 23 ° C. After immersion in water for 24 hours, the weight when the cured product is taken out from the ion-exchanged water. The cured product after W3: W2 measurement is further immersed in ion-exchanged water at 23 ° C. for 24 hours, and the cured product is ion-exchanged. Weight when taken out from water: Wn: Weight after taking Wn-1 measurement after further immersing in ion exchange water at 23 ° C. for 24 hours, and weight when taking out the cured product from ion exchange water. The rate is calculated, and if the difference in water absorption calculated from W2 and W3 is less than 0.1%, the measurement is terminated, and this is defined as the water absorption rate. When the difference in water absorption is 0.1% or more, the same measurement as described above is repeated until it becomes less than 0.1%.

Tg of hardened | cured material is 0 degreeC or more, Preferably it is 5-50 degreeC. When Tg of hardened | cured material is less than 0 degreeC, the volume resistivity after wet heat processing will become low, and will become a preferable volume resistivity of less than 1 * 10 < ¹¹ > (omega | ohm) cm.

The volume resistivity of the cured product is preferably 1 × 10 ¹¹ Ωcm or more in terms of volume resistivity after wet heat treatment (60 ° C., 90% RH, 500 hours). When the volume resistivity after the wet heat treatment of the cured product is less than 1 × 10 ¹¹ Ωcm, when an electronic circuit laminate is produced using the composition, the electronic device malfunctions.
In the present invention, the volume resistivity means a value measured according to JISK6271-2008 (double ring electrode method).

7). The active energy ray-curable adhesive film or sheet. The composition of the present invention can employ various usage methods depending on the purpose. Specifically, the present invention is applied to a release-treated substrate. An active energy ray curable adhesive film or sheet (AE curable film) that can be produced by applying the composition of the above and drying to form a coating and then bonding another release-treated substrate together. It is preferably used for the production of
Hereinafter, the production method of the AE curable film and the production of the laminate using the same will be described. In the following, a part of the description will be given with reference to FIGS.

7-1. Method for producing AE curable film
An AE curable film may be produced by a conventional method, for example, by applying the composition to a substrate.
FIG. 1 shows a preferred method for producing an AE curable film composed of a base material / dry film (hereinafter referred to as “adhesive layer”) / release-treated protective film (hereinafter referred to as “release film”). An example is shown.
In FIG. 1, (1) means a substrate, and (3) means a release film.
When the composition is a solventless type (FIG. 1: A1), the composition is applied to a substrate [FIG. 1: (1)]. When the composition contains an organic solvent or the like (FIG. 1: A2), the composition is applied to a substrate [FIG. 1: (1)] and then dried to evaporate the organic solvent (FIG. 1: 1). -1).
By these methods, an adhesive layer is formed on the substrate [FIG. 1: (2)], and an AE curable film is produced (FIG. 1: B1).
In the AE curable film B1, it is preferable to laminate a release material (3) as a protective film on the adhesive layer as required (FIG. 1: B2).
In the above, if a release material is used as the substrate (1), an AE curable film composed of a release material / adhesive layer / release material can be produced.

As a base material, the material (henceforth a to-be-adhered body) for the purpose of adhesion | attachment may be sufficient, and the mold release material which can be released irrespective of a to-be-adhered body may be sufficient.
Specific examples of the material of the base material include metals such as glass and aluminum, vapor deposition films of metals and metal oxides, silicon, and polymers.
Polymers include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamide, polyimide, polycarbonate, epoxy resin, polyurethane, polylactic acid, polyethylene, polypropylene, cycloolefin polymer, acrylic resin, methacrylic resin, polystyrene, methacrylic / styrene, polyvinyl acetate. , Polyvinyl alcohol, triacetyl cellulose, cellulose acetate butyrate, hydroxypropyl cellulose, polyether sulfone, copolymers of the above polymers, liquid crystal polymers and fluororesins.
The polymer is preferably a sheet or film.
In the case where the substrate is an adherend, examples include members composed of the materials described above, and preferably include members used in image display devices.
Examples of the release film include PET film, OPP film and the like which have been subjected to release treatment such as silicone treatment, long-chain alkyl treatment, and fluorine treatment.
When the polymer is adhered, an activation treatment can be performed on one or both surfaces in order to increase the interlayer adhesion. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, surface roughening treatment, etching treatment, and flame treatment, and these may be used in combination.

The coating amount of the composition of the present invention may be appropriately selected according to the application to be used, but the coating film thickness after drying the organic solvent or the like is 0.5 to 500 μm Preferably, it is 5-200 micrometers.
As a coating method, it may be appropriately set according to the purpose, and a method of coating with a conventionally known bar coat, doctor blade, knife coater, comma coater, reverse roll coater, die coater, gravure coater, micro gravure coater, etc. Is mentioned.

When the composition contains an organic solvent or the like, it is dried after coating to evaporate the organic solvent or the like.
What is necessary is just to set drying conditions suitably according to the organic solvent etc. to be used, and the method etc. which heat to the temperature of 40-120 degreeC are mentioned.

  After production of the AE curable film, as described above, it is preferable to laminate a release film [FIG. 1: (3)] as a protective film on the adhesive layer (FIG. 1: B2), and release as a base material. A mold film is used, and the adhesive film can also be used in a form in which a release film is laminated.

The obtained AE curable film can achieve sufficient temporary fixing properties at the time of application before curing, and has adhesiveness and reliability after curing.
By using such an AE curable film, insulation reliability can be imparted.

7-2. How to use AE curable film
The AE curable film of the present invention is useful as an adhesive between the same or different materials such as fiber, composite material, ceramic, glass, rubber, concrete, paper, metal, plastic and the like.
Specifically, manufacturing of building materials such as wallpaper, laminated plywood, crime prevention glass, manufacturing of window glass with UV cut filter for automobiles, adhesion of labels to beverage bottles, cans, bottles, etc., to show windows, etc. Adhesion of exhibits, optical disk substrates, non-contact IC cards, IC chips, organic EL lighting cover glasses, projection TVs, and displays such as organic EL displays with a completely solid sealing structure Adhesive materials, Adhesion of touch panel and liquid crystal panel, Adhesion of touch panel and front window, Touch panel inside touch panel, Various optical films used for flat panel display (brightness enhancement film, prism sheet, light diffusion sheet, Fresnel lens, lenticular Lens, polarizing film, retardation film Color filter, light guide plate, antiglare film, antireflection film, reflection sheet, conductive film, near-infrared cut filter, electromagnetic wave shielding film, viewing angle control film, viewing angle compensation film, heat ray reflection film, gas barrier film, Various materials and members such as adhesion of thin film transistors and the like and adhesion of laminated plates used in electric circuits can be suitably used for adhesion and production of laminates.

  Among the above, the AE curable film of the present invention can be preferably used for the production of an electronic / electric circuit laminate of an image display device.

Examples of the active energy rays include ultraviolet rays, visible rays, X-rays, and electron beams. Since an inexpensive apparatus can be used, it is preferable to use ultraviolet rays or / and visible rays. Various light sources can be used as the light source in the case of curing with ultraviolet rays and / or visible light. Suitable light sources include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, UV electrodeless lamps, and LEDs that emit ultraviolet or / and visible light.
What is necessary is just to set suitably irradiation conditions, such as irradiation intensity | strength in active energy ray irradiation, according to the composition to be used, a base material, the objective, etc.

FIG. 2 shows an example in which an AE curable film laminated with a release film is used and irradiated with active energy rays from the base sheet side to be cured. In the AE curable film B2 of FIG. 2, (1) means a base sheet, (2) means an adhesive layer, and (3) means a release film.
In FIG. 2, the release film is released from the AE curable film immediately before use (FIG. 2: 2-1), and the adhesive layer and the adherend (4) are brought into close contact (FIG. 2: 2- 2) An active energy ray is irradiated from the base material sheet side (FIG. 2: 2-3), and a laminated body (FIG. 2: 2-4) is manufactured.

FIG. 3 shows an example in which a laminate is manufactured by using an AE curable film laminated with two release sheets and bonding two adherends together. In the AE curable film B3 of FIG. 3, (2) means an adhesive layer and (3) means a release material.
In FIG. 3, the release sheet is released from the AE curable film immediately before use (FIG .: 3-1), and the adhesive layer and the adherend [FIG. 2: (5)] are brought into close contact (FIG. 3). 3: 3-2), the other release sheet is released (FIG .: 3-3), and the adhesive layer and another adherend [FIG. 2: (4)] are brought into close contact (FIG. 3). 3: 3-4), active energy rays are irradiated from the adherend (1) side (FIG. 3: 3-5), and a laminate (FIG. 3: 3-6) is manufactured.

As described above, the AE curable film of the present invention can be preferably used for production of an electronic / electric circuit laminate of an image display device.
In this case, examples of the image display unit constituting the image display device include a transmissive or reflective liquid crystal display unit, a plasma display unit, an organic EL (OLED) unit, and an image display unit such as electronic paper.
An additional functional layer (single layer or multiple layers), for example, a polarizing plate or the like can be provided on the display surface of the image display unit. A touch panel may be present on the display surface of the image display unit.

The touch panel image display device can be used for various electronic devices.
Specific examples of the electronic device include a mobile phone, a smart phone, a portable information terminal, a portable game machine, an electronic book, a car navigation system, a portable music player, a clock, a tablet computer, a video camera, a video player, a digital camera, Examples include a positioning system (GPS) device and a personal computer (PC).

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, “part” means part by weight, and “%” means weight%.
The meanings of the abbreviations used in the production examples are as follows.

・ Monomer (a)
THPI: Compound represented by the following formula (11)

・ Monomer (b)
HEA: 2-hydroxyethyl acrylate
・ Monomer (c)
CHMA: cyclohexyl methacrylate IBXA: isobornyl acrylate MMA: methyl methacrylate BA: butyl acrylate 2-EHA: 2-ethylhexyl acrylate 2-EHMA: 2-ethylhexyl methacrylate
・ Monomer (d)
AOI: 2-acryloyloxyethyl isocyanate
Polymerization initiator V-65: 2,2′-azobis (2,4-dimethylvaleronitrile)
AMBN: 2,2′-azobis (2-methylbutyronitrile)
Chain transfer agent DM: dodecyl mercaptan
Organic solvent EtAc: ethyl acetate BuAc: butyl acetate

1. Production example
1) Production Example 1 [Production of Component (A)]
The following compounds were charged in a flask equipped with a stirrer, a thermometer, and a cooler at room temperature in the following amounts, and dissolved uniformly while blowing nitrogen at a flow rate of 50 mL / min.
THPI: 2.5 g, HEA: 2.5 g, IBXA: 35.0 g, BA: 10.0 g, EtAc: 63 g, V-65: 0.1 g
While continuing nitrogen blowing, the temperature was raised thereafter, and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 2.5 g, HEA: 2.5 g, IBXA: 35.0 g, BA: 10.0 g, EtAc: 16 g, V-65: 0.4 g
The resulting copolymer solution had a non-volatile content of 56.0%, the copolymer Mw was 154,000, and Mn was 26,000.

2) Production Example 2 [Production of Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 2.5 g, HEA: 2.5 g, CHMA: 25.0 g, BA: 15.0 g, MMA: 5.0 g, EtAc: 63 g, V-65: 0.1 g
While continuing nitrogen blowing, the temperature was raised thereafter, and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 2.5 g, HEA: 2.5 g, CHMA: 25.0 g, BA: 15.0 g, MMA: 5.0 g, EtAc: 48 g, V-65: 0.4 g
The resulting copolymer solution had a nonvolatile content of 47.5%, the copolymer Mw was 256,000, and Mn was 64,000.

3) Production Example 3 [Production of Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 2.5 g, HEA: 2.5 g, CHMA: 25.0 g, BA: 17.5 g, MMA: 2.5 g, EtAc: 63 g, V-65: 0.1 g
While continuing nitrogen blowing, the temperature was raised thereafter, and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 2.5 g, HEA: 2.5 g, CHMA: 25.0 g, BA: 17.5 g, MMA: 2.5 g, EtAc: 48 g, V-65: 0.4 g
The obtained copolymer solution had a non-volatile content of 47.3%, the copolymer Mw was 268,000, and Mn was 54,000.

4) Production Example 4 [Production of Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 2.5 g, HEA: 2.5 g, CHMA: 25.0 g, BA: 20.0 g, EtAc: 63 g, V-65: 0.1 g
While continuing nitrogen blowing, the temperature was raised thereafter, and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 2.5 g, HEA: 2.5 g, CHMA: 25.0 g, BA: 20.0 g, EtAc: 48 g, V-65: 0.4 g
The resulting copolymer solution had a nonvolatile content of 46.2%, the copolymer Mw was 316,000, and Mn was 83,000.

5) Production Example 5 [Production of component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 2.5 g, HEA: 2.5 g, IBXA: 25.0 g, BA: 20.0 g, EtAc: 63 g, V-65: 0.1 g
While continuing nitrogen blowing, the temperature was raised thereafter, and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 2.5 g, HEA: 2.5 g, IBXA: 25.0 g, BA: 20.0 g, EtAc: 16 g, V-65: 0.4 g
The resulting copolymer solution had a nonvolatile content of 57.7%, the copolymer Mw was 183,000, and Mn was 26,000.

6) Production Example 6 [Production of Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 2.5 g, HEA: 2.5 g, CHMA: 20.0 g, BA: 21.0 g, EHA: 4.0 g, EtAc: 63 g, V-65: 0.1 g
While continuing nitrogen blowing, the temperature was raised thereafter, and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 2.5 g, HEA: 2.5 g, CHMA: 20.0 g, BA: 21.0 g, 2-EHA: 4.0 g, EtAc: 48 g, V-65: 0.4 g
The resulting copolymer solution had a non-volatile content of 46.5%, the copolymer Mw was 353,000, and Mn was 81,000.

7) Production Example 7 [Production of component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
IBXA: 35.0 g, BA: 10.0 g, HEA: 2.5 g, EtAc: 63 g, V-65: 0.1 g
While continuing nitrogen blowing, the temperature was raised thereafter, and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
IBXA: 35.0 g, BA: 10.0 g, HEA: 2.5 g, EtAc: 59 g, V-65: 0.4 g
After cooling to room temperature, 5% oxygen / 95% nitrogen mixed gas was blown at a flow rate of 50 mL / min, and BHT: 0.1 g and DBTDL: 0.1 g were added and dissolved uniformly. Thereafter, the temperature was raised to 80 ° C. and held for 1 hour, then AOI: 5.0 g was charged all at once and reacted at 80 ° C. for 2 hours to obtain an ethylenically unsaturated group-containing copolymer solution.
The resulting copolymer solution had a non-volatile content of 46.4%, Mw of 177,000, and Mn of 30,000.

8) Production Example 8 [Production of component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 15.0 g, HEA: 10.0 g, MMA: 14.5 g, BA: 10.5 g, EtAc: 63 g, V-65: 0.10 g, DM: 0.01 g
Thereafter, the temperature was raised and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 15.0 g, HEA: 10.0 g, MMA: 14.5 g, BA: 10.5 g, EtAc: 38 g, V-65: 0.40 g, DM: 0.05 g
The resulting copolymer solution had a non-volatile content of 49.8%, Mw 223,000, and Mn 15,300.

9) Production Example 9 [Production of Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 6.0 g, HEA: 12.0 g, EHMA: 18.0 g, BA: 24.0 g, BuAc: 76.0 g, AMBM: 0.12 g
While continuing nitrogen blowing, the temperature was raised thereafter, and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 6.0 g, HEA: 12.0 g, EHMA: 18.0 g, BA: 24.0 g, BuAc: 76.0 g, AMBM: 0.12 g
The resulting copolymer solution had a nonvolatile content of 42.0%, Mw of 294,000, and Mn of 20,000.

10) Production Example 10 [Production of Component (A)]
The following compounds were charged in the same manner as in Production Example 1 and dissolved uniformly.
THPI: 0.5 g, HEA: 3.75 g, CHMA: 10.0 g, BA: 15.0 g, EHA: 20.75 g, EtAc: 63 g, V-65: 0.1 g
While continuing nitrogen blowing, the temperature was raised thereafter, and the mixture was stirred in the same manner and under the same conditions as in Production Example 1, and then the following mixed solution was added dropwise, followed by stirring.
THPI: 0.5 g, HEA: 3.75 g, CHMA: 10.0 g, BA: 15.0 g, EHA: 20.75 g, EtAc: 48 g, V-65: 0.4 g
The resulting copolymer solution had a nonvolatile content of 47.4%, Mw of 337,000, and Mn of 47,000.

About the polymer of the (A) component obtained by manufacture examples 1-10, the monomer and other component which were used were put together in Table 1, and were described. In Table 1, the number of parts is shown so that the total amount of the used monomers (a), (b), and (c) is 100 parts.
Further, the non-volatile content and molecular weight of these polymers were measured according to the following method. The results are shown in Table 1.

(1) Non-volatile content (%)
The obtained copolymer solution was dried under the conditions of 150 ° C. × 1 hour, and the nonvolatile content was calculated from the weight before and after the drying of the sample.

(2) Molecular weight GPC (manufactured by Tosoh Corporation: HLC-8120, column: TSKgel-GMHxl × 2, eluent: THF 1 mL / min, detector: RI) was used to measure the molecular weight in terms of polystyrene. Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.

2. Examples 1 to 9 and Comparative Examples 1 to 4
1) Manufacture of composition After putting the compound shown in Table 2 into the stainless steel container in the ratio shown in Table 2, stirring at room temperature until uniform with a magnetic stirrer, active energy ray-curable adhesive composition I got a thing.

2) Production of AE curable film 300 mm x length 300 mm Mitsubishi Plastics release film “Diafoil MRV” (silicone-treated polyethylene terephthalate film, thickness 75 μm) after drying the obtained composition The film was coated with an applicator so that the film thickness was 50 μm, and dried with a hot air dryer at 90 ° C. for 10 minutes. Thereafter, a release film “Diafoil MRQ” (silicone-treated polyethylene terephthalate film, thickness 38 μm) manufactured by Mitsubishi Plastics Co., Ltd. having a width of 300 mm and a length of 300 mm was laminated on the resin layer to obtain an AE curable film.
The obtained AE curable film was evaluated by the following method. The results are shown in Table 3.

3) Evaluation method
(1) Tg of cured product
The cured product of the AE curable film was produced by irradiating ultraviolet rays (illuminance of 365 nm light: 200 mW / cm ² , integrated light amount: ² J / cm ² ) through a release film with a high-pressure mercury lamp.
The Tg of the cured product obtained after peeling the release film was measured under the following conditions using DSC-6220 manufactured by Seiko Instruments Inc. The results are shown in Table 3.
・ Measurement conditions: Temperature rising rate 10 ° C / min

(2) Water absorption of cured product The cured product of the AE curable film is produced by irradiating ultraviolet rays (365 nm light illuminance 200 mW / cm ² , integrated light amount ² J / cm ² ) through a release film with a high-pressure mercury lamp. did.
In order to adjust the state of the cured film, the cured product from which the release film was peeled was heat-treated at 50 ° C. for 24 hours or more. Then, it cooled to 23 degreeC within a desiccator, and the hardened | cured material weight (W1) in that case was measured.
The cured product was immersed in ion-exchanged water at 23 ° C. for 24 hours, and then the cured product film was taken out from the ion-exchanged water, and water on the film surface was removed with Ben cotton, and the weight (W2) of the cured product film was measured. .
The cured product was further immersed in ion-exchanged water for 24 hours, and the weight (W3) of the cured product film was measured in the same manner as the W2 measurement.
The water absorption is calculated from the following formula, and the measurement is terminated when the difference in water absorption calculated from W2 or W3 is less than 0.1%. When the difference in water absorption was 0.1 or more, the operation of measuring the weight by immersing again in ion-exchanged water for 24 hours until it became less than 0.1 was repeated.
Water absorption (%) = [(Wn−W1) / W1] × 100
n: integer greater than or equal to 2

(3) The AE curable film to be evaluated for volume resistivity of the cured product was cut into a size of 100 mm × 100 mm, the release film on one side of the AE curable film was peeled off, and transferred to a 0.1 mm thick aluminum plate. Thereafter, a cured film was produced by a method of irradiating ultraviolet rays (illuminance of 365 nm light: 200 mW / cm ² , integrated light amount: ² J / cm ² ) from a AE curable film side through a release film through a high-pressure mercury lamp.
Thereafter, the release film is peeled off, and the condition is adjusted for 12 hours or more at room temperature. Then, in accordance with JISK6271-2008 (double ring electrode method), the state at 25 ° C. after ultraviolet irradiation, 60 ° C., 90%, 500 hours. The volume resistivity of the treated state was measured.
In addition, it means that insulation is so high that volume resistivity is high.

(4) Haze of cured product The haze of the cured product was measured in order to evaluate the transparency of the cured product.
Using an AE curable film to be evaluated, a slide glass and an easily adhesive PET film (A4300 manufactured by Toyobo Co., Ltd.) were bonded together.
A cured product was prepared by a method of irradiating ultraviolet rays from a high-pressure mercury lamp (illuminance of 365 nm light: 200 mW / cm ² , integrated light amount: ² J / cm ² ) over the A4300 side.
One day after the UV curing, haze was measured using a turbidimeter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.).

The abbreviations in Table 2 mean the following.
Component (E) EtAc: ethyl acetate BuAc: butyl acetate
(B) Component / DCPA: dimethylol-tricyclodecane diacrylate, light acrylate DCPA manufactured by Kyoeisha Chemical Co., Ltd.
M315: Isocyanuric acid ethylene oxide-modified di- and triacrylate, Aronix M-315 manufactured by Toagosei Co., Ltd.
M450: Pentaerythritol tri- and tetraacrylate, Aronix M-450 manufactured by Toagosei Co., Ltd.
M313: Isocyanuric acid ethylene oxide-modified di- and triacrylate, Aronix M-313 manufactured by Toagosei Co., Ltd.
M1200: Polyester urethane acrylate, Aronix M-1200 manufactured by Toagosei Co., Ltd., viscosity at 25 ° C. = 2,000,000 mPa · s
M140: N-acryloyloxyethylhexahydrophthalimide, Aronix M-140 manufactured by Toagosei Co., Ltd.
Component (C) : TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, Ciba Specialty Chemicals, DAROCUR TPO
-PBZ: 4-phenylbenzophenone-Irg184: 1-hydroxy-cyclohexyl-phenyl-ketone, IRGACURE184 manufactured by BASF
(D) Component P301: Trifunctional isocyanate compound, “Duranate P301-75E” manufactured by Asahi Kasei Chemicals Corporation
CO-L: Trifunctional isocyanate compound, Nippon Polyurethane Co., Ltd. Coronate L
TPA100: Trifunctional isocyanate compound, “Duranate TPA-100” manufactured by Asahi Kasei Chemicals Corporation
Component (F) KBM: 3-acryloxypropyltrimethoxysilane, “KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.
(G) Component T622: HALS-based degradation inhibitor, “TINUVIN 622SF” manufactured by BASF Japan Ltd.
135A: Phosphite antioxidant, “ADEKA STAB 135A” manufactured by ADEKA Corporation
AO80: phenolic antioxidant, "ADEKA STAB AO-80" manufactured by ADEKA Corporation
3010: Phosphite antioxidant, “ADEKA STAB 3010” manufactured by ADEKA Corporation
Others • DBTDL: Di-n-butyltin dilaurate • FTR8120: Petroleum resin, manufactured by Mitsui Chemicals Co. Also, in the column “(A) + (F)”, the upper part is a blending ratio as a copolymer solution, and the lower part is The compounding ratio of each component is meant, and “solid” means solid content.

The compositions of Examples 1 to 9 had a volume resistivity of 1 × 10 ¹¹ Ω · cm or more after the moisture and heat resistance test of the cured product, and were excellent in electrical insulation. Also, the haze was small and the transparency was excellent.
In addition, the compositions of Examples 1 to 9 were separately applied to glass and various plastic films, and then subjected to an adhesion test on those cured by irradiation with ultraviolet rays. It was excellent.
On the other hand, although the composition of Comparative Example 1 having a water absorption rate of the cured product of 2.1% exceeding the lower limit of the present invention has a high volume resistivity at 25 ° C., the volume resistivity after the wet heat test is 1 It was far below × 10 ¹¹ Ω · cm, and the insulation was insufficient.
In the compositions of Comparative Example 2, 3 and 4, the Tg of the cured product is −18 ° C., −26 ° C. and −5 ° C., respectively, and the volume resistivity after the wet heat test is 1 × 10 ¹¹ Ω · cm. The insulation was insufficient.

  The active energy ray-curable adhesive composition of the present invention can be preferably used for the production of an AE-curable adhesive film. Further, the AE curable adhesive film can be preferably used for the production of a laminate having various adherends adhered thereto, and the cured product of the composition of the present invention has excellent insulating properties. It can preferably be used for the production of an electronic / electrical circuit laminate of the image display apparatus.

Claims (23)

A composition comprising the following components (A) to (D),
An active energy ray-curable adhesive composition having a water absorption of 1% or less and a glass transition temperature of 0 ° C. or higher after irradiation with active energy rays.
(A) Component: Polymer (B) Component: Compound having one or more ethylenically unsaturated groups in the molecule (C) Component: Photopolymerization initiator and / or sensitizer (D) Component: Thermosetting type Cross-linking agent 2. The active energy ray-curable adhesive according to claim 1, wherein the volume resistivity after the wet heat treatment (60 ° C., 90% RH, 500 hours) of the cured product after irradiation with active energy rays is 1 × 10 ¹¹ Ωcm or more. Composition. The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the component (A) is a polymer having a weight average molecular weight of 10,000 to 2,000,000. (A) A component is a polymer of glass transition temperature -8-50 degreeC, The active energy ray hardening-type adhesive composition of any one of Claims 1-3. (A) A component is a polymer which has an ethylenically unsaturated group, The active energy ray hardening-type adhesive composition of any one of Claims 1-4. 6. The active energy ray-curable adhesive according to claim 5, wherein the component (A) is a polymer (A1-1) having a maleimide group represented by the following general formula (1) as an ethylenically unsaturated group. Composition.

[However, in General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, or R ¹ and R ² are combined to form a 5-membered ring. Alternatively, it represents a hydrocarbon group forming a 6-membered ring. ] The active energy ray-curable adhesive composition according to claim 6, wherein the component (A) is a polymer (A1-1) obtained by copolymerizing the following monomers (a) to (c) at the following ratio. .
Monomer (a): a compound having a maleimide group represented by the general formula (1) and an ethylenically unsaturated group other than the maleimide group; 0.1 to 50% by weight
Monomer (b): a compound having a hydroxyl group or / and a carboxyl group and an ethylenically unsaturated group; 0.1 to 30% by weight
Monomer (c): Compound other than monomers (a) and (b) having an ethylenically unsaturated group; 20 to 99.8% by weight The active energy ray-curable adhesive composition according to claim 7, wherein the component (A) is a polymer (A1-1) obtained by copolymerizing the monomers (a) to (c) in the following ratio. .
Monomer (a): 0.1 to 10% by weight
Monomer (b): 0.1 to 10% by weight
Monomer (c): 80 to 99.8% by weight The active energy ray-curable adhesive composition according to claim 7 or 8, wherein the monomer (a) is a compound represented by the following general formula (2).

[However, in Formula (2), R < ¹ > and R < ² > are synonymous with the above. R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6. ] The active energy ray-curable adhesive according to any one of claims 7 to 9, wherein the monomer (c) is a compound having an aromatic ring and / or an alicyclic skeleton and an ethylenically unsaturated group. Adhesive composition. The active energy ray-curable adhesive composition according to claim 5, wherein the component (A) is a polymer (A1-2) having a (meth) acryloyl group as an ethylenically unsaturated group. Component (A) is a functional group-containing copolymer 100 in which the following monomer (c) is copolymerized in a proportion of 70 to 99.9 wt% and the following monomer (d) is 0.1 to 30 wt%. For weight percent
The active energy ray-curable pressure-sensitive adhesive composition according to claim 11, which is a polymer (A1-2) obtained by reacting 0.1 to 20 parts by weight of the following monomer (d ′).
Monomer (c): Compound other than monomers (a) and (b) having an ethylenically unsaturated groupMonomer (d): Hydroxyl group, carbosyl group, isocyanate group, epoxy group and acid anhydride Compound / monomer (d ′) having any functional group of a group and an ethylenically unsaturated group: a compound having a functional group that reacts with the functional group of monomer (d) and a (meth) acryloyl group Component (A) is a functional group-containing copolymer 100 obtained by copolymerizing 70 to 99.9% by weight of the monomer (c) and 0.1 to 10% by weight of the monomer (d). For weight percent
The active energy ray-curable adhesive composition according to claim 12, which is a polymer (A1-2) obtained by reacting 0.1 to 10 parts by weight of the monomer (d '). Component (A) is 0.1 to 50% by weight of the monomer (a), 20 to 99.8% by weight of the monomer (c), and 0.1 to 0.1% of the monomer (d). A polymer (A1-2) obtained by reacting 0.1 to 20 parts by weight of the monomer (d ′) with respect to 100% by weight of a functional group-containing copolymer copolymerized at a rate of 30% by weight. The active energy ray hardening-type adhesive composition of any one of Claims 12-13. The active energy ray-curable adhesive according to any one of claims 12 to 14, wherein the monomer (c) is a compound having an aromatic ring and / or an alicyclic skeleton and an ethylenically unsaturated group. Adhesive composition. The activity according to any one of claims 1 to 15, wherein the component (B) is a compound having an aromatic ring and / or an alicyclic skeleton and one or more ethylenically unsaturated groups in the molecule. Energy ray curable adhesive composition. The active energy ray hardening-type adhesive composition of any one of Claims 1-16 containing 1-100 weight part of (B) component with respect to 100 weight part of (A) component. For 100 parts by weight of the solid content of the composition,
(C) 0.1-10 weight part of component (D) Active energy ray hardening-type adhesive composition of any one of Claims 1-17 containing 0.01-3 weight part of component. object. Furthermore, the active energy ray hardening-type adhesive composition of any one of Claims 1-18 containing (E) organic solvent. Furthermore, the active energy ray hardening-type adhesive composition of any one of Claims 1-19 containing (F) silane coupling agent. Furthermore, the active energy ray hardening-type adhesive composition of any one of Claims 1-20 containing (G) degradation inhibitor. A release-treated substrate, an active energy ray-curable adhesive layer obtained from the composition according to any one of claims 1 to 21, and a release-treated substrate are formed in this order. An active energy ray curable adhesive film or sheet. 23. A step of peeling off one release-treated substrate of the active energy ray-curable adhesive film or sheet according to claim 22 and causing the exposed surface of the composition to adhere to the adherend, the other release A method for producing a laminate comprising a step of peeling off the treated substrate, causing the other surface of the exposed composition to adhere to the adherend, and a step of irradiating active energy rays from the side of any adherend .

Images