KR20170039600A - Active energy ray-curable adhesive composition excellent in insulating property - Google Patents

Abstract

The object of the present invention is to provide an active energy ray-curable adhesive composition, an adhesive sheet, and a method for producing a laminate obtainable from the same, which have adhesiveness enabling temporary adherence to a substrate, and can be made to react upon irradiation with an active energy ray and thereby be bonded to the substrate, have high optical transparency, and show insulating capacities with high specific resistivity even under high-temperature and high-humidity conditions. The active energy ray-curable adhesive composition is a composition comprising the components (A) to (D), wherein a cured material thereof following irradiation with an active energy ray has an absorption rate of 1% or less, and a glass transition temperature of 0 deg. C or higher. According to the present invention, the component (A) is a polymer; the component (B) is a compound having at least one ethylenically unsaturated group in molecules; the component (C) is a photopolymerization initiator and/or a sensitizer; and the component (D) is a heat-curable crosslinker.

Description

TECHNICAL FIELD [0001] The present invention relates to an active energy ray-curable pressure-sensitive adhesive composition,

The present invention relates to an active energy ray-curable pressure-sensitive adhesive composition capable of adhering to an adherend with adhesiveness and capable of adhering an adherend by crosslinking or curing by irradiation with an active energy ray, Active energy ray-curable pressure-sensitive adhesive sheets, and laminates produced using the compositions, and belong to these technical fields.

The pressure-sensitive adhesive is also referred to as a pressure-sensitive adhesive, a kind of adhesive having adhesiveness at room temperature (also called tackiness), and in JIS K 6800, it is defined as "a substance having adhesiveness at room temperature and adhered to an adherend with light pressure" .

The pressure-sensitive adhesive is widely used for an adhesive tape, an adhesive label and an adhesive film in that the adherends can be adhered 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 cross-linking agent is often used to improve cohesive strength.

In the case where the adherend is to be developed for use in applications where the adherend is likely to be exposed to high temperatures, such as automobiles and displays, it is necessary to increase the cohesive force at high temperatures. Therefore, And other measures. However, since adhesive strength and heat resistance generally have a trade-off relationship and peeling strength is sacrificed when it is desired to improve the cohesive force at a high temperature, it is very difficult to obtain a pressure-sensitive adhesive that balances both at a high level.

From such technical background, a so-called " point adhesive " which improves the cohesive force by reacting and solidifying after irradiation with heat or an active energy ray after joining has a simplicity of a pressure-sensitive adhesive at the time of bonding in order to compensate for the drawbacks of the conventional pressure- Has been proposed.

Japanese Patent Application Laid-Open No. 02-016942 discloses a crosslinking agent selected from the group consisting of 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- Curable pressure-sensitive adhesive composition comprising a photo-curable pressure-sensitive adhesive composition comprising a photo-curable pressure-sensitive adhesive composition having a (meth) acryloyl group and a photo-polymerizable compound which does not react with a) and b) A pressure-sensitive adhesive molded article has been proposed.

Japanese Unexamined Patent Publication (Kokai) No. 2006-111651 discloses a process for producing a polymer (A) having a carboxyl group, a hydroxyl group, a glycidyl group, an isocyanate group or an amide group on a base sheet or a release sheet, an unsaturated group- B) and a photopolymerization initiator (C) is applied and dried to form a pressure-sensitive adhesive layer.

(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 at least one carbon-carbon double bond, and (c) an initiator for use in an optical recording medium.

However, in these pressure-sensitive adhesives and viscous adhesives, since the polymer itself as a main component does not have a photosensitive property, the crosslink density after irradiation with active energy rays can not be increased and the heat resistance of the viscous adhesive is insufficient. Furthermore, the compositions disclosed in Japanese Unexamined Patent Application Publication No. 2006-111651 and Japanese Unexamined Patent Publication (Kokai) No. 2004-303404 have a problem that a point adhesive is protruded from a sheet when the adhesive is formed after the production of the adhesive sheet.

Japanese Unexamined Patent Publication (Kokai) No. 2005-239856 discloses a process for producing an urethane (meth) acrylate polymer having an ethylenically unsaturated group-containing acrylic polymer (A), a polyol containing at least one (meth) acryl- (Meth) acrylate oligomer (B), a photopolymerization initiator (C) and a crosslinking agent (D).

This pressure-sensitive adhesive has photosensitivity because the polymer itself, which is the main component, contains an ethylenic unsaturated group. Therefore, it is possible to increase the crosslinking density after irradiation with active energy rays, and there is an advantage that the heat resistance of the adhesive can be increased.

However, this pressure-sensitive adhesive has a problem that when the crosslinking density is increased, shrinkage at the time of curing becomes large, it is difficult to achieve both heat resistance and adhesion.

As described above, the conventional pressure sensitive adhesive has a problem in that the balance between adhesive force and heat resistance is not sufficient and the heat resistance of the pressure sensitive adhesive is insufficient when the polymer is non-photosensitive, and it is difficult to achieve both heat resistance and adhesion when the pressure sensitive adhesive is photosensitive . In addition, when the pressure-sensitive adhesive sheet is produced and stored, there is a problem that a point-adhesive agent is protruded from the substrate.

The inventors of the present invention have found that when bonding with an adherend, the adherend can be adhered and adhered, the adherend can be adhered firmly by reaction with an active energy ray, in particular, both heat resistance and adhesion can be achieved, There has been proposed an active energy ray curable pressure-sensitive adhesive composition comprising a polymer having a maleimide group as an active energy ray-curable pressure-sensitive adhesive composition which does not have a problem in that a point adhesive is projected from a substrate during storage of the sheet (Japanese Patent Laid- 261029).

However, in the case of producing an insulating sheet using the above-mentioned conventional point-adhesive sheet obtained from a point adhesive, there is a problem that it can not be used as an insulating sheet because of its low volume resistivity under high temperature and high humidity conditions. In addition, the conventional point-stick adhesives sometimes become turbid and deteriorate in transparency, making them unsuitable for optical applications.

INDUSTRIAL APPLICABILITY The present invention relates to a thermoplastic resin composition which can be adhered to an adherend when it is adhered to an adherend and can be adhered to an adherend by reaction with an active energy ray and has a high optical transparency and a low volume resistivity An active energy ray-curable pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having high insulation performance, and a process for producing a laminate obtained by using the same.

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that the active energy ray-curable pressure-sensitive adhesive composition contains a polymer, a compound having an ethylenic unsaturated group, a photopolymerization initiator and / or a sensitizer and a thermosetting crosslinking agent And that the volume resistivity becomes higher than a specific value under the conditions of high temperature and high humidity by setting the water absorption rate and Tg of the cured product after irradiation with active energy rays to a specific value.

Hereinafter, the present invention will be described in detail.

The active energy ray-curable pressure-sensitive adhesive composition of the present invention can be adhered to an adherend with adhesive property and can be adhered by crosslinking and curing by irradiation with active energy rays, The optical transparency is high and the insulating property of the cured film is high. Therefore, it can be used for applications requiring insulation of the image display device.

Fig. 1 shows an example of the production of an active energy curable pressure-sensitive adhesive film or sheet (hereinafter referred to as " AE curable film ") using the composition of the present invention.
Fig. 2 shows an example of producing a laminate using the AE curable film of the present invention.
Fig. 3 shows an example of the production of a laminate using the AE curable film of the present invention.

The present invention relates to a composition containing the following components (A) to (D): an active energy ray-curable pressure-sensitive adhesive composition having an absorption rate of a cured product after irradiation with active energy rays of 1% or less and a Tg of 0 ° C or more.

(A) Component: Polymer

(B): a compound having at least one ethylenic unsaturated group in the molecule

Component (C): a photopolymerization initiator and / or a sensitizer

(D) Component: Thermosetting crosslinking agent

Hereinafter, the components (A) to (E), other components, and the active energy ray-curable pressure-sensitive adhesive composition will be described.

In the present specification, the active energy ray-curable pressure-sensitive adhesive composition is also simply referred to as a "pressure-sensitive adhesive composition" or "composition". The crosslinked product or cured product obtained by irradiating the composition with an active energy ray is collectively referred to as " cured product ". Further, acrylate or methacrylate is referred to as (meth) acrylate, acryloyl or methacryloyl is referred to as (meth) acryloyl group, and acrylic acid or methacrylic acid is referred to as (meth) acrylic acid. The description of " xx to yy " indicates a numerical range including xx and yy.

1. Component (A)

The component (A) of the present invention is a polymer.

The molecular weight of the component (A) is preferably from 10,000 to 2,000,000, more preferably from 50,000 to 1,500,000, in terms of a weight average molecular weight (hereinafter referred to as "Mw").

In the present invention, Mn and Mw are values obtained by converting tetrahydrofuran as a solvent and converting the molecular weight measured by gel permeation chromatography (hereinafter abbreviated as GPC) based on the molecular weight of polystyrene it means.

The component (A) is preferably a polymer having a Tg (glass transition temperature) of -8 to 50 캜, more preferably -5 to 40 캜. By setting the Tg of the component (A) to -8 캜 or higher, the cured product of the composition can be made excellent in insulation. By setting the Tg to 50 캜 or lower, the composition before UV curing can be made excellent in adhesiveness to a substrate.

In the present invention, Tg means a value measured at a heating rate of 10 ° C / minute using a differential scanning calorimeter (DSC), and a value at a glass transition temperature midpoint (Tmg) in the ΔT- Lt; / RTI >

As the component (A), various polymers can be used.

Examples thereof include polycondensation polymers such as polyesters, polyamides and alkyd resins, and polyamides such as polyurethane, ene-thiol compounds, novolak resins, urea-formaldehyde resins and xylene resins, And polymers obtained by copolymerizing monomers such as cyclic ethers.

Among these polymers, copolymers (hereinafter referred to as " (meth) acrylate polymers ") obtained by copolymerizing (meth) acrylates as vinyl monomers are used for the reasons .

Hereinafter, the (meth) acrylate-based polymer will be described.

1-1. (Meth) acrylate-based polymer

As the (meth) acrylate-based polymer, various polymers may be used as far as they contain (meth) acrylate as an essential constituent monomer unit.

As the (meth) acrylate-based polymer, a polymer obtained by copolymerizing the following monomers (b) and (c) is more preferable.

Monomer (b): a compound having a hydroxyl group and / or a carboxyl group and an ethylenic unsaturated group

Monomer (c): a compound other than the monomer (b) having an ethylenically unsaturated group

Hereinafter, the monomers (b) and (c) will be described.

1-1-1. The monomer (b)

The monomer (b) is a compound having a hydroxyl group and / or a carboxyl group and an ethylenic 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 far as they have a hydroxyl group and / or a carboxyl group, and a compound having one (meth) acryloyl group [hereinafter referred to as a monofunctional (meth) acrylate] Esters, and conjugated dienes.

Examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy- (Meth) acrylate such as 2-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; Alicyclic alkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate; Polyalkylene glycol mono (meth) acrylates such as glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and polyethylene glycol-polypropylene glycol copolymer; Hydroxyethyl (meth) acrylamide; And allyl alcohol.

Examples of the ethylenically unsaturated compound having a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid and maleic anhydride; Monoalkyl esters of unsaturated dicarboxylic acids such as itaconic acid monoethyl ester, fumaric acid monobutyl ester and maleic acid monobutyl ester; And carboxyl group-containing compounds such as ω-carboxypolycaprolactone (meth) acrylate, (meth) acrylic acid dimer, 2- (meth) acryloyloxyethylphthalic acid and 2- (meth) acryloyloxyethylhexahydrophthalic acid ) Acrylate, and the like.

Among these, hydroxyalkyl (meth) acrylate and (meth) acrylic acid are preferable because of their high adhesion to optical films.

The monomers (b) may be used alone or in combination of two or more.

1-1-2. The monomer (c)

The monomer (c) is copolymerized for the purpose of adjusting the physical properties such as the Tg, the adhesive strength and the adhesive force of the polymer. As the monomer (c), various compounds can be used as long as they have a copolymerization with the monomer (b) and other than the monomer (b), and monofunctional (meth) acrylates, vinyl compounds, vinyl esters, conjugated dienes, Amides and the like.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (Meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, (Meth) acrylate, n-decyl (meth) acrylate, i-decyl (meth) acrylate, (Meth) acrylates such as n-lauryl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate and n-stearyl (meth) acrylate;

(Meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl Alicyclic alkyl (meth) acrylates such as ethyl (meth) acrylate and tricyclodecane (meth) acrylate;

Methoxypolyethylene glycol such as 2-methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate and methoxytriethylene glycol (meth) (Meth) acrylate; alkoxy group-containing (meth) acrylates such as (meth) acrylate;

Benzyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, alkylphenol alkylene oxide modified (meth) acrylate, p-cumylphenol alkylene oxide modified (meth) acrylate and o- (Meth) acrylates having an aromatic ring such as an oxide-modified (meth) acrylate (examples of the alkylene oxides include ethylene oxide and propylene oxide); And

(Meth) acrylate, tetramethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and N- (meth) acryloyloxyethylhexahydrophthalimide. (Meth) acryloyloxyethylphosphate, mono [2- (meth) acryloyloxyethyl] phosphate, mono [2- (Meth) acryloyloxypropyl phosphate, mono [(meth) acryloyloxyethyl] phosphate monoethanolamine salt, mono [(meth) acryloyloxyethyl] phosphate, (Meth) acrylate] such as [methoxy] phosphate, [mono (diethylaminoethyl (meth) acrylate] salt, mono [(meth) acryloyloxyethyl] phosphate, Acrylate.

Examples of the vinyl compound include styrene, vinyltoluene, acrylonitrile, methacrylonitrile, N-vinylformamide, acryloylmorpholine, N-vinylpyrrolidone and N-vinylcaprolactam. .

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 dienes include butadiene, isoprene, chloroprene, and isobutylene.

(Meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxybutyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid and N-isopropyl .

1-1-3. (Meth) acrylate-based polymer

The method for producing the (meth) acrylate-based polymer is not particularly limited, and may be produced by a conventional method such as solution polymerization, emulsion polymerization and suspension polymerization.

As a method of producing by radical polymerization by a solution polymerization method, a method of dissolving a starting monomer to be used in an organic solvent and heating and stirring in the presence of a thermal polymerization initiator can be given.

If necessary, a chain transfer agent may be used to control the molecular weight of the polymer.

Examples of the thermal polymerization initiator to be used include peroxides, azo compounds and redox initiators which generate radical species by heat.

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, and azobis-4-methoxy-2,4-dimethylvaleronitrile. Examples of redox initiators include hydrogen peroxide-iron (II) salts, peroxosulfate-sodium hydrogen sulfite, cumene hydroperoxide-iron (II) salts and the like.

Examples of the organic solvent include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane;

Butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropanol Butoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene Alcohol-based solvents such as glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol and 1-ethoxy-2-propanol;

(2-methoxyethyl) ether, bis (2-ethoxyethyl) ether and bis (2-ethoxyethyl) ether, such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis Ethyl) ether, and polyethylene glycol bis (2-ethylhexoate);

But are not limited to, acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di- And ketone solvents such as methylcyclohexanone;

Butyl acetate, isobutyl formate, pentyl formate, methyl formate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, isopropyl acetate, Ester solvents such as pentyl acetate and isopentyl acetate;

N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, Nitrogen compound solvents such as acetamide, 2-pyrrolidone, N-methylpyrrolidone and? -Caprolactam; And

And sulfur compound solvents such as dimethyl sulfoxide and sulfolane.

Chain transfer agents include cyanoacetic acid; Alkyl esters of 1 to 8 carbon atoms in cyanoacetic acid; Bromoacetic acid; Alkyl esters of bromoacetic acid having 1 to 8 carbon atoms; Aromatic compounds such as anthracene, phenanthrene, fluorene, and 9-phenylfluorene; aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol and p-nitrotoluene; Benzoquinone derivatives such as benzoquinone and 2,3,5,6-tetramethyl-p-benzoquinone; Borane derivatives such as tributylborane; Halogenated hydrocarbons such as carbon tetrabromide, 1,1,2,2-tetrabromoethane, tribromoethylene trichloroethylene, bromotrichloromethane, tribromomethane and 3-chloro-1-propene; Aldehydes such as chloral, furaldehyde and the like; Alkyl mercaptans of 1 to 18 carbon atoms; Aromatic mercaptans such as thiophenol and toluene mercaptan; Mercaptoacetic acid; Alkyl esters of 1 to 10 carbon atoms in mercaptoacetic acid; Hydroxylalkylmercaptans having 1 to 12 carbon atoms; And terpenes such as binen and terpinolene.

The preferred copolymerization ratio of each constituent monomer unit in the (meth) acrylate-based polymer is as follows.

The amount of the monomer (b) is preferably from 0.1 to 30% by weight, more preferably from 1 to 10% by weight.

The amount of the monomer (c) is preferably from 20 to 99.8% by weight, and more preferably from 80 to 98% by weight.

When the copolymerization ratio of the monomer (b) is 0.1% by weight or more, the adhesive strength between the composition and the adherend can be increased, and when it is 30% by weight or less, the moisture resistance of the composition can be maintained. By setting the copolymerization ratio of the monomer (b) to 10% by weight or less, which is the more preferable upper limit range, the cured product of the obtained composition can be made to have a low water absorption rate.

When the copolymerization ratio of the monomer (c) is 20% by weight or more, the adhesive strength between the composition and the adherend can be increased, and when it is 99.8% by weight or less, the adhesion of the composition and the active energy ray curability can be maintained.

1-2. Polymers having an ethylenic unsaturated group

As the component (A) of the present invention, a polymer having an ethylenic unsaturated group (hereinafter referred to as "component (A1)") is preferred because of high crosslinking density after curing and excellent electrical characteristics.

Examples of the ethylenic unsaturated group of the component (A1) include a vinyl group, a (meth) acryloyl group, a (meth) acrylamide group and a maleimide group, and from the viewpoint of excellent curability by an active energy ray, And (meth) acryloyl groups are preferable.

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.

The molecular weight of the component (A1) is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 500,000 as the number average molecular weight (hereinafter referred to as " Mn ").

(Hereinafter also referred to as " Mw / Mn ") of the component (A1) is preferably 1 or more and less than 8.0, and more preferably 1 or more and 7.5 or less.

When the polydispersity of the component (A1) is less than 8.0, the composition before the ultraviolet curing can be made excellent in adhesiveness to the substrate.

The component (A1) is preferably a polymer having a Tg (glass transition temperature) of -8 to 50 캜, more preferably -5 to 40 캜. By setting the Tg of the component (A) to -8 캜 or higher, the cured product of the composition can be made excellent in insulation. By setting the Tg to 50 캜 or lower, the composition before UV curing can be made excellent in adhesiveness to a substrate.

As the component (A1), various polymers can be used as long as it is a polymer having an ethylenic unsaturated group. Among them, a polymer (A1-1) having a maleimide group [hereinafter referred to as "component (A1-1) Methacryloyl group-containing polymer (A1-2) [hereinafter referred to as "(A1-2) component").

Hereinafter, the components (A1-1) and (A1-2) will be described in detail.

1-2-1. (A1-1) Component

The component (A1-1) is a polymer having a maleimide group.

The maleimide group is preferably a group represented by the following general formula (1).

[Chemical 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 are taken together to form a 5-atom A hydrocarbon group which forms a ring or a six-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.

Examples of the aryl group include a phenyl group and the like.

As the hydrocarbon group forming one of the five-membered ring or the six-membered ring, the saturated hydrocarbon group includes a group -CH ₂ CH ₂ CH ₂ - and a group -CH ₂ CH ₂ CH ₂ CH ₂ - a group of the hydrocarbon group include groups -CH = CHCH ₂ -, and the like -, a group -CH ₂ CH = CHCH _2. Further, in the unsaturated hydrocarbon group, in order for the maleimide group to undergo dimerization reaction, it is necessary to select the finally obtained five-membered ring or six-membered ring not having aromaticity. As the hydrocarbon group, a saturated hydrocarbon group is preferable.

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

(2)

(3)

[Chemical Formula 4]

Examples of R ¹ and R ² include an alkyl group having one hydrogen atom and the other having 4 or less carbon atoms, an alkyl group having 4 or less carbon atoms both of R ¹ and R ² , and a saturated hydrocarbon group, Is preferable.

Among these, saturated hydrocarbon groups each of which is a carbon ring to form a carbon ring are particularly preferable because of their excellent adhesive strength and easy control of the optical dimerization of the maleimide group.

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 comprising an ethylenically unsaturated compound containing a maleimide group as an essential constituent monomer unit.

1-2) A polymer obtained by adding a maleimide group and an isocyanate group-containing compound to a copolymer having an unsaturated monomer containing a hydroxyl group as an essential monomer unit.

1-3) A polymer obtained by adding a maleimide group and a compound having an epoxy group or 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 isocyanate group-containing ethylenically unsaturated compound 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 maleimide group and a compound having a hydroxyl group to an acid anhydride group-containing copolymer containing an acid anhydride group-containing ethylenically unsaturated compound as an essential constituent monomer unit.

As the component (A1-1), the polymer of the above-mentioned 1-1) is preferable.

The polymer of the above 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 maleimide group represented by the general formula (1) and a compound having an ethylenic unsaturated group other than the maleimide group

Monomer (b): a compound having a hydroxyl group and / or a carboxyl group and an ethylenic unsaturated group

Monomer (c): a monomer other than the monomer (a) having an ethylenic unsaturated group and the monomer (b)

Hereinafter, the monomers (a) to (c) will be described.

1-2-1 [1]. The monomer (a)

The monomer (a) is a compound having an ethylenically unsaturated group other than the maleimide group and the maleimide group. The maleimide group as a photosensitive group can be introduced into the component (A1-1) by copolymerizing the monomer (a), and the active energy ray curability, adhesion, and elastic modulus of the resulting composition can be improved.

The maleimide group is preferably a group represented by the above-mentioned formula (1), and preferable examples thereof are also the same as above.

Examples of the ethylenic 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 ethylenic unsaturated groups may be used alone or in combination.

As the monomer (a), various compounds can be used as long as it is a compound having an ethylenic unsaturated group other than the maleimide group and the maleimide group described above. However, the compound represented by the following general formula (2) is easily produced, Therefore, it is preferable.

[Chemical Formula 5]

[Wherein, in formula (2), R ¹ and R ² have the same meanings as defined 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 , a compound in which one of the alkyl groups R ¹ and R ² in which one of them is a hydrogen atom and the other is a carbon number of 4 or less is an alkyl group having not more than 4 carbon atoms and a saturated hydrocarbon group in which each of R ¹ and R ² forms a carbon ring, A compound which is a saturated hydrocarbon group which forms a carbon ring by combining with each other is more preferable because there is no problem such as gelation in polymerization.

The alkylene group of R ³ may be linear or branched. More preferably an alkylene group having 1 to 6 carbon atoms.

1-2-1 [2]. The monomer (b)

The monomer (b) is a compound having a hydroxyl group and / or a carboxyl group and an ethylenic 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 may be used as long as they have a hydroxyl group and / or a carboxyl group and have a copolymerization with the monomer (a), and monofunctional (meth) acrylates, vinyl compounds, vinyl esters and conjugated dienes And the same compounds as described above.

Of these compounds, hydroxyalkyl (meth) acrylate and (meth) acrylic acid are preferred because of their high adhesion to optical films.

The monomers (b) may be used alone or in combination of two or more.

1-2-1 [3]. The monomer (c)

The monomer (c) is copolymerized for the purpose of adjusting the physical properties such as the Tg, the adhesion and the adhesive force of the polymer (A11). As the monomer (c), various compounds may be used as long as they have a copolymerization with the monomers (a) and (b), and the monomers (a) and (b), and monofunctional (meth) acrylates, vinyl compounds and vinyl esters , Conjugated dienes and (meth) acrylamides, and the same compounds as mentioned above can be mentioned.

These monomers (c) may be used alone or in combination of two or more.

As the monomer (c), it is preferable to use a compound having an aromatic ring and / or an alicyclic skeleton and an ethylenically unsaturated group among the above because the resulting component (A1-1) is hydrophobic and has a high Tg.

Examples of the compound having an aromatic ring and / or an alicyclic skeleton and an ethylenic unsaturated group include (a) a (meth) acrylate having an alicyclic alkyl (meth) acrylate and an aromatic ring described above and cyclohexyl And isobornyl (meth) acrylate are preferable, and cyclohexyl methacrylate and isobornyl acrylate are more preferable.

1-2-1 [4]. Process for producing polymer (A11)

The method for producing the polymer (A11) is not particularly limited, and it may be produced by a conventional method such as solution polymerization, emulsion polymerization and suspension polymerization.

As a concrete production method, the same method as the above-mentioned (meth) acrylate-based polymer production method can be mentioned.

A preferable copolymerization ratio of each constituent monomer unit in the polymer (A11) is as follows. The amount of the monomer (a) is preferably 0.1 to 50% by weight, more preferably 1 to 10% by weight. The amount of the monomer (b) is preferably from 0.1 to 30% by weight, more preferably from 1 to 10% by weight. The amount of the monomer (c) is preferably from 20 to 99.8% by weight, and more preferably from 80 to 98% by weight.

By setting the copolymerization ratio of the monomer (a) to 0.1% by weight or more, the resulting composition can exhibit sufficient activity energy ray curability, and when it is 50% by weight or less, the component (A1-1) , And further, the composition obtained is excellent in the adhesive force, and the coloring can be reduced. By setting the copolymerization ratio of the monomer (a) to a more preferable upper limit of 10% by weight or less, the cured product of the obtained composition can be made to have a low water absorption rate.

When the copolymerization ratio of the monomer (b) is 0.1% by weight or more, the adhesive strength between the composition and the adherend can be increased, and when it is 30% by weight or less, the moisture resistance of the composition can be maintained. By setting the copolymerization ratio of the monomer (b) to a more preferable upper limit of 10% by weight or less, the cured product of the resulting composition can be made to have a low water absorption rate.

When the copolymerization ratio of the monomer (c) is 20% by weight or more, the adhesive strength between the composition and the adherend can be increased, and when it is 99.8% by weight or less, the adhesion of the composition and the active energy ray curability can be maintained.

1-2-2. (A1-2) 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.

(D) (hereinafter referred to as " monomer (d) ") having a functional group of a hydroxyl group, a carboxyl group, an isocyanate group, an epoxy group and an acid anhydride group and an ethylenic unsaturated group other than the maleimide group And the monomer (c) is added to the functional group-containing polymer which is a copolymer of the monomer (c)

A polymer obtained by reacting a compound (d ') (hereinafter referred to as " monomer (d') ") having a functional group and a (meth) acryloyl group which react with the functional group of the monomer (d) desirable.

The functional group-containing polymer may be a copolymer obtained by further copolymerizing the monomer (a) in addition to the monomers (d) and (c). In this case, the resulting 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]. The monomer (d)

The monomer (d) is a compound having a functional group such as a hydroxyl group, a carboxylic acid group, an isocyanate group, an epoxy group and an acid anhydride group and an ethylenic unsaturated group other than the maleimide group (hereinafter simply referred to as "ethylenic unsaturated group" to be.

Examples of the ethylenic unsaturated group include a (meth) acryloyl group, a vinyl group and a vinyl ether group.

Specific examples of the monomer (d) include a compound having a hydroxyl group and an ethylenic unsaturated group (hereinafter referred to as a "hydroxyl group-containing unsaturated compound"), a compound having a carboxyl group and an ethylenic unsaturated group (hereinafter referred to as "carboxyl group- A compound having an isocyanate group and an ethylenically unsaturated group (hereinafter referred to as an " isocyanate group-containing unsaturated compound "), an acid anhydride group and a compound having an ethylenic unsaturated group (Hereinafter referred to as " unsaturated compound containing an acid anhydride group "), and the following compounds can be given.

○ Hydroxyl group-containing unsaturated compound

Examples of the compound include 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 compound

Glycidyl (meth) acrylate, vinylcyclohexene oxide, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like

○ Isocyanate group-containing unsaturated compound

(Meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate and allyl isocyanate

○ An acid anhydride group-containing unsaturated compound

Maleic anhydride, itaconic anhydride, citraconic anhydride, etc.

1-2-2 [2]. The monomer (d ')

The monomer (d ') is a compound having a functional group and a (meth) acryloyl group reacting with the functional group of the monomer (d).

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, as the monomer (d '), a hydroxyl group-containing unsaturated compound or a carboxylic acid-containing unsaturated compound is selected.

As specific examples of the monomer (d '), the same compounds as the monomer (d) can be used.

1-2-2 [3]. Production method of polymer (A1-2)

The process for producing the polymer (A1-2) is a process for producing the polymer (A1-2), which comprises reacting the monomer (c) and the monomer (d), and if necessary, further copolymerizing the monomer (a) (d ').

The above-mentioned functional group-containing polymer can be produced by the same method as the above-mentioned (meth) acrylate-based polymer production method.

Modification of the resultant functional group-containing polymer and the monomer (d) which reacts with the functional group is usually carried out at normal pressure and at a temperature of 50 to 100 캜 for 1 to 24 hours, using any catalyst as required.

In order to shorten the reaction time, known catalysts can be used if necessary. For example, when the reaction is carried out with a hydroxyl group or a carboxyl group and an isocyanate group, an organic tin compound such as dibutyltin dilaurate, an organic amine compound such as triethylamine, triethanolamine, dimethylbenzylamine, trioctylamine or 1,4-diazabicyclo [2.2. Tertiary amine compounds such as 1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5, acetic acid, capric acid , Organic acid salts such as acetylacetone metal salts such as cumene and naphthyl zinc, metal organic acid salts such as lead naphthenate and potassium acetate, and trialkylphosphine compounds such as triethylphosphine. have.

As the reaction between a carboxyl group and an epoxy group, a quaternary ammonium salt such as the above-mentioned tertiary amine compound and tetra-n-butylammonium bromide can be given.

The preferable copolymerization ratio and modification ratio of the respective constituent monomer units in the polymer (A1-2) are as follows.

The monomer (c) is preferably 70 to 99.9% by weight, and more preferably 90 to 99% by weight.

The content of the monomer (d) is preferably from 0.1 to 30% by weight, more preferably from 1 to 10% by weight.

When the total amount of the monomers (c) and (d) is 100% by weight, the amount of the monomer (d ') varies depending on the copolymerization amount of the monomer (d) To 10% by weight. Reaction of the monomer (d ') in excess of the copolymerization amount of the monomer (d) is not preferable because the unreacted component of the monomer (d') remains.

By setting the copolymerization ratio of the monomer (d) to 0.1% by weight or more, the obtained composition can exhibit sufficient activation energy ray curability, and when it is 30% by weight or less, the component (A1-2) In addition, it is possible to obtain an excellent adhesive force of the obtained composition. When the modifying ratio of the monomer (d ') is set to 0.1% by weight or more, the composition can have sufficient active energy ray curability, and when it is 40% by weight or less, the adhesion of the composition can be maintained.

When the functional group-containing polymer is further copolymerized with the monomer (a), it is as follows.

The amount of the monomer (a) is preferably 0.1 to 50% by weight, more preferably 1 to 10% by weight.

The amount of the monomer (c) is preferably from 20 to 99.8% by weight, and more preferably from 60 to 98% by weight.

The content of the monomer (d) is preferably from 0.1 to 30% by weight, more preferably from 1 to 10% by weight.

When the total amount of the monomers (a), (c) and (d) is 100% by weight, the amount of the monomer (d ') varies depending on the copolymerization amount of the monomer (d) Preferably 1 to 10% by weight.

2. Component (B)

(B) is a compound having at least one ethylenic unsaturated group in the molecule.

The component (B) is blended for the purpose of obtaining a composition exhibiting better adhesion and heat resistance to the composition.

Examples of the ethylenic unsaturated group in the 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) may be the same as the monomers (a) to (d).

(Meth) acrylate, a vinyl compound, a vinyl ester, a conjugated diene and (meth) acrylamide, and specific examples thereof include the same compounds as described above, and one or more An ethylenically unsaturated compound having a hydroxyl group and an ethylenically unsaturated compound having at least one carboxyl group, and specific examples thereof include the same compounds as described above.

Examples of the component (B) other than the above include a compound 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, (Meth) acrylate of neopentyl glycol di (meth) acrylate, neopentyl glycol hydroxypivalic acid di (meth) acrylate, neopentyl glycol caprolactone adduct di (meth) acrylate of neopentyl glycol alkylene oxide adduct, Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol modified trimethylol propane di (meth) acrylate, alkylene oxide adduct 1,6-hexanediol di Di (meth) acrylates of polyols such as acrylate and glycerin di (meth) acrylate;

Di (meth) acrylates of polyols having an alicyclic group 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) acrylates of di (meth) acrylate and bisphenol F alkylene oxide adduct of bisphenol A alkylene oxide adducts;

(Meth) acrylate of dipentaerythritol alkylene oxide adduct, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, glycerin alkylene oxide modified poly (meth) (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate of an erythritol alkylene oxide adduct, Di (meth) acrylate of isocyanuric acid alkylene oxide adducts, tri (meth) acrylate of isocyanuric acid alkylene oxide adducts, adduct of caprolactone adduct of isocyanuric acid caprolactone Di (meth) acrylate, tri (meth) acrylate of isocyanuric acid caprolactone adduct, ditrimethylol propane Tetra (meth) di (meth) acrylate of polyols, such as polyfunctional (meth) acrylate such as acrylate; And,

Di (2- (meth) acryloyloxyethyl] phosphate, and tris (meth) acryloyloxyethyl phosphate.

In the alkylene oxide adducts described above, as the alkylene oxide, an oxyalkylene group having 2 to 5 carbon atoms can be enumerated, and an ethylene oxide group and a propylene oxide group are preferable.

Further, oligomers having at least one (meth) acryloyl group in the molecule such as urethane (meth) acrylate, epoxy (meth) acrylate and polyester (meth) acrylate can be mentioned.

The urethane (meth) acrylate can be a reaction product of a polyhydric alcohol, a polyvalent isocyanate and a hydroxy (meth) acrylate compound, or a reaction product of a polyvalent isocyanate and a hydroxy (meth) acrylate compound without using a polyhydric alcohol .

Examples of polyhydric alcohols include polyether polyols such as polypropylene glycol and polytetramethylene glycol; polyester polyols obtained by the reaction between the polyhydric alcohol and the polybasic acid; and caprolactone obtained by the reaction between the polyhydric alcohol and the polybasic acid and? -Caprolactone A lactone polyol, and a polycarbonate polyol (e.g., a polycarbonate polyol obtained by reacting 1,6-hexanediol with diphenyl carbonate).

Examples of the organic polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, dicyclopentanyl diisocyanate, and the like. have.

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 resins and bisphenol F-type epoxy resins, and novolak-type epoxy resins. Examples of the bisphenol A type epoxy resin include Epicote 827 (trade name, the same applies hereinafter), Epicote 828, Epicote 1001 and Epicote 1004 manufactured by Japan Epoxy Resin Co., Ltd., and bisphenol F type epoxy resins , Epicoat 806, Epicoat 4004P, and the like. Examples of the novolak-type epoxy resin include Epicot 152, Epicot 154 and the like.

The polyester (meth) acrylate is a reaction product of a polyester polyol and (meth) acrylic acid.

The polyester polyol is obtained by a reaction between a polyhydric alcohol and a polybasic acid.

Examples of polyhydric alcohols include neopentyl glycol, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylol propane, 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 above-described compounds may be used.

Among the above-mentioned compounds, as the component (B), polyfunctional (meth) acrylate is preferable in that the Tg of the cured product of the composition can be increased.

As the component (B), among the above-mentioned compounds, a compound having an aromatic ring and / or an alicyclic skeleton and at least one ethylenic unsaturated group in the molecule is preferable because the cured product is excellent in hydrophobicity and has a high Tg Do.

Examples of the compound having an aromatic ring and / or an alicyclic skeleton and at least one ethylenic unsaturated group in the molecule include the above-mentioned alicyclic alkyl (meth) acrylates, (meth) acrylates having aromatic rings, aromatic diol alkylene oxide Di (meth) acrylate of poly (meth) acrylate of water, epoxy (meth) acrylate and polyol having alicyclic group, and di (meth) acrylate of polyol having alicyclic group is preferable, Cyclodecane dimethylol (meth) acrylate is more preferable.

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

3. Component (C)

The component (C) of the present invention is a photopolymerization initiator and / or a sensitizer. By including the component (C), the cured product can be made excellent in adhesive force and heat resistance.

Generally, when the ethylenic unsaturated group of the component (A) is a vinyl group or a (meth) acryloyl group, the photopolymerization of these groups is defined as a photopolymerization initiator, and when the ethylenic unsaturated group of the component (A) In the present invention, the term "photo polymerization initiator and / or sensitizer" is defined in the present invention because it is defined as a sensitizer, which promotes this photo-dimerization, although some compounds having both functions are difficult to be distinguished from each other.

Examples of the component (C) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2- Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy Hydroxy-2-methyl-propionyl) - < / RTI > 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane-1-one, 2-benzyl- 1- (4-morpholin-4-yl-phenyl) -butan-1-one , Adeka Optomer N-1414 (manufactured by ADEKA Corporation), phenylglyoxylic acid methyl ester, ethyl anthraquinone, and phenanthrenequinone;

Benzophenone, 4-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzo Phenanone, 4,4'-bis (diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzo Benzophenone-based compounds such as phenone 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 Acylphosphine oxide compounds such as 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;

Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl- -9H-thioxanthon-2-yl] oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;

Acridine-based compounds such as acridone and 10-butyl-2-chloroacridone;

(9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 Oxime] esters such as [yl] -1- (O-acetyloxime);

A dimer of 2- (o-chlorophenyl) -4,5-diphenylimidazole, a dimer of 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole, (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- methoxyphenyl) (P-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5- 2,4,5-triarylimidazole dimer such as diphenylimidazole 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 them, preferred are 1-hydroxycyclohexyl phenyl ketone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, 2,4-diethyl thioxanthone, isopropyl thioxanthone, and 1-chloro-4-propyl thioxanthone are preferable from the viewpoints of light reactivity, adhesive strength, heat resistance and coloring.

The mixing ratio of the component (C) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the solid content in the composition.

When the blending ratio of the component (C) is 0.1 parts by weight or more, the composition can be cured with an appropriate amount of ultraviolet light to improve the productivity. On the other hand, when the content is 10 parts by weight or less, the cured product is excellent in weatherability and transparency can do.

4. Component (D)

In the composition of the present invention, it is preferable that the thermosetting crosslinking agent of component (D) is blended because the coating before curing can provide excellent storage stability and peelability.

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 and dicyclopentanyl diisocyanate, A terminal isocyanate urethane prepolymer obtained by reacting a trimer of a bifunctional isocyanate compound, a bifunctional isocyanate compound and a polyol compound, a bifunctional isocyanate compound, a trimer of a bifunctional isocyanate compound, and a terminal isocyanate urethane prepolymer are reacted with a phenol, Blocked polyisocyanate compound block bodies and the like.

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.

Examples of the bisphenol A epoxy resin include Epikote 827 (trade name, the same applies hereinafter), Epikote 828, Epikote 1001 and Epikote 1004 manufactured by Japan Epoxy Resin Co., Ltd., and bisphenol F type epoxy resin Include Epicote 806, Epicote 4004P, and the like.

In addition to these, novolak type epoxy resins such as phenol novolac resin and cresol novolak type epoxy resin, glycidyl ether type epoxy resins such as polyalkylene polyol (neopentyl glycol, glycerol, etc.) polyglycidyl ether, Glycidylamine epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol and tetraglycidyl-m-xylenediamine, Epoxycyclohexylmethyl (3,4-epoxycyclohexane) glycidyl ester-based epoxy such as diglycidyl hexahydrophthalate and diglycidyl tetrahydrophthalate, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4- (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and cyclic aliphatic type such as triglycidylisocyanurate and glycidylglycidoxyalkylhydantoin. Epoxy resins and the like. Further, 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 can be mentioned.

Examples of the amino resin include a melamine resin, a guanamine resin, a urea resin, a melamine-urea co-condensation resin, and a melamine-phenol co-condensation resin.

Examples of the metal crosslinking agent include organic aluminum compounds such as aluminum trisacetylacetonate, aluminum tri-i-propionate, aluminum tri-s-butylate and ethylacetate aluminum di-i-propylate, Titanium tetra-2-ethylhexylate, triethanolamine titanium di-i-propylate, ammonium salts of titanium lactate, tetraoctyleneglycol titanate, polyalkyltitanate, polytitanium acylate (polymer of titanium tetrabutylate , And titanium oleate), organic zirconium compounds such as zirconium-s-butylate and zirconium diethoxy-t-butylate, other organic metals such as hafnium-t-butylate and antimony butylate Compounds, and the like.

The blending ratio of the component (D) is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the solid content of the composition.

By setting the mixing ratio of the component (D) within this range, the initial adhesive force of the adhesive layer of the composition is not excessively lowered, and the storage stability can be made excellent.

5. Other ingredients

The composition of the present invention contains the above components (A) to (D) as essential components, but other components may be incorporated depending on the purpose.

Examples of other preferable components include a silane coupling agent (hereinafter referred to as "component (E)"), an organic solvent (hereinafter referred to as "component (F)"), a deterioration inhibitor .

Hereinafter, the components (E) to (G) will be described.

The compounds exemplified as other components in the later stage may be used alone or in combination of two or more.

5-1. (E) Component

In the composition of the present invention, it is preferable to blend a silane coupling agent of component (E) in order to improve the adhesion with the base material and the resistance to moist heat and humidity.

The silane coupling agent is a compound having at least one alkoxysilyl group and at least one organic functional group in one molecule. The organic functional group is preferably a (meth) acryloyl group, an epoxy group, an amino group or a thiol group, more preferably a Meth) acryloyl group.

The compounding ratio of the silane coupling agent is preferably 0.5 part by weight to 5 parts by weight based on 100 parts by weight of the solid content of the composition from the viewpoints of improvement in wet heat resistance and outgassing.

5-2. (F) Component

The composition of the present invention preferably contains an organic solvent as the component (F) for the purpose of improving the coatability of the substrate. As the organic solvent, the organic solvent used in the production of the component (A) may be used as is or separately. Specific examples of the component (F) include organic solvents used in the production of the component (A).

The proportion of the component (F) may be appropriately set, but it is preferably 10 to 90% by weight, more preferably 30 to 80% by weight, based on 100% by weight of the composition.

5-3. (G) Component

The composition of the present invention is preferably blended with a deterioration inhibitor of the component (G) in order to improve the storage stability and prevent the deterioration (coloration, unfolding, etc.) of the time-lapse adhesive layer.

As the deterioration preventing agent, a polymerization inhibitor and / or an antioxidant, an ultraviolet absorber and a light stabilizer may be used.

Polymerization inhibitor and / or antioxidant

Examples of the polymerization inhibitor and / or the antioxidant include phenol compounds such as hydroquinone and hydroquinone monomethyl ether, hindered phenol compounds such as 2,6-di-tert-butyl-4-methylphenol and the like, Various phenolic antioxidants, hindered amine type, sulfur type secondary antioxidant, phosphorus secondary antioxidant, tetramethylpiperidine-1-oxyl (TEMPO), 1-oxyl-2,2,6,6-tetra Methyl-4-hydroxypiperidine (TEMPOL), aluminum-coupuron complex (Couperon Al), and the like.

● Ultraviolet absorber

Examples of ultraviolet absorbers include triazine-based ultraviolet absorbers such as TINUVIN 400, TINUVIN 405, TINUVIN 460 and TINUVIN 479 manufactured by BASF, and benzotriazole-based ultraviolet absorbers such as TINUVIN 900, TINUVIN 928 and TINUVIN 1130.

● 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.

Antioxidants and light stabilizers described in Osawa Zenshirowa et al., &Quot; Degradation and Stabilization of Polymeric Materials ", Shimushi Co., Ltd., p135 to 142 and p240 to 246 may be used as the deterioration preventing agent.

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

Other components other than the components (E) to (G) may be blended into the composition of the present invention, if necessary.

Specifically, a photo polymerization initiator, a catalyst, an inorganic material, a leveling agent, and the like can be given.

These components are described below.

● Photopolymerization initiator

To improve the reactivity, the composition of the present invention may be added as a photopolymerization initiator.

Examples of the photopolymerization initiator include aliphatic amines and aromatic amines such as diethylaminophenone, dimethylaminobenzoate and isoamyl dimethylaminobenzoate.

The blending ratio of the photopolymerization initiator 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 between the component (E) and the component (A), a known catalyst may be used if necessary. For example, when the reaction is carried out with a hydroxyl group or a carboxyl group and an isocyanate group, an organic tin compound such as dibutyltin dilaurate, an organic amine compound such as triethylamine, triethanolamine, dimethylbenzylamine, trioctylamine or 1,4-diazabicyclo [2.2. Tertiary amine compounds such as 1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5, acetic acid, capric acid , Organic acid salts such as acetylacetone metal salts such as cumene and naphthyl zinc, metal organic acid salts such as lead naphthenate and potassium acetate, and trialkylphosphine compounds such as triethylphosphine. have.

As the reaction between a carboxyl group and an epoxy group, a quaternary ammonium salt such as the above-mentioned tertiary amine compound and tetra-n-butylammonium bromide can be given.

● Inorganic materials

The inorganic material may be blended for the purpose of alleviating the deformation during curing of the composition or improving the adhesive strength.

Examples of the inorganic material include colloidal silica, silica, alumina, talc and clay.

The mixing ratio of the inorganic material is preferably 0 to 50% by weight, more preferably 0 to 30% by weight, and even more preferably 0 to 10% by weight, based on 100 parts by weight of the solid content of the composition.

● Leveling agent

Examples of the leveling agent include a silicon-based compound and a fluorine-based compound.

The blending ratio of the leveling agent is preferably 0.5% by weight or less based on 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 pressure-sensitive adhesive composition

The composition of the present invention essentially comprises the above components (A) to (D).

The composition of the present invention can be prepared by a conventional method and can be obtained by mixing the components (A) to (D), and optionally (E) to (G) and other components with stirring and mixing. If necessary, the mixing time can be shortened by heating.

In addition, the composition of the present invention needs to have a water absorption rate of 1% or less and a Tg (glass transition temperature) of 0 占 폚 or more after curing with active energy rays.

Thereby, the insulation reliability is excellent and can be preferably used as an insulating sheet.

The water absorption rate of the cured product is 1% or less, preferably 0.5% or less. When the water absorption rate exceeds 1%, water is absorbed during the wet heat treatment, and the volume resistivity is lowered, which results in a preferable volume resistivity of less than 1 x 10 < ¹¹ >

In the present invention, the water absorption rate means a value calculated by the following formula.

Absorption rate (%) = [(Wn - W1) / W1] x100

n: an integer greater than or equal to 2

W1: weight of the cured product after being heated at 50 캜 for 24 hours or more and then cooled to 23 캜 in a desiccator

W2: Weight when the cured product after the measurement of W1 is immersed in ion-exchanged water at 23 占 폚 for 24 hours and the cured product is taken out from the ion-exchanged water

W3: Weight when the cured product after the measurement of W2 is further immersed in ion-exchanged water at 23 DEG C for 24 hours and the cured product is taken out from the ion-exchanged water

Wn: Weight when the cured product after the measurement of Wn-1 is further immersed in ion-exchanged water at 23 ° C for 24 hours and the cured product is taken out from the ion-exchanged water

From the above equation, the water absorption rate is calculated. When the difference between the water absorption rates calculated from W2 and W3 is less than 0.1%, the measurement is terminated. When the difference in the water absorption is 0.1% or more, the same measurement is repeated until the water absorption becomes less than 0.1%.

The Tg of the cured product is 0 ° C or higher, preferably 5 to 50 ° C. If the Tg of the cured short of 0 ℃ is, the wet heat becomes low, the volume resistivity after the treatment is to be the desired volume resistivity of less than 1 × 10 ¹¹ Ω㎝.

The volume resistivity of the cured product is preferably 1 x 10 < ¹¹ > OMEGA cm or more in volume resistivity after wet heat treatment (60 DEG C, 90% RH, 500 hours). When the volume resistivity of the cured product after the wet heat treatment is less than 1 x 10 < ¹¹ > OMEGA cm, when the electronic circuit laminate is manufactured using the composition, the electronic device may malfunction.

In the present invention, the volume resistivity refers to a value measured in accordance with JIS K 6271-2008 (double ring electrode method).

7. Active energy ray-curable pressure-sensitive adhesive film or sheet

The composition of the present invention can be used in various ways depending on the purpose. More specifically, after the composition of the present invention is coated on the substrate subjected to the release treatment and dried to form a coating, (AE curable film) which is capable of being produced by cementing other release-treated substrates.

Hereinafter, the production method of the AE curable film and the production of the laminate using the same will be described. In the following, some explanation will be given based on Fig. 1 to Fig.

7-1. Method for producing AE-curable film

The AE curable film can be produced by a conventional method, for example, by applying the composition to a substrate.

Fig. 1 shows an example of a preferred method of producing an AE curable film composed of a substrate / dry film (hereinafter referred to as a "pressure-sensitive adhesive layer") / protective film subjected to a release treatment (hereinafter referred to as "release film").

In Fig. 1, (1) means base material and (3) means release film.

When the composition is a non-solvent type (Fig. 1: A1), the composition is applied to the substrate (Fig. 1 (1)). In the case where the composition contains an organic solvent or the like (Fig. 1: A2), the composition is coated on the substrate (Fig. 1: (1)) and then dried to evaporate the organic solvent or the like (Fig.

By these methods, an AE curable film is produced in which a point-adhesive layer is formed on a substrate (Fig. 1: (2)) (Fig.

In this AE curable film B1, it is preferable to laminate the releasing member 3 as a protective film to the point-adhesive layer if necessary (Fig. 1B2).

In the above, if the release material is also used as the base material 1, an AE curable film composed of release material / point-adhesive layer / release material can be produced.

The substrate may be a material for adhesion (hereinafter, referred to as an adherend), or may be a releasable material that is releasable from an adherend.

Specific examples of the material of the substrate include metals such as glass and aluminum, vapor-deposited films of metals and metal oxides, and silicon and polymers.

Examples of the polymer include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polyimides, polycarbonates, epoxy resins, polyurethanes, polylactic acid, polyethylene, polypropylene, cycloolefin polymers, acrylic resins, methacrylic resins, And examples thereof include polystyrene, methacryl / styrene, polyvinyl acetate, polyvinyl alcohol, triacetylcellulose, cellulose acetate butyrate, hydroxypropylcellulose, polyethersulfone, copolymer of the above polymer, liquid crystal polymer and fluororesin.

As the polymer, a sheet or a film is preferable.

In the case where the base material is coated, a member made of the above-mentioned material and the like are exemplified, and a member which is preferably used in an image display device is exemplified.

Examples of the release film include a PET film and an OPP film which have been subjected to release treatment such as silicone treatment, long-chain alkyl treatment, fluorine treatment and the like.

When a polymer is bonded, activation treatment may be performed on one or both surfaces in order to increase interlaminar adhesion. Examples of the surface activation treatment include a plasma treatment, a corona discharge treatment, a chemical solution treatment, a roughening treatment, an etching treatment and a flame treatment, and these may be used in combination.

The coating amount of the composition of the present invention may be appropriately selected depending on the intended use. It is preferable to coat the organic solvent or the like so that the film thickness after drying is 0.5 to 500 탆, more preferably 5 to 200 Mu m.

The coating method may be appropriately set according to the purpose, and a coating method may be applied by conventionally known coating methods such as a bar coater, a doctor blade, a knife coater, a comma coater, a reverse roll coater, a die coater, a gravure coater and a micro gravure coater .

When the composition contains an organic solvent or the like, it is dried after application and the organic solvent or the like is evaporated.

The drying conditions may be appropriately set according to the organic solvent to be used and the like, and a method of heating at a temperature of 40 to 120 캜.

After the production of the AE curable film, it is preferable to laminate the release film (FIG. 1: (3)) as a protective film on the pressure-sensitive adhesive layer as described above (FIG. 1: B2) Further, a release film may be laminated on the pressure-sensitive adhesive layer.

The obtained AE curable film can attain sufficient rigidity at the time of sticking 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 Curing Film

The AE curable film of the present invention is useful as an adhesive between homogeneous or heterogeneous materials such as fibers, composites, ceramics, glass, rubber, concrete, paper, metal, plastic and the like.

Concretely, there are manufacturing of building materials such as wall paper, laminated plywood, security glass, manufacture of glass window with UV cut filter for automobile, display of label adhesion, show window for beverage bottle, cans, bottle etc. Adhesion of an optical disc substrate, adhesion of a contactless IC card, adhesion of an IC chip, adhesion of an organic EL light-emitting cover glass, adhesion of a display member such as an organic EL display in which a projection television and a sealing structure are completely solid, Adhesion of a touch panel to a liquid crystal panel, adhesion of a touch panel such as a touch panel, a front window, and a touch panel, and various optical films (a brightness enhancement film, a prism sheet, a light diffusion sheet, a Fresnel lens, A lens, a polarizing film, a retardation film, a color filter, a light guide plate, an antiglare film, an antireflection film, a reflective sheet, a conductive film, Various materials or members such as a film, a viewing angle control film, a viewing angle compensating film, a heat ray reflective film, a gas barrier film, a thin film transistor, and the like, and a laminate used in an electric circuit are preferably used .

The AE curable film of the present invention can be suitably used, among the above, by the production of an electronic / electrical circuit laminate of an image display apparatus.

Examples of the active energy ray include ultraviolet rays, visible rays, X-rays and electron beams, and it is preferable to use ultraviolet rays and / or visible rays in order to use a low-cost apparatus. As the light source for curing by ultraviolet light and / or visible light, various ones can be used. Preferable light sources include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, UV non-electrode lamps, and LEDs emitting ultraviolet rays and / or visible rays.

The irradiation conditions such as the irradiation intensity in the active energy ray irradiation may be suitably set in accordance with the composition, substrate and purpose of use.

Fig. 2 shows an example in which an AE curable film laminated with a release film is used, and an active energy ray is irradiated from the base sheet side to be cured. In the AE-curable film B2 of Fig. 2, (1) means a base sheet, (2) a pressure-sensitive adhesive layer, and (3) a release film.

2, the release film is released from the AE curable film immediately before use (Fig. 2: 2-1), and the pressure-sensitive adhesive layer and the adherend 4 are brought into close contact with each other An active energy ray is irradiated (Fig. 2: 2-3) to produce a laminate (Fig. 2: 2-4).

Fig. 3 shows an example in which an AE-curable film laminated with two release sheets is used and two adherends are adhered to produce a laminate. In the AE curable film B3 of Fig. 3, (2) means a pressure-sensitive adhesive layer and (3) means a release material.

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) (Fig. 3: 3-4) after the adhesive layer and another adherend (Fig. 2: (4)) are adhered to each other (Fig. 3: 3-5) to produce a laminate (Fig. 3: 3-6).

As described above, the AE curable film of the present invention can be suitably used for producing an electronic / electrical circuit laminate of an image display device.

In this case, the image display unit constituting the image display device includes a transmissive or reflective liquid crystal display unit, a plasma display unit, an organic EL (OLED) unit, and an image display unit such as an electronic paper.

An additional functional layer (one layer or multiple layers), for example, a polarizing plate or the like can be formed on the display surface of the image display unit. Further, the touch panel may be present on the display surface of the image display unit.

The touch panel type image display apparatus can be used for various electronic apparatuses.

Specific examples of the electronic device include mobile phones, smart phones, portable information terminals, portable game machines, electronic books, car navigation systems, portable music players, watches, tablet computers, video cameras, video players, digital cameras, A Positioning System (GPS) device, and a personal computer (PC).

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. In the following description, " part " means weight part and "% " means weight%.

The meanings of the abbreviations used in the production examples are as follows.

The monomer (a)

THPI: Compound represented by the following formula (11)

[Chemical Formula 6]

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. Manufacturing Example

1) Production Example 1 [Preparation of component (A)

A flask equipped with a stirrer, a thermometer and a condenser was charged with the following compound at room temperature in the following amount, and dissolved uniformly while blowing nitrogen at a flow rate of 50 ml / min.

2.5 g of THPI, 2.5 g of HEA, 35.0 g of IBXA, 10.0 g of BA, 63 g of EtAc, 0.1 g of V-65

The mixture was heated while continuing the nitrogen injection, and after stirring under the same conditions and conditions as in Production Example 1, the following mixed solution was added dropwise and then stirred.

2.5 g of THPI, 2.5 g of HEA, 35.0 g of IBXA, 10.0 g of BA, 16 g of EtAc, 0.4 g of V-65

The nonvolatile fraction of the obtained copolymer solution was 56.0%, the Mw of the copolymer was 154,000, and the Mn was 26,000.

2) Production Example 2 [Production of component (A)

The following compounds were injected and dissolved uniformly in the same manner as in Preparation Example 1.

2.5 g of THPI, 2.5 g of HEA, 25.0 g of CHMA, 15.0 g of BA, 5.0 g of MMA, 63 g of EtAc, 0.1 g of V-65

The mixture was heated while continuing the nitrogen injection, and after stirring under the same conditions and conditions as in Production Example 1, the following mixed solution was added dropwise and then stirred.

2.5 g of THPI, 2.5 g of HEA, 25.0 g of CHMA, 15.0 g of BA, 5.0 g of MMA, 48 g of EtAc, 0.4 g of V-65

The nonvolatile fraction of the obtained copolymer solution was 47.5%, the Mw of the copolymer was 256,000, and the Mn was 64,000.

3) Production Example 3 [Preparation of component (A)

The following compounds were injected and dissolved uniformly in the same manner as in Preparation Example 1.

2.5 g of THPI, 2.5 g of HEA, 25.0 g of CHMA, 17.5 g of BA, 2.5 g of MMA, 63 g of EtAc, 0.1 g of V-65

The mixture was heated while continuing the nitrogen injection, and after stirring under the same conditions and conditions as in Production Example 1, the following mixed solution was added dropwise and then stirred.

2.5 g of THPI, 2.5 g of HEA, 25.0 g of CHMA, 17.5 g of BA, 2.5 g of MMA, 48 g of EtAc, 0.4 g of V-65

The nonvolatile fraction of the obtained copolymer solution was 47.3%, the Mw of the copolymer was 268,000, and the Mn was 54,000.

4) Production Example 4 [Production of component (A)

The following compounds were injected and dissolved uniformly in the same manner as in Preparation Example 1.

2.5 g of THPI, 2.5 g of HEA, 25.0 g of CHMA, 20.0 g of BA, 63 g of EtAc, 0.1 g of V-65

The mixture was heated while continuing the nitrogen injection, and after stirring under the same conditions and conditions as in Production Example 1, the following mixed solution was added dropwise and then stirred.

2.5 g of THPI, 2.5 g of HEA, 25.0 g of CHMA, 20.0 g of BA, 48 g of EtAc, 0.4 g of V-65

The nonvolatile fraction of the obtained copolymer solution was 46.2%, the Mw of the copolymer was 316,000, and the Mn was 83,000.

5) Preparation Example 5 [Preparation of component (A)

The following compounds were injected and dissolved uniformly in the same manner as in Preparation Example 1.

2.5 g of THPI, 2.5 g of HEA, 25.0 g of IBXA, 20.0 g of BA, 63 g of EtAc, 0.1 g of V-65

The mixture was heated while continuing the nitrogen injection, and after stirring under the same conditions and conditions as in Production Example 1, the following mixed solution was added dropwise and then stirred.

2.5 g of THPI, 2.5 g of HEA, 25.0 g of IBXA, 20.0 g of BA, 16 g of EtAc, 0.4 g of V-65

The non-volatile content of the obtained copolymer solution was 57.7%, the Mw of the copolymer was 183,000, and the Mn was 26,000.

6) Production Example 6 [Preparation of component (A)

The following compounds were injected and dissolved uniformly in the same manner as in Preparation Example 1.

2.5 g of THPI, 2.5 g of HEA, 20.0 g of CHMA, 21.0 g of BA, 4.0 g of EHA, 63 g of EtAc, 0.1 g of V-65

The mixture was heated while continuing the nitrogen injection, and after stirring under the same conditions and conditions as in Production Example 1, the following mixed solution was added dropwise and then stirred.

2.5 g of THPI, 2.5 g of HEA, 20.0 g of CHMA, 21.0 g of BA, 4.0 g of 2-EHA, 48 g of EtAc, 0.4 g of V-65

The nonvolatile fraction of the obtained copolymer solution was 46.5%, the Mw of the copolymer was 353,000, and the Mn was 81,000.

7) Preparation Example 7 [Preparation of component (A)

The following compounds were injected and dissolved uniformly in the same manner as in Preparation Example 1.

35.0 g of IBXA, 10.0 g of BA, 2.5 g of HEA, 63 g of EtAc, 0.1 g of V-65

The mixture was heated while continuing the nitrogen injection, and after stirring under the same conditions and conditions as in Production Example 1, the following mixed solution was added dropwise and then stirred.

35.0 g of IBXA, 10.0 g of BA, 2.5 g of HEA, 59 g of EtAc, 0.4 g of V-65

After cooling to room temperature, 0.1 g of BHT and 0.1 g of DBTDL were added while blowing a 5% oxygen / 95% nitrogen gas mixture at a flow rate of 50 ml / min and dissolved uniformly. Thereafter, the temperature was raised to 80 DEG C and maintained for 1 hour. Then, 5.0 g of AOI was injected in a batch, and the reaction was carried out at 80 DEG C for 2 hours to obtain an ethylenically unsaturated group-containing copolymer solution.

The nonvolatile matter content of the obtained copolymer solution was 46.4%, Mw 177,000 and Mn 30,000.

8) Preparation Example 8 [Preparation of component (A)

The following compounds were injected and dissolved uniformly in the same manner as in Preparation Example 1.

15.0 g of THPI, 10.0 g of HEA, 14.5 g of MMA, 10.5 g of BA, 63 g of EtAc, 0.10 g of V-65, 0.01 g of DM

Thereafter, the temperature was raised, and the mixture was stirred under the same conditions and conditions as in Production Example 1, followed by dropwise addition of the following mixture, followed by stirring.

15.0 g of THPI, 10.0 g of HEA, 14.5 g of MMA, 10.5 g of BA, 38 g of EtAc, 0.40 g of V-65, 0.05 g of DM

The nonvolatile fraction of the obtained copolymer solution was 49.8%, Mw of 223,000 and Mn of 15,300.

9) Preparation Example 9 [Preparation of component (A)

The following compounds were injected and dissolved uniformly in the same manner as in Preparation Example 1.

6.0 g of THPI, 12.0 g of HEA, 18.0 g of EHMA, 24.0 g of BA, 76.0 g of BuAc, 0.12 g of AMBM

The mixture was heated while continuing the nitrogen injection, and after stirring under the same conditions and conditions as in Production Example 1, the following mixed solution was added dropwise and then stirred.

6.0 g of THPI, 12.0 g of HEA, 18.0 g of EHMA, 24.0 g of BA, 76.0 g of BuAc, 0.12 g of AMBM

The nonvolatile fraction of the obtained copolymer solution was 42.0%, Mw was 294,000, and Mn was 20,000.

10) Preparation Example 10 [Preparation of component (A)

The following compounds were injected and dissolved uniformly in the same manner as in Preparation Example 1.

0.5 g of THPI, 3.75 g of HEA, 10.0 g of CHMA, 15.0 g of BA, 20.75 g of EHA, 63 g of EtAc, 0.1 g of V-

The mixture was heated while continuing the nitrogen injection, and after stirring under the same conditions and conditions as in Production Example 1, the following mixed solution was added dropwise and then stirred.

0.5 g of THPI, 3.75 g of HEA, 10.0 g of CHMA, 15.0 g of BA, 20.75 g of EHA, 48 g of EtAc, 0.4 g of V-65

The non-volatile content of the obtained copolymer solution was 47.4%, Mw was 337,000, and Mn was 47,000.

The monomers and other components used for the polymer (A) obtained in Production Examples 1 to 10 are summarized in Table 1. Further, in Table 1, the number of the monomers (a), (b), and (c) used is indicated as 100 in total.

The non-volatile matter and the molecular weight of these polymers were measured by 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 占 폚 for 1 hour, and the nonvolatile content was calculated from the weight of the sample before and after drying.

(2) Molecular weight

The molecular weight in terms of polystyrene was measured using GPC (Hsokko-8120 manufactured by Toso Co., Ltd., column: TSKgel-GMHxl x 2, eluent: THF 1 ml / min, detector: RI). Mw is the weight average molecular weight, and Mn is the number average molecular weight.

2. Examples 1 to 9 and Comparative Examples 1 to 4

1) Preparation of composition

The compounds shown in the following Table 2 were put into a container made of stainless steel at the ratios shown in Table 2 and stirred at room temperature with a magnetic stirrer until homogeneous to obtain an active energy ray curable pressure-sensitive adhesive composition.

2) Preparation of AE curable film

The resulting composition was applied to an adhesive film "Diafoyle MRV" (siliconized polyethylene terephthalate film, thickness 75 μm), manufactured by Mitsubishi Plastics Co., Ltd., having a width of 300 mm and a length of 300 mm by means of an applicator so as to have a film thickness of 50 μm after drying And dried in a hot air drier at 90 占 폚 for 10 minutes. Thereafter, a release film "Dia Foil MRQ" (silicone-treated polyethylene terephthalate film, thickness 38 μm) manufactured by Mitsubishi Resin 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 the cured product

The cured product of the AE-curable film was produced by irradiating ultraviolet ray (365 nm light with an illuminance of 200 mW / cm 2, cumulative light quantity 2 J / cm 2) by a high-pressure mercury lamp beyond the release film.

The Tg of the cured product obtained after peeling off the release film was measured using DSC-6220 manufactured by Seiko Instruments Inc. under the following conditions. The results are shown in Table 3.

· Measurement conditions: temperature rise rate 10 ° C / minute

(2) Water absorption rate of the cured product

The cured product of the AE-curable film was produced by irradiating ultraviolet ray (365 nm light with an illuminance of 200 mW / cm 2, cumulative light quantity 2 J / cm 2) by a high-pressure mercury lamp beyond the release film.

In order to adjust the state of the cured film, the cured product from which the release film was peeled was subjected to heat treatment at 50 占 폚 for at least 24 hours. Thereafter, it was cooled down to 23 DEG C in a desiccator, and the weight (W1) of the cured product at that time was measured.

The cured product was immersed in ion-exchanged water at 23 DEG C for 24 hours. Thereafter, the cured film was taken out from the ion-exchanged water. Water on the surface of the film was removed with Ben Cotton and the weight (W2) of the cured film was measured.

The cured product was further immersed in ion-exchanged water for 24 hours, and the weight (W3) of the cured film was measured similarly to the measurement of W2.

The absorption rate is calculated from the following formula. When the difference in the absorption rate calculated from W2 or W3 is less than 0.1%, the measurement is terminated. When the difference in the water absorption rate became 0.1 or more, the operation of repeatedly immersing in ion-exchanged water for 24 hours and measuring the weight was repeated until the difference became less than 0.1.

Absorption rate (%) = [(Wn - W1) / W1] x100

n: an integer greater than or equal to 2

(3) Volume resistivity of the cured product

The AE curable film to be evaluated was cut into a size of 100 mm x 100 mm, and the release film on one side of the AE curable film was peeled off and transferred to an aluminum plate having a thickness of 0.1 mm. Thereafter, a cured film was produced from the side of the AE curable film by irradiating ultraviolet ray (365 nm light intensity of 200 mW / cm 2, cumulative light quantity of 2 J / cm 2) with a high-pressure mercury lamp beyond the release film.

Thereafter, the release film was peeled off, and the state was adjusted at room temperature for 12 hours or more. Thereafter, the state at 25 占 폚 after irradiation with ultraviolet ray and the state at 60 占 폚, 90%, 500 The volume resistivity in the time-treated state was measured.

The higher the volume resistivity, the higher the insulating property.

(4) Haze of cured product

The haze of the cured product was measured to evaluate the transparency of the cured product.

Using an AE-curable film to be evaluated, a slide glass and an easy-to-adhere PET film (A4300, manufactured by Toyobo Co., Ltd.) were bonded.

A cured product was prepared by irradiating an ultraviolet ray (365 nm light with an illuminance of 200 mW / cm 2, and a cumulative light amount of 2 J / cm 2) with a high-pressure mercury lamp beyond the A4300 side.

After one day from the ultraviolet curing, the haze was measured using a turbidimeter (NDH2000 manufactured by Nippon Seimei Kogyo Co., Ltd.).

The abbreviations in Table 2 indicate the following.

(F) Component

EtAc: ethyl acetate

BuAc: butyl acetate

Component (B)

DCPA: Dimethylol-tricyclodecane diacrylate, Light acrylate DCPA (manufactured by Kyowa Chemical Industry Co., Ltd.)

M315: ethylene oxide-modified di- and triacrylate of isocyanuric acid, Aronix M-315 manufactured by TOA Corporation

M450: pentaerythritol tri and tetraacrylate, Aronix M-450 manufactured by TOA Corporation

M313: ethylene oxide-modified di- and triacrylate of isocyanuric acid, Aronix M-313 manufactured by TOA Corporation

M1200: Polyester-based urethane acrylate, Aronix M-1200 manufactured by TOA Corporation (Synthesis), viscosity at 25 ° C = 2,000,000 mPa · s

M140: N-acryloyloxyethylhexahydrophthalimide, ARONIX M-140 manufactured by TOA Corporation

(C) Component

TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, Chiba Specialty Chemicals, DAROCUR TPO

PBZ: 4-phenylbenzophenone

Irg 184: 1-Hydroxy-cyclohexyl-phenyl-ketone, IRGACURE 184 from BASF

(D) Component

P301: Tertiary isocyanate compound, "Dyuranate P301-75E" manufactured by Asahi Chemical Industry Co., Ltd.

· CO-L: trifunctional isocyanate compound, manufactured by Nippon Polyurethane Co., Ltd. Colonate L

TPA100: trifunctional isocyanate compound, "Dyuranate TPA-100" manufactured by Asahi Chemical Industry Co., Ltd.

(E) Component

KBM: 3-acryloxypropyltrimethoxysilane, "KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd.

(G) Component

T622: HALS deterioration inhibitor, "Tinuvin 622SF" manufactured by BASF Japan Ltd.

135A: Phosphite antioxidant, Adekastab 135A manufactured by ADEKA Co., Ltd.

AO80: phenolic antioxidant, Adekastab AO-80 manufactured by ADEKA Co., Ltd.

3010: Phosphite antioxidant, Adekastab 3010 manufactured by ADEKA Co., Ltd.

etc

DBTDL: di-n-butyltin dilaurate

· FTR8120: petroleum resin, manufactured by Mitsui Chemicals, Inc.

In the column of "(A) + (F)", the upper part indicates the mixing ratio as the copolymer solution and the lower part indicates the mixing ratio of each component, and "high" means the solid content.

The compositions of Examples 1 to 9 were excellent in electrical insulation with a volume resistivity of 1 x 10 < ¹¹ > OMEGA .cm or more after the moisture-heat resistance test of the cured product. In addition, haze was small and transparency was excellent.

Further, the compositions of Examples 1 to 9 were separately coated with glass and various plastic films and then subjected to an adhesion test to cure them by irradiating ultraviolet rays, all of which were excellent in adhesion.

On the contrary, the composition of Comparative Example 1 in which the water absorption rate of the cured product is higher than the lower limit of the present invention is 2.1%, the volume resistivity at 25 캜 is high, but the volume resistivity after the heat and humidity test is significantly lower than 1 × 10 ¹¹ Ω · cm , Insufficient insulating property.

The compositions of Comparative Examples 2, 3, and 4 were such that the Tg of the cured product was -18 캜 and -26 캜 and -5 캜, respectively, and the volume resistivity after the heat and humidity test was less than 1 횞 10 ¹¹ Ω · cm, It was insufficient.

The active energy ray-curable pressure-sensitive adhesive composition of the present invention can be suitably used for producing an AE-curable pressure-sensitive adhesive film. In addition, the AE-curing type pressure-sensitive adhesive film can be suitably used in the production of a laminate to which various adherends are adhered, and the cured product of the composition of the present invention is excellent in insulating properties, And can be suitably used for the production of laminated plates.

Claims (23)

A composition comprising the following components (A) to (D)
Wherein the water absorption rate of the cured product after irradiation with active energy rays is 1% or less and the glass transition temperature is 0 占 폚 or more.
(A) Component: Polymer
(B): a compound having at least one ethylenic unsaturated group in the molecule
Component (C): a photopolymerization initiator and / or a sensitizer
(D) Component: Thermosetting crosslinking agent The method according to claim 1,
Wherein the volume resistivity after the wet heat treatment (60 DEG C, 90% RH, 500 hours) of the cured product after irradiation of the active energy ray is not less than 1 x 10 < ¹¹ > The method according to claim 1,
(A) is a polymer having a weight average molecular weight of 10,000 to 2,000,000. The method according to claim 1,
(A) is a polymer having a glass transition temperature of -8 to 50 占 폚. The method according to claim 1,
Wherein the component (A) is a polymer having an ethylenically unsaturated group. 6. The method of claim 5,
Wherein the component (A) is a polymer (A1-1) having a maleimide group represented by the following general formula (1) as an ethylenic unsaturated group.
[Chemical Formula 1]

[Wherein 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 together form a 5-membered ring or 6-atom Represents a hydrocarbon group which forms a ring.] The method according to claim 6,
Wherein the component (A) is a polymer (A1-1) obtained by copolymerizing the following monomers (a) to (c) in the following proportions:
Monomer (a): a compound having a maleimide group represented by the general formula (1) and an ethylenic unsaturated group other than the maleimide group; 0.1 to 50 wt%
Monomer (b): a compound having a hydroxyl group and / or a carboxyl group and an ethylenic unsaturated group; 0.1 to 30 wt%
Monomer (c): a compound other than the monomers (a) and (b) having an ethylenically unsaturated group; 20 to 99.8 wt% 8. The method of claim 7,
Wherein the component (A) is a polymer (A1-1) obtained by copolymerizing the monomers (a) to (c) in the following proportions:
Monomer (a): 0.1 to 10 wt%
Monomer (b): 0.1 to 10 wt%
Monomer (c): 80 to 99.8 wt% 8. The method of claim 7,
An active energy ray curable pressure-sensitive adhesive composition wherein the monomer (a) is a compound represented by the following general formula (2).
(2)

[Wherein, in formula (2), R ¹ and R ² have the same meanings as defined 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.] 8. The method of claim 7,
The active energy ray-curable pressure-sensitive adhesive composition wherein the monomer (c) is a compound having an aromatic ring and / or a cycloaliphatic skeleton and an ethylenically unsaturated group. 6. The method of claim 5,
Wherein the component (A) is a polymer (A1-2) having a (meth) acryloyl group as an ethylenic unsaturated group. 12. The method of claim 11,
Wherein the component (A) is a copolymer comprising 100% by weight of a copolymer of a functional group containing 70 to 99.9% by weight of the following monomer (c) and 0.1 to 30% by weight of the following monomer (d)
Is a polymer (A1-2) obtained by reacting 0.1 to 20 parts by weight of the following monomer (d ').
Monomer (c): a monomer other than the monomer (a) having an ethylenic unsaturated group and the monomer (b)
Monomer (d): a compound having a functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, an epoxy group and an acid anhydride group and an ethylenically unsaturated group
Monomer (d '): a compound having a functional group reacting with the functional group of the monomer (d) and a (meth) acryloyl group 13. The method of claim 12,
Wherein the component (A) is a copolymer of 100% by weight of a functional group-containing copolymer obtained by copolymerizing 70 to 99.9% by weight of the monomer (c) and 0.1 to 10% by weight of the monomer (d)
Is a polymer (A1-2) obtained by reacting 0.1 to 10 parts by weight of the monomer (d '). 13. The method of claim 12,
Wherein the component (A) is a copolymer of a functional group-containing copolymer obtained by copolymerizing the monomer (a) in an amount of 0.1 to 50% by weight, the monomer (c) in an amount of 20 to 99.8% by weight and the monomer (d) Is 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 the polymer (A1'). 13. The method of claim 12,
The active energy ray-curable pressure-sensitive adhesive composition wherein the monomer (c) is a compound having an aromatic ring and / or a cycloaliphatic skeleton and an ethylenically unsaturated group. The method according to claim 1,
(B) is a compound having an aromatic ring and / or an alicyclic skeleton and at least one ethylenic unsaturated group in the molecule. The method according to claim 1,
(B) is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the component (A). The method according to claim 1,
With respect to 100 parts by weight of the solid content of the composition,
(C) in an amount of 0.1 to 10 parts by weight
(D) in an amount of 0.01 to 3 parts by weight
Wherein the active energy ray-curable pressure-sensitive adhesive composition comprises: The method according to claim 1,
Further comprising (E) an organic solvent. The method according to claim 1,
Further comprising (F) a silane coupling agent. The method according to claim 1,
Further comprising (G) a deterioration inhibitor. An active energy ray-curable pressure-sensitive adhesive film or sheet having an active energy ray-curable pressure-sensitive adhesive layer obtained from the composition according to any one of claims 1 to 21 and a substrate subjected to the release treatment in this order. A process for peeling off one of the release-treated base materials of the active energy ray-curable pressure-sensitive adhesive film or sheet according to claim 22, adhering the exposed surface of the composition and the adherend, peeling off the other release- A step of adhering an adherend to the other side of the composition, and a step of irradiating an active energy ray from the side of any adherend.

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