JP2003034708A - Resin composition and its cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition whose cured material can be suitably used for a sealing material having excellence in adhesion and moisture resistance for a liquid crystal panel and an organic EL panel, and its cured material. SOLUTION: The resin composition is characterized by comprising a product (A) obtained by reacting a monocarboxylic acid (b) containing a maleimide group with an epoxy resin (a) at a ratio of 0.05 to 0.9 equivalent carboxy group in (b) to 1 equivalent epoxy group in (a), and a polymerizable compound (B) other than the component (A).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various coating materials, surface treatment materials, sealants, optical waveguide materials, laminated plates, adhesives, pressure sensitive adhesives, printing inks, sealing agents, color resists, liquid resist inks, etc. The present invention relates to a resin composition and a cured product thereof which can be used as a sealing material for liquid crystal display panels, organic EL panel display panels, solar cells and the like.

[0002]

2. Description of the Related Art In a liquid crystal cell, a liquid crystal is usually injected into a gap between a pair of electrode substrates surrounded by a sealing material layer from a gap in the sealing material layer, and then the injection hole is sealed with a sealing material. It is manufactured by sealing treatment.

By the way, conventionally, as the sealing material, an organic material, particularly a two-pack type epoxy resin composition and a one-pack type epoxy resin composition are mainly used.

However, the two-pack type epoxy resin composition has a problem that the pot life is short and the viscosity is easily increased, so that it has to be adjusted for each lot and the production efficiency is poor. On the other hand, the one-pack type epoxy resin composition is 150 to 200
Since it is necessary to heat at a high temperature of ℃ for several tens of minutes, the production efficiency is still insufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and has a characteristic that it is cured by ultraviolet irradiation in a short time and at room temperature, and has an adhesive property and a moisture resistance. Another object of the present invention is to provide a resin composition which is useful for a sealing material which forms a cured layer excellent in stain resistance and flexibility, and a cured product thereof.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that 1 equivalent of the epoxy group in the epoxy resin (a) is equivalent to 0.05 of the carboxyl group in the maleimide group-containing monocarboxylic acid (b). It has been found that the above object can be achieved by using as a main component a product (A) obtained by reacting ˜0.9 equivalents and a polymerizable compound (B) other than the component (A), and arrived at the present invention. .

That is, according to the present invention, (1) 1 to 1 equivalent of the epoxy group in the epoxy resin (a) is added to the carboxyl group in the maleimide group-containing monocarboxylic acid (b) in an amount of 0.05 to
A resin composition comprising a product (A) obtained by reacting 0.9 equivalents and a polymerizable compound (B) other than the component (A), and (2) polymerizability other than the component (A). The compound (B) is one or more selected from the group consisting of compounds having a (meth) acryloyloxy group, the resin composition according to (1), (3) containing a thermoset (C) (1) or (2) The resin composition, (4) The thermosetting component (C) is an epoxy resin, (3) The resin composition, (5),
A cured product of the resin composition according to any one of (1) to (4).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention comprises 0.05 equivalent of the carboxyl group in the maleimide group-containing monocarboxylic acid (b) to 1 equivalent of the epoxy group in the epoxy resin (a).
It is a mixture of a product (A) obtained by reacting ˜0.9 equivalents and a polymerizable compound (B) other than the component (A).

In the present invention, a product obtained by reacting 1 equivalent of the epoxy groups in the epoxy resin (a) with 0.05 to 0.9 equivalents of the carboxyl groups in the maleimide group-containing monocarboxylic acid (b) ( Use A). As a specific example of the component (A), it can be obtained, for example, by reacting an epoxy resin (a-1) having two or more epoxy groups in one molecule with a maleimide group-containing monocarboxylic acid (b). Specific examples of the epoxy resin (a-1) having two or more epoxy groups in one molecule include bisphenol A.
Type epoxy resin, bisphenol F type epoxy resin biphenyl diglycidyl ether, bi (tetramethylphenyl) diglycidyl ether,

[0010]

[Chemical 1]

[0011]

[Chemical 2]

Phenol / novolak type epoxy resin,
Aromatic group-containing epoxy resin (a-1-1) such as cresol / novolak type epoxy resin, trisphenolmethane type epoxy resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-bis (2 ', 3'-epoxypropyl) perfluoro-n-butane,

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

[Chemical 5]

Aliphatic epoxy resin (a-1-2) such as silicone modified epoxy resin can be used.

Specific examples of the maleimide group-containing monocarboxylic acid (b) include, firstly,

[0018]

[Chemical 6]

As shown by the formula (1), a known technique [for example, D.
H. Reich (D.H.Rich) and others "Journal
Of Medical Chemistry (Journal o
f Medical Chemistry) "18th
Vol. 1004-1010 (1975)], secondly compound (b-1), secondly hydroxyl group-containing maleimide compound (c) and compound having one acid anhydride group in the molecule. Half ester compound with (d) (b-
2) etc. can be mentioned.

Examples of the primary aminocarboxylic acid include asparagine, alanine, β-alanine, arginine, isoleucine, glycine, glutamine, tryptophan, trionine, valine, phenylalanine, homophenylalanine, α-methylphenylalanine, lysine, leucine. , Cycloleucine, 3-aminopropionic acid, α-aminobutyric acid, 4-aminobutyric acid, aminovaleric acid,
6-aminocaproic acid, 7-aminoheptanoic acid, 2-aminocaprylic acid, 3-aminocaprylic acid, 6-aminocaprylic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 2-aminocapric acid, 9-aminocaprin Acid, 1
5-aminopentadecanoic acid, 2-aminopalmitic acid,
Examples thereof include 16-aminopalmitic acid, but are not limited thereto.

Examples of the hydroxyl group-containing maleimide compound (c) include those represented by the reaction formula

[0022]

[Chemical 7]

As shown by the formula, from maleimide and formaldehyde, or the reaction formula

[0024]

[Chemical 8]

As shown by the formula (1), it can be synthesized from maleic anhydride and a primary amino alcohol by using a known technique (see, for example, US Pat. No. 2,526,517, JP-A-2-268155).

Examples of the primary amino alcohols include 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol and 2-amino-.
2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-3-phenyl-1
-Propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-3-methyl-1-
Butanol, 2-amino-4-methylthio-1-butanol, 2-amino-1-pentanol, (1-aminocyclopentane) methanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 2 Examples thereof include, but are not limited to,-(2-aminoethoxy) ethanol and the like.

Specific examples of the compound (d) having one acid anhydride group in the molecule include maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride and methyl-hexahydro. Examples thereof include phthalic anhydride.

The above half ester compound (b-2)
By reacting 1 chemical equivalent of the hydroxyl group in the maleimide compound (c) containing a hydroxyl group with about 1 chemical equivalent of the anhydride group in the compound (d) having one acid anhydride group in the molecule. Obtainable. The reaction temperature is 60 to 10
0 ° C. is preferable, and the reaction time is preferably 1 to 10 hours.
If necessary, an organic solvent may be used during the reaction.

The above reaction of the epoxy resin (a) with the maleimide group-containing monocarboxylic acid (b) is carried out without solvent or with solvents such as acetone, ethylmethylketone, ketones such as cyclohexanone; benzene, toluene,
Aromatic hydrocarbons such as xylene and tetramethylbenzene; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and triethylene glycol dimethyl ether; ethyl acetate, butyl acetate, methyl Esters such as cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate; cyclic esters such as γ-butyrolactone; petroleum ether, petroleum naphtha Petroleum solvents such as solvent naphtha can be preferably used.

During the reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst used is 0.1 to 10% by weight based on the reactant. Specific examples of the catalyst are
Examples thereof include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octanoate and zirconium octanoate.

During the reaction, a polymerization inhibitor may be used for the purpose of preventing polymerization. Specific examples of the polymerization inhibitor include P-
Methoxyphenol, hydroquinone, methylhydroquinone, phenothiazine and the like can be mentioned. The amount of the polymerization inhibitor used is 0.05 to 3% by weight based on the reaction product.

The reaction ratio between the components (a) and (b) is
It is preferable to react 0.05 to 0.9 equivalents of the carboxylic acid in the component (b), and particularly preferably 0.2 to 0.7 equivalents, to 1 equivalent of the epoxy group in the component (a). Let The reaction temperature is 60 to 110 ° C., preferably 80.
~ 100 ° C. At the time of the reaction or after the reaction, the above-mentioned solvents and the polymerizable compound (B) other than the component (A) described below may be added.

In the present invention, a polymerizable compound (B) other than the component (A) is used. Specific examples of the component (B) include
A compound having a (meth) acryloyloxy group (B-
1), a compound (B-2) having a vinyl ether group, N
-A compound (B-3) having a vinyl group, a maleimide compound (B-4) other than the component (A), a (meth) acrylamide compound (B-5), an unsaturated polyester (B-6) and the like can be mentioned.

(Meth) usable in the resin composition of the present invention
When a compound having an acryloyloxy group is roughly classified,
(Poly) ester (meth) acrylate (B-1-
1); Urethane (meth) acrylate (B-1-2);
Epoxy (meth) acrylate (B-1-3); (Poly) ether (meth) acrylate (B-1-4); Alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-5); Aromatic ring Having (meth) acrylate (B-1-6); having an alicyclic structure (meth)
Examples thereof include acrylate (B-1-7), but are not limited thereto.

(Poly) usable in the resin composition of the present invention
The ester (meth) acrylate (B-1-1) is a generic term for (meth) acrylate having one or more ester bonds in the main chain and is a urethane (meth) acrylate (B-.
1-2) is a general term for (meth) acrylates having one or more urethane bonds in the main chain, and is epoxy (meth)
Acrylate (B-1-3) is a general term for (meth) acrylate obtained by reacting a monofunctional or higher functional epoxy compound with (meth) acrylic acid, and is a (poly) ether (meth) acrylate (B-1- 4) is a general term for (meth) acrylate having at least one ether bond in the main chain, and alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-5) is a straight-chain alkyl having a main chain. , Branched alkyl, and (meth) acrylate (B-1-6) having an aromatic ring as a general term for (meth) acrylate which may have a halogen atom and / or a hydroxyl group at a straight chain or at a terminal are the main chains. Or, as a general term for (meth) acrylates having an aromatic ring in the side chain, (meth) acrylate (B-1-7) having an alicyclic structure means that the main chain or side chain has an acid as a structural unit. As a general term that also contain an atom or a nitrogen atom having a good alicyclic structure-containing (meth) acrylate is used, respectively.

(Poly) usable in the resin composition of the present invention
Examples of the ester (meth) acrylate (B-1-1) include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth ) Acrylate, monofunctional (poly) ester (meth) acrylates such as caprolactone modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, caprolactone modified hydroxypivalic acid ester neopentyl glycol di ( (Meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; 1 mol or more of ε- per 1 mol of trimethylolpropane or glycerin
Mono-, di- or tri (meth) acrylate of triol obtained by adding a cyclic lactone compound such as caprolactone, γ-butyrolactone, δ-valerolactone;

1 mol or more of ε-caprolactone per 1 mol of pentaerythritol or ditrimethylolpropane,
Mono-, di-, tri- or tetra (meth) acrylate of triol obtained by adding a cyclic lactone compound such as γ-butyrolactone and δ-valerolactone; 1 mol or more of ε-caprolactone and γ-butyrolactone per 1 mol of dipentaerythritol , A monool of triol obtained by adding a cyclic lactone compound such as δ-valerolactone, or a mono (meth) acrylate of polyhydric alcohol such as triol, tetraol, pentaol or hexaol of poly (meth) acrylate, or poly (Meth) acrylate;

(Poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5
-Diol components such as pentanediol and hexanediol and maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium (Meth) acrylate of polyester polyol which is a reaction product of polybasic acids such as sulfoisophthalic acid and their anhydrides; the diol component and polybasic acids and their anhydrides and ε-caprolactone, γ-
Examples thereof include, but are not limited to, polyfunctional (poly) ester (meth) acrylates such as (meth) acrylate of a cyclic lactone-modified polyester diol composed of butyrolactone, δ-valerolactone and the like.

The urethane (meth) acrylate (B-1-2) usable in the resin composition of the present invention includes a hydroxy compound (B-1-2) having at least one (meth) acryloyloxy group and an isocyanate. Compound (B
It is a general term for (meth) acrylates obtained by the reaction with (1-2).

Examples of the hydroxy compound (B-1-2) having at least one (meth) acryloyloxy group are, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxy. Butyl (meth) acrylate, 4-
Hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy-
Examples thereof include (meth) acrylate compounds having various hydroxyl groups such as 3-phenoxypropyl (meth) acrylate, and ring-opening reaction products of the above-mentioned (meth) acrylate compounds having hydroxyl groups with ε-caprolactone.

Isocyanate compound (B-1-2)
As, for example, p-phenylene diisocyanate,
m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-
Aromatic diisocyanates such as tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, hydrogenated xylene diisocyanate, Aliphatic or alicyclic diisocyanates such as norbornene diisocyanate and lysine diisocyanate;
Examples include polyisocyanates such as burettes of one or more types of isocyanate monomers or isocyanates obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by urethanization reaction between the above isocyanate compounds and the above polyol compounds.

The epoxy (meth) acrylate (B-1-3) usable in the resin composition of the present invention is obtained by reacting an epoxy resin having a monofunctional or higher epoxy group with (meth) acrylic acid. It is a general term for the (meth) acrylates obtained. Examples of the epoxy resin that is a raw material for the epoxy (meth) acrylate include the above-mentioned compound (a) having an epoxy group.

(Poly) that can be used in the resin composition of the present invention
Examples of the ether (meth) acrylate (B-1-4) include butoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, epichlorohydrin-modified butyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate. , 2-
Ethoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth)
Monofunctional (poly) ether (meth) acrylates such as acrylate and nonylphenoxy polyethylene glycol (meth) acrylate;

Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; ethylene oxide and Propylene oxide copolymers, propylene glycol-tetrahydrofuran copolymers, polyisoprene glycols, hydrogenated polyisoprene glycols, polybutadiene glycols, hydrogenated polybutadiene glycols and other polyhydric hydroxyl compounds such as hydrocarbon-based polyols (meth) Polyfunctional (meth) acrylates derived from acrylic acid; neopentyl glycol 1
Di (meth) acrylate of diol in which 1 mole or more of a cyclic ether such as ethylene oxide, propylene oxide, butylene oxide is added to a mole;

Di (meth) acrylates of modified alkylene oxides of bisphenols such as bisphenol A, bisphenol F and bisphenol S; hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenols such as alkylene oxides Modified di (meth) acrylate; mono-, di- or tri (meth) acrylate of triol obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide to 1 mol of trimethylolpropane or glycerin. ;

Mono-, di-, tri- or tetra (meth) acrylate of triol obtained by adding 1 mole or more of a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide to 1 mole of pentaerythritolyl or ditrimethylolpropane; dipenta Hexaol 3- to 6-functional (meth) in which 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide is added to 1 mol of erythritol.
Examples thereof include polyfunctional (poly) ether (meth) acrylates such as acrylate.

Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-5) usable in the resin composition of the present invention include octyl (meth) acrylate, isooctyl (meth) acrylate and decyl ( Monofunctional (meth) acrylates such as (meth) acrylate and dodecyl (meth) acrylate;

Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, 1,
Hydrocarbon diol di (meth) acrylates of 10-decanediol di (meth) acrylate;

Trimethylolpropane mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate
Acrylate (hereinafter, “poly” is used as a general term for polyfunctional such as di, tri, tetra, etc.), mono (meth) acrylate or poly (meth) acrylate of glycerin, mono- or poly (meth) acrylate of pentaerythritol, ditri. Methylol propane mono or poly (meta)
Acrylate, triol such as dipentaerythritol mono- or poly (meth) acrylate, tetraol,
Mono- or poly (meth) acrylates of polyhydric alcohols such as hexaol;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4
-Hydroxyl group-containing (meth) acrylates such as hydroxybutyl (meth) acrylate; and the like.

The aromatic ring-containing (meth) acrylate (B-1-6) usable in the resin composition of the present invention includes:
For example, monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Examples thereof include, but are not limited to, di (meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate.

Examples of the (meth) acrylate (B-1-7) having an alicyclic structure which can be used in the resin composition of the present invention include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate and isobornyl (meth). Monofunctional (meth) acrylates having an alicyclic structure such as acrylate and dicyclopentenyl (meth) acrylate; Di (meth) acrylate of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F; tricyclodecanedi Examples include polyfunctional (meth) acrylates having a cyclic structure such as methylol di (meth) acrylate; alicyclic (meth) acrylates having an oxygen atom in the structure such as tetrafurfuryl (meth) acrylate, and the like. However, it is not limited to this.

The compound (B-) having a (meth) acryloyloxy group that can be used in the resin composition of the present invention.
As 1), in addition to the above compounds, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate or a reaction product of a glycidyl (meth) acrylate polymer and (meth) acrylic acid (Meth) acrylic polymer (meth) acrylate; (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; isocyanuric (meth) such as tris ((meth) acryloxyethyl) isocyanurate
Acrylate; (meth) acrylate having a polysiloxane skeleton; polybutadiene (meth) acrylate; melamine (meth) acrylate and the like can also be used.

Next, the compound (B-2) having a vinyl ether group which can be used in the resin composition of the present invention is roughly classified into an alkyl vinyl ether (B- which may have a halogen atom or a hydroxyl group at the other end). 2-1), cycloalkyl vinyl ether (B-2-2) in which the other end may be substituted with a halogen atom or a hydroxyl group, alkyl in which the vinyl ether group is bonded to an alkylene group and may further have a substituent A group having a structure in which at least one group selected from the group consisting of a group, a cycloalkyl group and an aromatic group is bonded to at least one group selected from the group consisting of an ether bond, a urethane bond and an ester bond. , Di and polyvinyl ether (B-2-
3), etc., but not limited to these.

The above-mentioned alkyl vinyl ether (B-2-
As 1), for example, hydroxymethyl vinyl ether, chloromethyl vinyl ether, hydroxyethyl vinyl ether, 2-chloroethyl vinyl ether, 1,
4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 4-hydroxybutyl vinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether and the like can be mentioned, but not limited thereto.

Cycloalkyl vinyl ether (B
Examples of -2-2) include, but are not limited to, 2-hydroxycyclopropyl vinyl ether, cyclohexyl vinyl ether, cyclohexane dimethanol mono- or divinyl ether, cyclohexane diol mono- or divinyl ether, and the like.

As the above-mentioned mono-, di- and polyvinyl ethers (B-2-3), compounds having an ether bond (B-2-3-), (B-2-3-), compounds having an ester bond ( B-2-3-) and the like. Examples of the compound (B-2-3-) having an ether bond include ethylene glycol methyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol methyl vinyl ether, dipropylene glycol divinyl ether, ditetramethylene glycol divinyl ether, and the like. Can be mentioned.

Compound having urethane bond (B-2-3
-) Is a monovinyl ether (m) of (poly) alkylene glycol having one hydroxyl group in one molecule.
And a compound (n) having at least one isocyanate group in one molecule can be obtained by a urethanization reaction.

Having one hydroxyl group in one molecule (poly)
Examples of the alkylene glycol monovinyl ether (m) include 2-hydroxyethyl vinyl ether,
4-hydroxybutyl vinyl ether, polyethylene glycol monovinyl ether and the like can be mentioned.

On the other hand, the compound (n) containing at least one isocyanate group in one molecule is, for example,
The above-mentioned isocyanate compound (B-1-2) and the like can be mentioned.

Compound having ester bond (B-2-3
-) Is a dehydrohalogenated compound (l) having a monovinyl ether (m) of (poly) alkylene glycol having one hydroxyl group in the molecule and at least one carboxylic acid halide in the molecule. Can be obtained by the esterification reaction with.

Examples of the compound (l) having at least one carboxylic acid halide in one molecule include known carboxylic acid halides such as chloride and bromide. Specific examples of the carboxylic acid include acetic acid, propionic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, dimer acid, sebacic acid, tetrahydrophthalic acid and azelaic acid.

Next, N which can be used in the resin composition of the present invention.
Examples of the compound (B-3) having a vinyl group include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide and the like.

Examples of the maleimide compound (B-4) other than the component (A) usable in the resin composition of the present invention include, for example, Nn-butylmaleimide, N-hexylmaleimide and 2-maleimide. Ethyl carbonate, 2
-Monofunctional aliphatic maleimides such as maleimidoethyl-propyl carbonate, N-ethyl- (2-maleimidoethyl) carbamate; alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N, N'-hexamethylenebismaleimide , Polypropylene glycol-bis (3-maleimidopropyl) ether, aliphatic bismaleimides such as bis (2-maleimidoethyl) carbonate; fats such as 1,4-dimaleimidocyclohexane and isophorone bisurethane bis (N-ethylmaleimide) Cyclic bismaleimide; maleimide compound obtained by esterification of maleimide acetic acid and polytetramethylene glycol, and maleimide compound obtained by esterification of maleimide caproic acid with tetraethylene oxide adduct of pentaerythritol. (Poly) obtained by esterifying a ruboximaleimide derivative with various (poly) ols
Examples thereof include ester (poly) maleimide compounds,
It is not limited to these.

(Meth) that can be used in the resin composition of the present invention
Examples of the acrylamide compound (B-5) include monofunctional (meth) acrylamides such as acryloylmorpholine and N-isopropyl (meth) acrylamide; and polyfunctional (meth) such as methylenebis (meth) acrylamide.
Examples thereof include acrylamides.

Unsaturable polyester (B-6) that can be used
Examples thereof include fumaric acid esters such as dimethyl maleate and diethyl malate; esterification reaction products of polyunsaturated carboxylic acids such as maleic acid and fumaric acid, and polyhydric alcohols.

The polymerizable compound (B) that can be used in the resin composition of the present invention is not limited to the above-mentioned compounds, and if it is a compound copolymerizable with the component (A), The compounds of one kind or a plurality of kinds can be used together without any particular limitation. In particular, as the component (B), it is preferable to use one or more selected from the group consisting of the compounds having the (meth) acryloyloxy group.

In the resin composition of the present invention, the ratio of the components (A) and (B) to be used is not particularly limited, but the ratio (B) to 100 parts by weight of the component (A) is used. )
It is preferable to use 10 to 1000 parts by weight of the components, 1
It is particularly preferred to use 0 to 500 parts by weight.

The resin composition of the present invention is a cured product having sufficient performance, which is cured by the irradiation of ultraviolet rays by using the above-mentioned components (A) and (B), and is further thermally cured if necessary. However, for the purpose of further improving the performance, a thermosetting component (C), a photopolymerization initiator, a thermosetting agent, a silane coupling agent, a filler and other additives can be used.

Specific examples of the thermosetting component (C) include epoxy resins, melamine compounds, urea compounds and phenol compounds. As an epoxy resin,
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin,
Examples thereof include phenol / novolak type epoxy resin, bisphenol type epoxy resin, rubber modified epoxy resin, epoxy modified polybutadiene and the like. Examples of the melamine compound include melamine and a melamine resin which is a polycondensation product of melamine and formalin. As the urea compound, urea, urea resin which is a polycondensation product of urea and formalin,

As the phenol compound, catechol,
Examples thereof include bisphenol A, resorcin, hydroquinone, pyrogallol, and resole.

As the preferable thermosetting component (C), the above-mentioned epoxy resin and the like can be mentioned. The blending ratio is preferably 0 to 30% by weight in the resin composition.

Specific examples of the photopolymerization initiator include radical photopolymerization initiators such as α-diketones such as benzyl and diacetyl; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Acyloin ethers; thiophenone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like; acetophenone , P-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophenone, P-methoxyacetophenone, 2
-Methyl-4- (methylthio) phenyl-2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-
Acetophenones such as on; anthraquinone, 1,4
-Quinones such as naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -S-triazine; acylphosphine oxide such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide To be

As the cationic photopolymerization initiator, triallyl sulfonium salt, diallyl iodonium salt and the like can be used. Examples of commercially available products include Adeka Optomer SP-150 and Adeka Optomer SP-170.
(Above, Asahi Denka Co., Ltd., trade name), Syracure U
VI-6990 (Union Carbide Co., Ltd., trade name)
Etc.

These photopolymerization initiators may be used alone or in combination of two or more. The mixing ratio is preferably 10% by weight or less in the resin composition.

Specific examples of the thermosetting agent include the above-mentioned epoxy resin as the thermosetting component (C) or the thermosetting agent for reacting the epoxy group in the component (A), 2-ethyl-4-methylimidazole. , 1-cyanoethyl-2-
Ethyl-4-methylimidazole, 2-phenyl-4-
Imidazoles such as methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenylimidazolium-trimellitate, 2,4-diamino-6- [2-methylimidazole- (1)]-ethyl-S-triazine; amber Organic acid hydrazides such as acid dihydrazide, adipic acid hydrazide and salicylic acid dihydrazide; acid anhydrides; amines; Lewis acids; dicyandiamide and the like. As a thermosetting agent for reacting the maleimide group of the component (A) and the ethylenically unsaturated group of the component (B), 1,
1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide,
Examples thereof include organic peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, lauroyl peroxide, and benzoyl peroxide.

One kind or two or more kinds of these thermosetting agents are used. The blending ratio is preferably 15% by weight or less in the resin composition.

Specific examples of the silane coupling agent include:
Vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and other vinylsilane-based compounds, γ-methacryloxypropyltrimethoxysilane and other acrylsilane-based compounds, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , Γ-glycidoxypropyltrimethoxysilane and other epoxysilanes, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Examples thereof include aminosilane-based compounds such as methoxysilane, and γ-mercaptopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane. The blending ratio is preferably 20% by weight or less in the resin composition of the present invention.

Specific examples of the filler include spencer talc such as transparent glass beads, kaolin, clay, barium sulfate, quartz, magnesium carbonate, calcium carbonate, silica, fine silica, titanium oxide, aluminum oxide, aluminum hydroxide and silica. Inorganic filler such as aluminum oxide,
Examples thereof include spacers such as plastic beads, fine acrylic polymers, organic fillers such as fine butyl nitrile rubber, and the like. The particle size of these fillers is preferably 1.5 μm or less because the thixotropy is improved. The compounding ratio is 50 in the resin composition of the present invention.
It is preferably not more than wt%.

Other additives include, for example, colorants,
Leveling agents, defoaming agents, polymerization inhibitors and the like can be mentioned.

The resin composition of the present invention comprises:
Component (B), component (C) for the purpose of improving performance, and further, if necessary, a photopolymerization initiator, an epoxy resin, a thermosetting agent, a silane coupling agent, a filler, and other additives are mixed and dissolved, Then, it can be obtained by kneading with a triple roll or the like.

The resin composition of the present invention can be cured by irradiation with ultraviolet rays. The curing conditions are
A high-pressure mercury lamp is usually used for UV curing, and the irradiation conditions vary depending on the type of lamp used, the composition and amount of the resin composition, the distance from the lamp, etc., and may be adjusted according to these conditions, with no particular limitation. Although not a thing, for example, the energy amount is 500 mJ / cm ^{2 to} 5000 mJ /
Irradiation conditions of about cm ² are adopted.

When heat curing is carried out, it varies depending on the type of the heat curing agent used, the type of other materials, the compounding ratio, etc., and is not particularly limited, but is, for example, 60 to 150.
Conditions of about 1 hour or more at ℃ are usually adopted.

[0084]

The present invention will be further described below with reference to specific examples and comparative examples, but the present invention is not limited to those described in these examples. Example 1 Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, epoxy equivalent 180) 3
60 g, maleimidocaproic acid 207 g, P-methoxyphenol 0.2 g and triphenylphosphine 1.7
g was charged and reacted at 90 ° C. for about 10 hours. When the acid value (mgKOH / g) of the reaction solution became 1.0 or less, the reaction was terminated to obtain a product [component (A)]. 70 parts of this product, 30 parts of a diacrylate ester of bisphenol A diglycidyl ether, 40 parts of pentaerythritol triacrylate, (P-tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate 3
Parts, talc 50 parts as an inorganic filler and fine silica 10
Parts and 5 parts of γ-glycidoxypropylmethoxysilane as a coupling agent were kneaded in a three-roll mill, and then further adjusted resin composition for a sealing material 10
A spacer for liquid crystal display panel was prepared by mixing 5 parts of the spacer with 0 part of the spacer. (Preparation of liquid crystal display panel) The prepared sealing material is screen-printed on a glass substrate (around) with a transparent electrode,
Next, after filling the fluorine-based liquid crystal composition from the center of the glass substrate, a second glass substrate with a transparent electrode was attached to the glass substrate and pressure-bonded thereto, and then the high pressure mercury lamp (2
KW) was used to irradiate it with ultraviolet rays at about 8 J / cm ² , and then it was heated at 80 ° C. for 10 minutes to cure the sealing material to obtain a liquid crystal display panel. The resulting liquid crystal display panel was evaluated for adhesion and moisture resistance. The results are shown in Table 1.

Comparative Example 1 A liquid crystal display panel was prepared in the same manner as in Example 1 except that 70 parts of the product of the component (A) [component (A)] in Example 1 was changed to 0 part. The results are shown in Table 1.

Evaluation method Adhesion: The liquid crystal cell was placed in an environment of 80 ° C. × 95% RH for 20
1 hour left for 0 hours, 10 hours indoors for 1 cycle,
After a 10-cycle test, the state of cell peeling was examined with a knife. ○ ・ ・ ・ ・ No peeling △ ・ ・ ・ ・ Peeling somewhat difficult × ・ ・ ・ ・ Peeling somewhat easy

Moisture resistance: After leaving the liquid crystal cell in an environment of 80 ° C. × 95% RH for 1000 hours, 5 V, 50 Hz between terminals
Was applied, and the reliability was judged by the rate of change from the current value. Good ... Reliability with small fluctuation (current value is less than twice the initial value). △ ・ ・ ・ ・ There is some fluctuation (current value is 2 to 3 in the initial stage)
Times), somewhat unreliable. × ... ・ Variable (current value exceeds 3 times the initial value) and poor reliability.

[0088]

As is clear from the evaluation results in Table 1, the resin composition of the present invention is sufficiently cured by irradiation with ultraviolet rays and heat, and the cured product has excellent adhesion and moisture resistance.

[0090]

Since the resin composition of the present invention is an ultraviolet curable type, it cures in a short time and is already cured by irradiation of ultraviolet rays during heat treatment. It is possible to obtain a highly reliable liquid crystal cell or organic EL cell because the upper and lower substrates are not misaligned due to slippage or difference in thermal expansion of different substrates, and the adhesiveness and moisture resistance are excellent. became.

Continued front page    F-term (reference) 2H089 MA04Y MA05Y                 4J027 AA02 AA04 AB02 AB06 AB07                       AB15 AB16 AB18 AB19 AB23                       AB25 AC01 AC02 AC03 AC04                       AC08 AE01 AE02 AE03 AE04                       AE05 AE06 AF05 AG01 AG03                       AG04 AG09 AG23 AG24 AG27                       AJ08 BA04 BA07 BA08 BA13                       BA14 BA15 BA19 BA20 BA21                       BA23 BA24 BA26 BA29 CA10                       CC05 CD06                 4J036 AA01 AB01 AB05 AB07 AC02                       AD07 AD08 AD09 AE07 AF06                       AF08 CB22 HA02 JA07

Claims (5)

[Claims] 1. A product (A) obtained by reacting 0.05 to 0.9 equivalents of a carboxyl group in a maleimide group-containing monocarboxylic acid (b) with 1 equivalent of an epoxy group in an epoxy resin (a). A resin composition containing a polymerizable compound (B) other than the component (A). 2. The resin composition according to claim 1, wherein the polymerizable compound (B) other than the component (A) is at least one selected from the group consisting of compounds having a (meth) acryloyloxy group. 3. The resin composition according to claim 1, which contains a thermosetting component (C). 4. The resin composition according to claim 3, wherein the thermosetting component (C) is an epoxy resin. 5. A cured product of the resin composition according to any one of claims 1 to 4.