JP2000256428A - Hardening resin and composition thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable and/or thermosetting resin having a high ink sensitivity and a tack-free property (adhesion resistance), and a resin composition thereof. SOLUTION: The hardening resin comprises a compound (A) possessing a linkable bivalent group between an unsaturated group and a carboxyl group, and a modified copolymer obtained by adding an epoxy group-containing unsaturated compound (C) to a portion of acid groups in a copolymer (B) having a Tg (glass transition temperature) of 50 deg.C or higher, obtained from a (meth) acrylic acid and (meth)acrylic ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable resin and a composition thereof. More specifically, the present invention relates to a photosensitive resin and a composition thereof, which can easily form an image by exposure to light and development with a dilute aqueous alkali solution after formation of a film. In particular, it is useful as a binder resin for a resist ink such as a printed wiring board related to electronics, an LSI, a color filter attached to a liquid crystal, and a sealant.

[0002]

2. Description of the Related Art In recent years, there has been a shift from solvent development to dilute alkaline aqueous solution development in various fields for reasons such as environmental problems, resource saving, energy saving, and improvement in workability. In the field of printing and wiring board processing, the resist ink has shifted from the solvent developing type to the dilute alkaline aqueous solution developing for the same reason.
In a printed wiring board, a solder resist resin is widely used as a permanent protective film for a substrate circuit. The solder resist is formed on the entire surface of the substrate circuit conductor except for the portion to be soldered. Its main role is to prevent solder from adhering to unnecessary parts when soldering electronic components to a printed wiring board, and to prevent oxidation and corrosion of circuit conductors. Conventionally, when a solder resist is formed on a printed wiring board, a thermosetting resist ink is printed by a screen printing method, and a transfer portion is heat-cured or ultraviolet-cured. However, the screen printing method causes a phenomenon such as bleeding, bleeding, and sagging at the time of printing, and cannot respond to recent high-density circuit boards. To solve this problem, photographic methods were developed.
The photographic method is a method of forming a target pattern by exposing through a film on which a pattern is formed, and developing the exposed film.

[0003] Organic solvents have conventionally been used for developing such a photo solder resist ink. However, in recent years, there has been a tendency to shift to a type that can be developed with a dilute alkaline aqueous solution due to the problem of environmental pollution. Such a resist ink is obtained by adding a polybasic anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monocarboxylic acid as described in Japanese Patent Publication No. 1-54390. Compounds are used as main components. The solder resist ink obtained using this compound as a main component has excellent heat resistance and is widely used even today. Further, compositions using a half ester compound of a copolymer of styrene and maleic anhydride described in JP-A-63-11930 and JP-A-63-20564 have been proposed. However, since the ink using the above compound has a benzene ring skeleton, it has disadvantages such as (1) absorption of ultraviolet rays, resulting in lower sensitivity of the ink, and (2) deterioration of electrical characteristics. I was In addition, inks using the above compounds may have tackiness during predrying to remove the solvent, that is, tackiness may remain.Preliminary drying is performed to completely remove the tack in order to prevent the negative film from being stained during contact exposure. Strengthen conditions. Generally, the heat treatment time is extended by increasing the temperature because the ink hardens due to heat and developability after exposure deteriorates. For this reason, the pre-drying time is a rate-determining step in the manufacturing process of the printed wiring board, which is an obstacle to efficient production. In order to solve the above problems, Japanese Patent Application Laid-Open
Japanese Patent Application Laid-Open No. 289820/1989 and Japanese Patent Application Laid-Open No. 6-138659 discloses a resin composition in which an alicyclic epoxy-containing unsaturated compound is added to poly (meth) acrylic resin. However, it is not enough in terms of sensitivity.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light and / or thermosetting resin having excellent ink sensitivity and having tack-free properties (adhesion resistance), and a resin composition thereof.

[0005]

Means for Solving the Problems The present inventors have proposed compounds (A), (meth) acrylic acid and (meth) acrylate having a divalent group capable of bonding between an unsaturated group and a carboxyl group. A curable resin comprising a modified copolymer obtained by adding an epoxy group-containing unsaturated compound to a part of the acid groups of a copolymer having a specific Tg (glass transition temperature) obtained from the above is solved. The inventors have found that the present invention has been completed.

That is, the present invention relates to a compound (A) having a divalent group capable of binding between an unsaturated group and a carboxyl group,
Epoxy group-containing unsaturated compound (C) is added to some acid groups of copolymer (B) having a Tg (glass transition temperature) of 50 ° C. or higher obtained from (meth) acrylic acid and (meth) acrylate. Provided is a curable resin comprising a modified copolymer obtained by the above method. The present invention relates to a curable resin in which the compound (A) having a divalent group capable of binding between an unsaturated group and a carboxyl group in the curable resin is β-carboxyethyl (meth) acrylate; A curable resin wherein the saturated compound (C) is 3,4-epoxycyclohexylmethyl (meth) acrylate. The present invention also provides a curable resin composition soluble in the above-mentioned curable resin and a dilute aqueous alkaline solution comprising a diluent monomer or oligomer. Further, the present invention provides a curable resin composition soluble in a dilute aqueous alkali solution, comprising the above-mentioned curable resin, photopolymerization initiator and diluent monomer or oligomer. The present invention also provides a resin composition wherein each of the above-mentioned curable resin compositions further contains an epoxy compound and / or an epoxy resin, and / or a pigment. Further, the present invention provides a curable resin composition containing a resin obtained by modifying a novolak or bisphenol-based epoxy resin with (meth) acrylic acid and then adding an acid anhydride. The present invention provides the curable resin composition used as a component of a liquid resist, a dry film, a color filter for a liquid crystal display, a pigment resist for a black matrix, or a protective film for coating.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The modified copolymer has a Tg obtained from a compound (A) having a divalent group capable of bonding between an unsaturated group and a carboxyl group, (meth) acrylic acid and (meth) acrylate.
Is obtained by adding an epoxy group-containing unsaturated compound (C) to some of the acid groups of the copolymer (B) at 50 ° C. or higher, and constitutes a curable resin. In the present invention, by introducing a unit of a monomer having a divalent group capable of bonding between an unsaturated group and a carboxyl group into the modified copolymer skeleton, the sensitivity to light and / or heat is improved, Tack-free property is also given at the same time. Examples of the compound (A) having a divalent group capable of bonding between an unsaturated group and a carboxyl group include β-carboxyethyl (meth) acrylate,
Such as acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, lactone-modified unsaturated monocarboxylic acid having an ester bond, modified unsaturated monocarboxylic acid having an ether bond, etc. Things.

Specific examples of the modified unsaturated monocarboxylic acid include compounds of the general formula (1) obtained by modifying lactone of (meth) acrylic acid; CH ₂ ＣC (R ¹ ) CO [O (CR ² R ³ ) _m CO] _n OH (1)

A lactone-modified compound of the general formula (2) wherein the terminal hydroxyl group is acid-modified with an acid anhydride; CH ₂ C (R ¹ ) COOCH ₂ CH ₂ O [CO (CR ² R ³ ) _m O] _n COR ⁴ COOH (2) (wherein, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ each represent a hydrogen atom, a methyl group or an ethyl group. R ⁴ has 1 to 10 carbon atoms. It represents a divalent aliphatic saturated or unsaturated hydrocarbon, a divalent alicyclic saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, p-xylene, phenylene group and the like.
m represents an integer of 4 to 8, and n represents an integer of 1 to 10. )

A compound of the general formula (3) in which a terminal hydroxyl group having an ether bond is acid-modified with an acid anhydride: CH ₂ ＣC (R ¹ ) COO [(CR ² R ³ ) _m O] _n COR ⁴ COOH (3 (Wherein, R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group; and R ⁴ has 1 to 10 carbon atoms. Represents a divalent aliphatic saturated or unsaturated hydrocarbon, a divalent alicyclic saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, p-xylene, phenylene group, etc. m and n are 1 to 10 Represents an integer.). Introduction of compound (A) having a divalent group capable of binding between an unsaturated group and a carboxyl group, which is necessary for improving sensitivity while maintaining resin Tg at 50 ° C. or higher by mixing with (meth) acrylic acid Being able to increase the amount, β
-Carboxyethyl (meth) acrylate is preferred.

The (meth) acrylic acid and (meth) acrylic acid ester used in the present invention are a general term including methacrylic acid, acrylic acid and their esters. Examples of the (meth) acrylate used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and adamantyl. (Meth) such as (meth) acrylate, norbornyl (meth) acrylate
Alkyl acrylates, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate,
(Meth) acrylates having a hydroxyl group such as caprocactone-modified 2-hydroxyethyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, and hydroxynorbornyl (meth) acrylate; methoxydiethylene glycol (meth) acrylate; ethoxydiethylene glycol (meth) (Meth) acrylates such as acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate.

Further, if necessary, other monomers such as vinylphenols may be used. Alternatively, a compound containing two or more carboxyl groups such as maleic acid in the molecule may be copolymerized. These may be used alone or as a mixture.

[0013] Polymerization to obtain a normal acrylic copolymer from compound (A) having a divalent group capable of bonding between an unsaturated group and a carboxyl group, (meth) acrylic acid and (meth) acrylic acid ester The modified copolymer is obtained by adding an epoxy group-containing unsaturated compound (C) to some of the acid groups of the copolymer (B) obtained by reacting under the conditions. The epoxy group-containing unsaturated compound (C) is a compound having one radically polymerizable unsaturated group and an alicyclic epoxy group in one molecule. Specific examples include an alicyclic epoxy group-containing unsaturated compound represented by the following general formula. Of these, 3,4-epoxycyclohexylmethyl (meth)
Acrylates are preferably used.

[0014]

Embedded image

Further, there may be mentioned aliphatic-containing unsaturated compounds such as glycidyl methacrylate, β-methylglycidyl methacrylate and allyl glycidyl ether. These unsaturated compounds containing an epoxy group may be used alone or in combination of two or more.

The ratio of the compound (A) having a divalent group capable of bonding between the unsaturated group and the carboxyl group constituting the copolymer (B), (meth) acrylic acid and (meth) acrylate is as follows: , 0.1-80 / 10 to 89 / 10-8
9.9% by weight, further 1 to 80/10 to 80/10 to 8
A range of 0% by weight is preferred. The copolymer (B) has a Tg
(Transition temperature) 50 ° C. or higher, preferably 50 to 200 ° C.
If the Tg is less than 50 ° C. in the stage of the copolymer (B), it is not preferable because the tack-free property as a modified copolymer (curable resin) is lowered.

The addition amount of the epoxy group-containing unsaturated compound (C) is 5 to 99 relative to the carboxyl group of the modified copolymer.
It is preferably in the range of equivalents, more preferably 30 to 90 equivalents. If the addition amount is less than 5 equivalents, the ultraviolet curability is poor,
The physical properties of the cured film decrease. If it exceeds 99 equivalents, the storage stability of the resin deteriorates.

Examples of the catalyst used for adding the epoxy group-containing unsaturated compound (C) to the copolymer (B) include tertiary compounds such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine and tri-n-octylamine. Amines, tetramethylammonium chloride, tetramethylammonium bromide, quaternary ammonium salts such as tetrabutylammonium bromide, alkylureas such as tetramethylurea, alkylguanidines such as tetramethylguanidine, metal compounds represented by cobalt naphthenate, Examples thereof include organometallic complexes, phosphines such as triphenylphosphine and salts thereof, and tertiary phosphines represented by triphenylphosphine are preferred. The above catalysts may be used alone or in combination. These catalysts are preferably used in an amount of 0.01 to 10% by weight, more preferably 0.5 to 3.0% by weight, based on the epoxy compound. When the amount is less than 0.01% by weight, the catalytic effect is low, and it is not necessary to add an amount exceeding 10% by weight.

Further, the epoxy group-containing unsaturated compound (C)
The solvent at the time of the addition reaction is not particularly limited as long as it dissolves the raw materials to be used, for example, benzene, toluene, aromatic hydrocarbons such as xylene, methanol,
Alcohols such as ethanol and 2-propanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether, dibutyl ether and dioxane, ethyl acetate, isobutyl acetate, ethylene glycol monoacetate and propylene glycol monoacetate; Esters such as dipropylene glycol monoacetate, ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ethers, butylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether Diethylene dialkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, dimethyl formamide, amides such as dimethylacetamide, carbon tetrachloride, halogenated hydrocarbons such as chloroform can be used. These solvents may be used alone or as a mixture.
Conditions for adding the epoxy group-containing unsaturated compound (C) are not particularly limited.
The reaction may be performed for a time.

The modified copolymer thus obtained has an acid value of 10 to 150 KOH-mg / g, more preferably 30 to 1 KOH-mg / g.
It is preferably in the range of 30 KOH-mg / g. If the acid value is less than 10 KOH-mg / g, it is difficult to remove the uncured film with a dilute aqueous alkali solution,
If the amount exceeds mg / g, the water resistance and electrical properties of the cured film may be deteriorated. The modified copolymer has a weight average molecular weight of 5,000 to 150,000, and more preferably 5,000.
Those in the range of ~ 100,000 are preferred. When the weight average molecular weight is 5,000 or less, (1) the tack-free performance may be inferior, (2) the moisture resistance of the coating film after exposure may be poor, and film thinning may occur during development, and the resolution may be significantly inferior. . When the weight average molecular weight is 150,000 or more, (1) the developability may be significantly deteriorated,
(2) Storage stability may be poor. The curable resin of the present invention is composed of this modified copolymer.

From the curable resin and the diluting monomer or oligomer, a curable resin composition soluble in a dilute aqueous alkali solution can be obtained. This resin composition has thermosetting properties or electron beam curing properties. Further, a curable resin composition soluble in a dilute alkaline aqueous solution can be obtained from the curable resin, the photopolymerization initiator, and the diluent monomer or oligomer, and has photocurability. These curable resin compositions may further contain an epoxy compound and / or an epoxy resin, a resin obtained by acid-modifying a novolak or bisphenol-based epoxy resin with (meth) acrylic acid and then adding an acid anhydride, and / or a pigment. Good. The epoxy compound to be added is, for example, an epoxidized resin having an unsaturated group such as an epoxidized polybutadiene or an epoxidized butadiene styrene block copolymer, and commercially available products thereof include Eporide PB and ESBS manufactured by Daicel Chemical Industries, Ltd. is there. Examples of the alicyclic epoxy resin include Celloxide 2 manufactured by Daicel Chemical Industries, Ltd.
021, EHPE, EPOMIC VG manufactured by Mitsui Chemicals, Inc.
-3101, E-103 manufactured by Yuka Shell Epoxy Co., Ltd.
1S, TETRAD-X, TE manufactured by Mitsubishi Gas Chemical Co., Ltd.
TRAD-C, EPB-13, EP manufactured by Nippon Soda Co., Ltd.
B-27 and the like. As the copolymerizable epoxy resin, for example, a copolymer of glycidyl methacrylate and styrene, or a copolymer of glycidyl methacrylate, styrene and methyl methacrylate manufactured by NOF Corporation
50M, CP-50S, or a copolymer of glycidyl methacrylate and cyclohexylmaleimide.

Other examples include epoxidized resins having a special structure. As the novolak type epoxy resin, for example, novolaks obtained by reacting phenols such as phenol, cresol, halogenated phenols and alkylphenols with formaldehyde under an acidic catalyst are reacted with epichlorohydrin and / or methyl epichlorohydrin. And the like. As a commercially available product, EO manufactured by Nippon Kayaku Co., Ltd.
CN-103, EOCN-104S, EOCN-102
0, EOCN-1027, EPPN-201, BREN
-S, DEN-431, DEN- manufactured by Dow Chemical Company
439, manufactured by Dainippon Ink and Chemicals, Inc., N-73, V
H-4150 and the like. Examples of the bisphenol-type epoxy resin include those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A with epichlorohydrin, and condensation of the diglycidyl ether of bisphenol A with the bisphenols And a resin obtained by reacting a substance with epichlorohydrin. The commercially available product is Epikote 100 manufactured by Yuka Shell Co., Ltd.
4, Epicoat 1002, DER- manufactured by Dow Chemical Company
330 and DER-337. A resin obtained by reacting epichlorohydrin and / or methyl epichlorohydrin such as trisphenol methane and triscresol methane, as a commercial product, EP manufactured by Nippon Kayaku Co., Ltd.
PN-501, EPPN-502 and the like. Tris (2,3-epoxypropyl) isocyanurate, biphenyl diglycidyl ether and the like can also be used. Further, among the above epoxy resins, a resin obtained by modifying a novolak or bisphenol-based epoxy resin with (meth) acrylic acid and then adding an acid anhydride (acid-modified epoxy resin) can be used in combination with a curable resin.

These epoxy resins and acid-modified epoxy resins may be used alone or as a mixture. These epoxy compounds are used in required amounts, for example, modified copolymer 1
It is preferably added in an amount of 0 to 100 parts by weight, more preferably 0 to 80 parts by weight based on 00 parts by weight. The amount of epoxy compound is 1
When the amount is more than 00 parts, the characteristics of the curable resin are reduced.

The photopolymerization initiator used in the curable resin composition of the present invention includes, for example, benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone , Diethoxyacetophenone, diphenyl disulfite, etc., alone or as a mixture. These photoinitiators can contain a synergistic agent, such as a tertiary amine, to enhance the conversion of the light absorption energy to the polymerization initiation free radical. The amount of the photopolymerization initiator to be used is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the curable resin. When the curable resin composition of the present invention is cured by electron beam irradiation, it is not always necessary to add a photopolymerization initiator.

The diluting monomer or oligomer is a compound having a radical polymerizable double bond represented by an acrylate or methacrylate compound, a vinyl aromatic compound such as styrene, or an amide unsaturated compound. Representative acrylates or methacrylates include the following. Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate; 2-hydroxyethyl (Meth) acrylates having a hydroxyl group such as (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone-modified 2-hydroxyethyl (meth) acrylate; methoxydiethylene glycol (meth) acrylate, ethoxy Diethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, methoxy Triethylene glycol (meth) acrylate, methoxy polyethylene glycol # 400-
(Meth) acrylates such as (meth) acrylate;
Bifunctional (meth) acrylates such as 1,6-hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate; trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate Are used. As the polymerizable prepolymer, for example, (meth) of a polyester polyol
Acrylic esters, (meth) acrylic esters of polyether polyols, adducts of polyepoxy with (meth) acrylic acid, and resins in which hydroxy (meth) acrylate is introduced into polyol via polyisocyanate, etc. .

The above-mentioned diluent monomers and oligomers are
The modified copolymer (curable resin) can be blended in an amount necessary for 100 parts by weight, for example, preferably in the range of 1 to 300 parts by weight, more preferably 1 to 100 parts by weight. When the amount of the diluting monomer and oligomer is more than 300 parts, the characteristics of the curable resin composition are reduced.

Other additives may include a thermal polymerization inhibitor, a surfactant, a light absorber, a thixotropy-imparting agent, a dye, and the like, as necessary. Further, a thermoplastic resin, a thermosetting resin, or the like can also be blended. The curable resin and the curable resin composition of the present invention can be cured by being applied as a thin film on a substrate. As a method of forming a thin film, spraying, brushing, roll coating, curtain coating, electrodeposition coating, electrostatic coating and the like are used. Curing is preferably performed in an inert gas atmosphere, but curing can also be performed in an air atmosphere. The curable resin and the curable resin composition according to the present invention are used in various coating fields such as ink, plastic paint, paper printing, film coating, furniture coating, FRP, lining, and furthermore, in insulating varnishes, insulating sheets and laminated plates in the field of electronics. It can be applied to many industrial fields, such as a printed substrate, a liquid resist, a dry film, a resist ink, a color filter for a liquid crystal display or a pigment resist for a black matrix, a component of a protective film for coating, and a semiconductor encapsulant. In addition, as light in the case of photocuring, ultraviolet rays, electron beams and the like can be mentioned.

[0028]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. still,
The evaluation was performed by the following method. Touch dryness test: After drying was completed, tackiness was evaluated according to the following criteria by finger touch. ：: a substance without tack △: a substance with slight tack ×: a substance with tack Sensitivity test: Evaluated using a 21-step tablet manufactured by Stoffer.

Synthesis Example of Curable Resin (Synthesis Example 1) Dipropylene glycol monomethyl ether (MFDG manufactured by Nippon Emulsifier Co., Ltd.) was placed in a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube. 325 g), and after heating to 110 ° C., βCEA (β carboxyethyl acrylate) 3
7.6 g, 201.9 g of methacrylic acid, 186.4 g of methyl methacrylate, 222 g of MFDG, and 21.7 g of t-butylperoxy-2-ethylhexanoate (Perbutyl O, manufactured by NOF CORPORATION) were added dropwise over 3 hours. After dropping, the mixture was aged for 3 hours to synthesize a trunk polymer having a Tg of 137 ° C (corresponding to the copolymer (B)). Next, 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A manufactured by Daicel Chemical Industries, Ltd.) was added to the trunk polymer solution.
200) 289.2 g, triphenylphosphine 2.9 g,
After adding 1.3 g of methylhydroquinone,
The reaction was performed for 0 hours. The reaction was performed under a mixed atmosphere of air / nitrogen. Thus, a curable resin solution (A-1) having an acid value of 100 KOH-mg / g, a double bond equivalent (g weight of resin per 1 mole of unsaturated group) of 450, and a weight average molecular weight of 15,000 was obtained.

(Synthesis Example 2) Into a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 325 g of dipropylene glycol nomomethyl ether (MMPG manufactured by Nippon Emulsifier) was introduced. 1
After heating to 10 ° C., 187.8 g of βCEA (β-carboxyethyl acrylate), 112.2 g of methacrylic acid, 125.9 g of methyl methacrylate, 222 g of MFDG and t-butylperoxy-2-ethylhexanoate
17.0 g (Perbutyl O, manufactured by NOF CORPORATION) was added dropwise over 3 hours. After dropping, the mixture was aged for 3 hours to synthesize a trunk polymer having a Tg of 62 ° C (corresponding to the copolymer (B)). Next, 289.2 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.), 2.9 g of triphenylphosphine, and 1.3 g of methylhydroquinone were added to the stem polymer solution, and 1
The reaction was performed at 00 ° C. for 10 hours. The reaction was performed under a mixed atmosphere of air / nitrogen. Thereby, acid value 100KOH-mg /
g, double bond equivalent (g weight of resin per mole of unsaturated group)
450, curable resin solution with weight average molecular weight of 20,000
(A-2) was obtained.

(Synthesis Example 3) 250 g of propylene glycol nomomethyl ether (MMPG manufactured by Daicel Chemical Industries, Ltd.) was introduced into a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube. After heating to 110 ° C., 187.8 g of βCEA (β-carboxyethyl acrylate) and 112.2 g of methacrylic acid
g, adamantyl acrylate 125.9 g, MFDG
222 g and 21.7 g of t-butyl peroxy-2-ethylhexanoate (Nippon Oil & Fats Co., Ltd. perbutyl O) were added dropwise over 3 hours. After dripping for 3 hours, Tg becomes 7
A backbone polymer (corresponding to the copolymer (B)) at 8 ° C was synthesized. Next, 289.2 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.), 2.9 g of triphenylphosphine, and 1.3 g of methylhydroquinone were added to the trunk polymer solution, and the mixture was heated at 100 ° C. The reaction was performed for 10 hours. The reaction is air /
The test was performed under a mixed atmosphere of nitrogen. Thereby, acid value 100
A curable resin solution (A-3) having a KOH-mg / g, a double bond equivalent (g weight of resin per mole of unsaturated group) of 450, and a weight average molecular weight of 14,000 was obtained.

(Synthesis Example 4) Into a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 325 g of dipropylene glycol nomomethyl ether (MMPG manufactured by Nippon Emulsifier) was introduced. 1
After the temperature was raised to 10 ° C., 375.7 g of βCEA (β carboxyethyl acrylate), 50.2 g of methyl methacrylate
g, MFDG 222 g and t-butylperoxy-2-
Ethyl hexanoate (Nippon Oil & Fats Perbutyl O) 2
1.7 g were added dropwise over 3 hours. After dripping, the mixture was aged for 3 hours to synthesize a trunk polymer having a Tg of 0 ° C (corresponding to the copolymer (B) having no (meth) acrylic acid structural unit). Next, 289.2 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.), 2.9 g of triphenylphosphine, and 1.3 g of methylhydroquinone were added to the trunk polymer solution, and the mixture was heated at 100 ° C. The reaction was performed for 10 hours. The reaction was performed under a mixed atmosphere of air / nitrogen. This gives an acid value of 100 KO
H-mg / g, double bond equivalent (resin weight per mole of unsaturated group)
450, curable resin solution with weight average molecular weight of 15,000
(A-4) was obtained.

(Synthesis Example 5) A cresol novolak type epoxy resin having an epoxy equivalent of 215 (YDCN- manufactured by Toto Kasei Co., Ltd.) was placed in a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube. 702) 1
090 g was introduced and heated and melted at 100 ° C. Then
Add 390 g of acrylic acid, 1.5 g of methylhydroquinone and 2 g of dimethylbenzylamine, and add
Allowed to react for hours. As a result, an acrylic acid-modified novolak-type epoxy compound having an acid value of 3.0 KOH-mg / g was synthesized. 250 g of ethyl carbitol acetate was introduced into 450 g of this product, heated at 80 ° C., and reacted with 0.5 mol of tetraphthalic anhydride to one hydroxyl group equivalent to obtain an acid value of 58 KO.
A curable resin solution having an unsaturated group and an acid group to which an acid anhydride is added after denaturation of an H-mg / g epoxy resin with acrylic acid (A-
5) was obtained.

(Examples 1 to 5 and Comparative Examples 1 and 2) Using the resin solutions A1 to 5 obtained in the synthesis examples, the curable resin (solid content) and trimethylolpropane 20 parts by weight of an acrylate, 20 parts by weight of a cresol novolac type epoxy resin having an epoxy equivalent of 220 (Epicoat 180S70 manufactured by Yuka Shell Epoxy Co., Ltd.), 7 parts by weight of benzyl methyl ketal as a photopolymerization initiator, and 2 parts of diethylthioxanthone as a photopolymerization initiator Parts by weight, 1.5 parts by weight of phthalocyanine green, 5 parts by weight of silica, 20 parts by weight of barium sulfate and 5 parts by weight of dicyandiamide were mixed and kneaded with three rolls to obtain a viscous ink composition.
This ink was applied to a thickness of 20 μm on a pattern-formed substrate using a bar coater, and dried with a blow dryer at 80 ° C. for 20 minutes. Thereafter, a negative film was brought into close contact with the film and irradiated with a light amount of 800 mJ / cm ² . In addition, 1%
Developed with aqueous sodium carbonate solution,
The coating was obtained by curing for 30 minutes in a blast oven. The coating film was evaluated for dryness to touch and sensitivity, and the results are shown in Table 1.

[0035]

[Table 1]

[0036]

As shown in the examples, according to the present invention, a curable resin and / or a photocurable resin composition of an ink material having high sensitivity and excellent tack-free property can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G59 / 20 C08G59 / 20 4J027 C08L 63/02 C08L 63/02 4J036 63/04 63/04 4J038 C09D 163 / 10 C09D 163/10 G02B 5/00 G02B 5/00 B 5/20 101 5/20 101 G03F 7/004 505 G03F 7/004 505 7/027 502 7/027 502 515 515 7/028 7/028 7 / 032 501 7/032 501 7/033 7/033 7/038 501 7/038 501 F term (reference) 2H025 AA01 AA04 AA15 AB11 AB13 AB15 AC01 AD01 BC13 BC31 BC53 BC83 BC85 BC86 BC97 BD03 BD23 BD53 CA00 CC12 FA17 2H042 AA09 AA15 AA26 2H048 BA47 BA48 BB37 BB42 4J002 BG04W BG05W CD19X CD20X EH078 FD096 FD207 GH01 GP00 4J011 QA03 QB02 QB29 QC04 SA01 SA21 SA31 SA83 UA01 WA01 4J027 AB03 AE02 AE03 AE07 AJ06 BA06 BA07 BA17 BA23 BA24 CC03 CD08 CD10 4J036 AK08 CA19 CA21 DB15 JA09 4J038 DB061 DB062 DB071 DB072 DB161 DB162 DB191 DB192 DB201 DB202 DB221 DB222 DB351 DB352 DB371 DB372 FA041 FA042 FA091 FA092 FA092 FA091 FA261 FA262 FA271 FA272 JA33 JA69 JC01 KA03 KA06 KA08 MA13 NA18 PA17 PA19 PB08

Claims (9)

[Claims] (1) The Tg (glass transition temperature) obtained from the compound (A) having a divalent group capable of binding between an unsaturated group and a carboxyl group, (meth) acrylic acid and (meth) acrylate ester is as follows: A curable resin comprising a modified copolymer obtained by adding an epoxy group-containing unsaturated compound (C) to some acid groups of the copolymer (B) at 50 ° C or higher. 2. The curable resin according to claim 1, wherein the compound (A) having a divalent group capable of binding between an unsaturated group and a carboxyl group is β-carboxyethyl (meth) acrylate. 3. An epoxy group-containing unsaturated compound (C) comprising:
The curable resin according to claim 1, which is 4-epoxycyclohexylmethyl (meth) acrylate. 4. A curable resin composition comprising the curable resin according to claim 3 and a diluent monomer or oligomer and soluble in a dilute aqueous alkali solution. 5. A curable resin composition comprising the curable resin according to claim 3, a photopolymerization initiator and a diluent monomer or oligomer, which is soluble in a dilute aqueous alkali solution. 6. The curable resin composition according to claim 4, further comprising an epoxy compound and / or an epoxy resin. 7. The curable resin composition according to claim 4, further comprising a pigment. 8. The curable resin composition according to claim 4, comprising a resin obtained by modifying a novolak or bisphenol-based epoxy resin with (meth) acrylic acid and then adding an acid anhydride. 9. The curable resin composition according to claim 4, which is used as a component of a liquid resist, a dry film, a color filter for a liquid crystal display, a pigment resist for a black matrix, or a protective film for coating.