JPH09278842A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which need only a short preheating period in resist formation for a printed circuit board and gives a resist capable of image formation through exposure and development with a dilute aqueous alkali solution. SOLUTION: The composition, soluble in a dilute aqueous alkali solution, comprises a modified copolymer, a photopolymerization initiator, and a diluting monomer or oligomer. The copolymer is obtained by adding glycidyl methacrylate and an alicyclic unsaturated epoxy compound to part of the carboxyl groups of a copolymer obtained from a (meth)acrylic ester and a compound having an unsaturated group and at least one carboxyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition that is soluble in a dilute alkaline aqueous solution and that is cured by light or heat. More specifically, the preheating time when forming a resist for a printed wiring board is short and the resist formation is The present invention relates to a curable resin composition capable of forming an image by subsequent exposure and development with a dilute alkaline aqueous solution.

[0002]

In the field of resists for printed wiring boards,
As a method for forming a resist on a printed wiring board, a photographic method has been developed in which a photosensitive film is exposed and developed into a predetermined pattern to form a desired resist pattern. As the resist material, a photosensitive film is often used because it is easy to operate, but a liquid resist is being actively used because it is inexpensive and has characteristics not found in the photosensitive film. Conventionally, there are a solvent development type and an alkali development type using a sodium carbonate aqueous solution as a developer for forming a resist. However, most of them are diluted with an alkaline aqueous solution due to ozone layer destruction and influence on a working environment. It has shifted to the development type.

As a resist material for such a dilute alkaline aqueous solution developing type printed wiring board, Japanese Patent Publication No. 1-5439.
No. 0, etc. disclose a compound obtained by adding a polybasic acid anhydride to a reaction product of a novolac type epoxy compound and an unsaturated monocarboxylic acid. The solder resist ink containing this compound as a main component has excellent heat resistance and is still used today. Further, JP-A-63-11930 and JP-A-63-20564 disclose compositions using a half ester compound of a copolymer of styrene and maleic anhydride.

[0004]

However, since the above resist material has a benzene ring skeleton, (1)
Absorbs UV light, resulting in low ink sensitivity,
(2) It has a drawback that the electric characteristics are deteriorated. Furthermore, the ink using the above compound may have tack, that is, stickiness, during predrying for removing the solvent,
The predrying condition is strengthened to completely tack the negative film in order to prevent the negative film from being soiled during contact exposure. 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.

To solve these problems, JP-A-1-289
Japanese Patent Application Laid-Open No. 820 and Japanese Patent Application Laid-Open No. 6-138659 disclose a resin composition in which an alicyclic epoxy-containing unsaturated compound is added to a poly (meth) acrylic resin. However, since the adhesion to the substrate is poor, the performance is insufficient under the severe conditions such as gold plating, which has been required more and more as the performance becomes higher.

On the other hand, among the photoresists for printed wiring boards, there is a photoresist for forming a permanent mask. This prevents solder from adhering to the circuit etc. wired on the printed wiring board when soldering electronic parts to the printed wiring board on which the circuit is wired, and also prevents oxidation and corrosion of the circuit conductor. It is a thing. Therefore, the permanent mask forming photoresist needs to be used on the entire surface of the printed wiring board. However, the alicyclic epoxy-containing unsaturated compound is expensive, and when only the alicyclic epoxy-containing unsaturated compound is used for the copolymer, the obtained resin composition becomes expensive, and its range of use is high. Limited.

[0007]

Means for Solving the Problems As a result of detailed investigations on a curable copolymer, the present inventors have confirmed that a specific copolymer is allowed to have not only an alicyclic epoxy group-containing unsaturated compound but also glycidyl methacrylate added thereto. By using the modified copolymer obtained in this way, a curable resin composition having a tack-free property and an adhesion property in harmony and being inexpensive can be obtained, and it was found that this is suitable as a resist material, and the present invention was completed. It was

That is, the present invention provides a copolymer obtained from (A) (meth) acrylic acid ester and a compound containing an unsaturated group and having at least one carboxyl group, in which a part of the carboxyl groups has glycidyl groups. A curable resin soluble in a dilute alkaline aqueous solution containing a modified copolymer having a methacrylate and an alicyclic epoxy group-containing unsaturated compound added thereto, (B) a photopolymerization initiator, and (C) a diluting monomer or oligomer. A composition is provided. The composition may also contain (D) an epoxy compound.
Further, the present invention provides the curable resin composition, wherein the modified copolymer (A) has an acid value in the range of 50 to 150. Further, the addition ratio of glycidyl methacrylate and the alicyclic epoxy group-containing unsaturated compound constituting the modified copolymer (A) is 30/70 to 70/30 mol%.
The above-mentioned curable resin composition is provided. Further, the present invention provides the curable resin composition, wherein the alicyclic epoxy group-containing unsaturated compound is 3,4-epoxycyclohexylmethyl (meth) acrylate. Further, the present invention provides the above-mentioned photocurable resin composition, which is used as one component of a liquid resist and a dry film. in addition,
The present invention provides the above-mentioned thermosetting resin composition, which is used as one component of a liquid resist. Hereinafter, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The modified copolymer (A) used in the curable resin composition of the present invention is a compound containing a (meth) acrylic acid ester and an unsaturated group and having at least one carboxyl group. A modified copolymer obtained by adding glycidyl methacrylate and an alicyclic epoxy group-containing unsaturated compound to a part of the carboxyl groups of the copolymer obtained from

Can be used in the modified copolymer (A) (meta)
As acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth)
(Meth) acrylic acid alkyl esters such as acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) Acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate and other (meth) acrylic acid esters having a hydroxyl group, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxy Triethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol ( Data) acrylate and the (meth) acrylate and the like.

The compound containing an unsaturated group and having at least one carboxyl group includes acrylic acid, methacrylic acid, and a modified unsaturated monocarboxylic acid having a chain extended between the unsaturated group and the carboxylic acid, for example, β -Carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid,
2-acryloyloxyethyl hexahydrophthalic acid,
Examples of the unsaturated monocarboxylic acid having an ester bond such as lactone modified and a modified unsaturated monocarboxylic acid having an ether bond can be given. Alternatively, it may contain two or more carboxyl groups such as maleic acid in the molecule. These may be used alone or as a mixture of two or more.

The modified copolymer (A) used in the present invention is
In the carboxyl group of the copolymer obtained from the copolymerization reaction of the (meth) acrylic acid ester and a compound containing an unsaturated group and having at least one carboxyl group,
It can be obtained by adding glycidyl methacrylate and an alicyclic epoxy group-containing unsaturated compound. The alicyclic epoxy group-containing unsaturated compound may be a compound having one radical-polymerizable unsaturated group and an alicyclic epoxy group in one molecule, and for example, the following general formulas (1) to ( 13)
The compound represented by In each formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent saturated aliphatic hydrocarbon having 1 to 6 carbon atoms. Among these, 3,4
-Epoxycyclohexylmethyl (meth) acrylate is preferred.

[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

[Chemical 6]

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

[Chemical 12]

[0025]

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The amount of addition of the alicyclic epoxy group-containing unsaturated compound and glycidyl methacrylate is such that the modified copolymer (A)
It is desirable to be in the range of 5 to 50 mol% with respect to the total monomers constituting If the addition amount is less than 5 mol%, the ultraviolet curability of the obtained curable resin composition is poor and the physical properties of the cured film are deteriorated. On the other hand, when it is 50 mol% or more, the stability of the curable resin composition is deteriorated.

The addition ratio of glycidyl methacrylate to the alicyclic epoxy group-containing unsaturated compound is 30/70.
To 70/30 mol% is preferable. This is because when the content is in this range, the tack-free performance and the adhesion performance are excellent in harmony as compared with the case where glycidyl methacrylate and the alicyclic epoxy group-containing unsaturated compound are added alone. That is, when the amount of the alicyclic epoxy group-containing unsaturated compound is 30 mol% or less, the same sensitivity as that of the glycidyl methacrylate alone is obtained. On the other hand, when the glycidyl methacrylate content is 30 mol% or more, the sensitivity is excellent but the adhesion to the substrate may be poor.

The catalyst used for epoxy ring-opening addition includes tertiary amines such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine, tri-n-octylamine, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide. And the like, alkylureas such as tetramethylurea, alkylguanidines such as tetramethylguanidine, phosphine compounds such as triphenylphosphine, and salts thereof. These may be used alone or in combination of two or more. These catalysts are preferably used in an amount of 0.01 to 10% by weight, 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 when the amount exceeds 10% by weight, the properties of the obtained curable resin composition are inferior.

A solvent can be used in the reaction. The solvent that can be used is not particularly limited, for example, benzene, toluene, aromatic hydrocarbons such as xylene, methanol, ethanol, alcohols such as 2-propanol, acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, Ethers such as diethyl ether, dibutyl ether and dioxane, ethyl acetate, isobutyl acetate, esters such as ethylene glycol monoacetate, propylene glycol monoacetate and dipropylene glycol monoacetate, ethylene glycol monoalkyl ethers and diethylene glycol monoalkyl ethers Propylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ethers, butylene glycol monoalkyl ethers,
Amides such as ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, dimethylformamide and dimethylacetamide, carbon tetrachloride, and chloroform And the like. You may use these individually or in mixture of 2 or more types.

The acid value of the obtained modified copolymer (A) is 5
It is preferably in the range of 0 to 150 KOHmg / g. When the acid value is less than 50 KOHmg / g, it is difficult to remove the uncured resin composition with a dilute alkaline aqueous solution,
This is because if the KOHmg / g is exceeded, the cured film may have poor moisture resistance and electrical properties.

The weight average molecular weight of the modified copolymer (A) is
Generally, the weight average molecular weight is preferably in the range of 10,000 to 150,000 when used in a solder resist or an etching resist, although it depends on the use. In particular, the weight average molecular weight is preferably in the range of 10,000 to 40,000 for better developability in applications where the coating film thickness is 30 μm or less such as solder resist and etching resist. Further, in an application such as a printing plate having a coating film thickness of about 100 μm, the weight average molecular weight is 100,000 to 15 in order to emphasize the sensitivity.
It is preferably in the range of 10,000. In any case, if the weight average molecular weight is less than 10,000, the tack-free performance may be poor, the moisture resistance of the coating film after exposure may be poor, and film slippage may occur during development, resulting in a large deterioration in resolution. on the other hand,
If the weight average molecular weight exceeds 150,000, the developability will be significantly deteriorated and the storage stability will be poor.

Examples of the photopolymerization initiator (B) usable in the present invention include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone and diethoxy. Acetophenone, diphenyl disulfite, etc. can be illustrated, and these can be used individually or in mixture of 2 or more types. The amount of the photopolymerization initiator added is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the modified copolymer, and a synergistic agent for enhancing conversion of light absorption energy into a polymerization initiation free radical, for example, A tertiary amine can be used together. In addition, when the curable resin composition of the present invention is cured by electron beam irradiation, it is not necessary to add a photopolymerization initiator.

The diluting monomer or oligomer (C) usable in the present invention has a radical-polymerizable double bond represented by an acrylic acid ester or methacrylic acid ester compound, a vinyl aromatic compound, an amide unsaturated compound and the like. A compound can be illustrated. Examples of acrylic acid ester or methacrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
(Meth) acrylic acid alkyl esters such as pentyl (meth) acrylate and hexyl (meth) acrylate,
2-Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate and other (meth) acrylic acid esters having a hydroxyl group, methoxydiethylene glycol (meth ) Alkoxy such as acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol # 400- (meth) acrylate (Meth) acrylates, 1,6
-Difunctional (meth) acrylic acid esters such as hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trifunctional (meth) acrylic acid esters such as trimethylolpropane tri (meth) acrylate, etc. It can be illustrated. Examples of the vinyl aromatic compound include styrene, vinyl toluene, and α-methylstyrene. Examples of the amide unsaturated compound include acrylamide and methacrylamide. Examples of the oligomer include (meth) acrylates of polyester polyols, (meth) acrylates of polyether polyols, adducts of polyepoxy and (meth) acrylic acid, and polyols containing hydroxy (meth) ) Resins into which acrylate is introduced. The amount of the diluting monomer or oligomer is the amount necessary for the modified copolymer (A),
For example, it can be blended in the range of more than 0 and 300 parts by weight, preferably more than 0 and 100 parts by weight. When the amount of the diluted monomer and oligomer exceeds 300 parts by weight, the feature of harmony between tack-free performance and adhesion performance of the curable resin composition of the present invention is reduced.

The curable resin composition of the present invention may contain the following epoxy compounds. Examples of the unsaturated group-containing epoxy compound include unsaturated group-containing epoxy compounds such as epoxidized polybutadiene and epoxidized butadiene styrene block copolymer, and "Epolide PB" and "ESBS" manufactured by Daicel Chemical Industries Ltd. Commercially available products can be used. As the alicyclic epoxy resin, "Celoxide 2021" manufactured by Daicel Chemical Industries, Ltd.,
"EHPE"; Mitsui Petrochemical Co., Ltd. "Epomic VG
-3101 "; Yuka Shell Epoxy Co., Ltd." E-10 "
31S ";" TETRAD- "manufactured by Mitsubishi Gas Chemical Co., Inc.
"X", "TETRAD-C"; manufactured by Nippon Soda Co., Ltd., "EP
B-13 "," EPB-27 ", etc. can be used. "CP-50M" and "CP-50" manufactured by NOF CORPORATION, which are copolymers of glycidyl methacrylate and styrene, and copolymers of glycidyl methacrylate, styrene and methyl methacrylate, as copolymerization type epoxy resins.
S ", a copolymer of glycidyl methacrylate and cyclohexylmaleimide, or the like can be used. An epoxidized resin having another special structure may be used.
As the novolac type epoxy resin, those obtained by reacting novolaks obtained by reacting phenols such as phenol, cresol, halogenated phenols and alkylphenols with formaldehyde under an acidic catalyst with epichlorohydrin and / or methyl epichlorohydrin, The commercially available product, “EOCN” manufactured by Nippon Kayaku Co., Ltd.
-103 "," EOCN-104S "," EOCN-1 "
020 "," EOCN-1027 "," EPPN-20 "
1 "," BREN-S ":" DEN "manufactured by Dow Chemical Company
-431 "and" DEN-439 ":" N-73 "and" VH-4150 "manufactured by Dainippon Ink and Chemicals, Inc. can be used. As the bisphenol type epoxy resin, those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin, and the condensates of diglycidyl ether of bisphenol A with the above bisphenols and epichlorohydrin And the commercially available products obtained by reacting with, are "Epicoat 1004" and "Epicoat 100" manufactured by Yuka Shell Co., Ltd.
2 ";" DER-330 "," DER "manufactured by Dow Chemical Company
-337 "can be used. "EPPN-501" and "EPPN-502" manufactured by Nippon Kayaku Co., Ltd. are used as products obtained by reacting with epichlorohydrin and / or methylepichlorohydrin such as trisphenolmethane and triscresolmethane, and commercial products thereof. be able to. Also, tris (2,3-epoxypropyl) isocyanurate and biphenyl diglycidyl ether can be used. These epoxy resins may be used alone or in combination of two or more. The blending amount of these epoxy compounds is the modified copolymer (A) 10
It is preferably within the range of 100 parts by weight with respect to 0 parts by weight. When the amount of the epoxy compound is more than 100 parts by weight, the characteristics of the obtained curable resin composition are reduced.

The curable resin composition of the present invention may contain a thermal polymerization inhibitor, a surfactant, a light absorber, a thixotropic agent, a dye, a pigment and the like as other additives, if necessary. . Further, a thermoplastic resin, a thermosetting resin or the like can be blended.

The curable resin composition of the present invention can be applied as a thin film on a substrate and cured. Spraying, brushing, roll coating, curtain coating, electrodeposition coating, electrostatic coating and the like are used as a method of forming a thin film.

When the curable resin composition of the present invention is used as one component of a liquid resist or a dry film, the curable resin composition can be applied onto a substrate and then cured by light. "Light" is a high-pressure mercury lamp,
Light such as ultraviolet light, EB, laser light and the like can be used. When used as one component of a liquid resist, it can be cured by heat. The curing conditions may be 100 to 200 ° C. and 1 to 90 minutes. Curing is preferably performed in an inert gas atmosphere, but curing can also be performed in an air atmosphere.

The curable resin composition according to the present invention can be used as a resist material for a printed wiring board, a resist ink, a pigment resist ink for a color filter, a semiconductor encapsulant, an ink, a plastic paint, a paper print, a film coating, and a furniture coating. And the like, and various industrial fields such as insulating varnishes, insulating sheets, and laminated plates in the field of FRP, lining, and electronics.

[0039]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

(Measurement Items and Measuring Method) (1) Ink State After preparation of the solder resist ink, the ink was allowed to stand at 40 ° C. for 3 months, and the change in ink viscosity was evaluated according to the following criteria. A: Almost no thickening of ink was observed. X: Thickening of ink. (2) Tack-free performance The tack-free performance was evaluated according to the following criteria by touching the finger after drying the solder resist. ◯: No tack Δ: Slight tack ×: Tack (3) Developability Developability was evaluated by the following criteria for developability with a 1% sodium carbonate aqueous solution. In the present invention, being soluble in a dilute alkaline aqueous solution means that the developability is within 30 seconds. ◯: Development is possible within 20 seconds. Δ: Development is possible within 20 to 30 seconds. X: It is necessary to exceed 30 seconds. (4) Sensitivity The sensitivity was evaluated using a 21-step step tablet manufactured by Stoffer. (5) Adhesion Adhesion was determined by the JI
A peeling test using a cellophane tape was performed according to SD0202. ◯: 100/100 Δ: 50/100 to 99/100 ×: 0/100 to 49/100 (6) Solder heat resistance The solder heat resistance is the state of the solder resist film after being immersed in a solder bath at 260 ° C. for 20 seconds. Was visually evaluated. ◯: There is no abnormality in the coating film Δ: Swelling and peeling are slightly observed in the coating film ×: Swelling and peeling are observed in the coating film

(Synthesis Example 1) A 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 300 g of dipropylene glycol monomethyl ether ("MFDG" manufactured by Nippon Emulsifier Co.). t
-Butyl peroxy 2-ethylhexanoate ("Perbutyl O" manufactured by NOF CORPORATION) was introduced, and the temperature was raised to 95 ° C. Then, 124 g of methacrylic acid, 196 g of methyl methacrylate, and 2,2'-azobis ( 2-Methylbutyronitrile) ("ABN-E" manufactured by Japan Hydrazine Industry Co., Ltd.)
Both 6.4 g and 200 g of MFDG were added dropwise over 3 hours. After dropping, the mixture was aged for 4 hours to synthesize a trunk polymer having a carboxyl group. Next, 79 g of glycidyl methacrylate (“Blenmer G” manufactured by Mitsubishi Rayon Co., Ltd.), 101 g of 3,4-epoxycyclohexylmethyl acrylate (“Cyclomer A200” manufactured by Daicel Chemical Industries, Ltd.), and triphenylphosphine 4 were added to the above trunk polymer solution.
g and methyl hydroquinone (1.0 g) were added and reacted at 100 ° C. for 10 hours. The reaction was performed under a mixed atmosphere of air / nitrogen. The obtained copolymer is referred to as a copolymer (1). The acid value of the copolymer (1) is 100 KOHmg / g, and the double bond equivalent (resin weight per mol of unsaturated group) is 45.
0, the weight average molecular weight was 20,000.

(Synthesis Examples 2 to 10) The compounds shown in Table 1 were used and operated in the same manner as in Synthesis Example 1 to obtain copolymers (2) to copolymers (10).

[0043]

[Table 1]

Example 1 100 parts by weight of the copolymer (1) (solid content) and 40 parts by weight of dipentaerythritol hexaacrylate (epoxy equivalent 220) cresol novolac type epoxy resin (Epiclon N695 manufactured by Dainippon Ink and Chemicals, Inc.). 20 parts by weight, 2 parts by weight of phthalocyanine green, and 15 parts by weight of "Irgacure 907" manufactured by Ciba-Geigy Co., Ltd. as an initiator, and then kneaded with a three-roll mill to obtain a viscous ink composition. The obtained ink composition was applied onto a patterned substrate with a bar coater to a thickness of 20 to 30 μm, and dried with a blow dryer at 80 ° C. for 20 minutes. Thereafter, a negative film was brought into close contact and irradiated with a light amount of 1,000 mJ / cm ² .
Thereafter, the film was developed with a 1% aqueous sodium carbonate solution, and the obtained coating film was cured in a blast oven at 150 ° C. for 30 minutes to obtain a solder resist film. After leaving this solder resist film at room temperature for 1 month, the ink state, tack-free performance after drying,
The developability, sensitivity, adhesion, and solder heat resistance were evaluated. Table 2 shows the results.

(Examples 2 to 8) Using the copolymers (2) to (8) obtained in Synthesis Examples 2 to 8, Example 1 was used.
The same operation as described above was performed to obtain a viscous ink composition. Using the obtained ink composition, the ink state, tack-free performance after drying, developability, sensitivity, adhesion, and solder heat resistance were evaluated in the same manner as in Example 1. Table 2 shows the results.

(Comparative Examples 1 and 2) Using the copolymers (9) and (10) obtained in Synthesis Examples 9 and 10, Example 1 was used.
The same operation as described above was performed to obtain a viscous ink composition. Using the obtained ink composition, the ink state, tack-free performance after drying, developability, sensitivity, adhesion, and solder heat resistance were evaluated in the same manner as in Example 1. Table 2 shows the results.

[0047]

[Table 2]

[0048]

EFFECTS OF THE INVENTION According to the present invention, a curable resin composition having excellent tack-free performance and excellent adhesion performance is provided by using an inexpensive material. The curable resin composition of the present invention is particularly useful for printed wiring boards related to electronics, L
It is useful as an SI relation, a color filter accompanying a liquid crystal, a resist material such as a sealant, and a binder resin for a resist ink. Since it is inexpensive and has excellent solder heat resistance, it can be used as a photoresist for forming a permanent mask.

Claims (7)

[Claims] 1. A curable resin composition which is soluble in a dilute alkaline aqueous solution and comprises the following (A), (B) and (C). (A) Containing glycidyl methacrylate and alicyclic epoxy group in a part of carboxyl groups of a copolymer obtained from (meth) acrylic acid ester and a compound containing an unsaturated group and having at least one carboxyl group Modified copolymer to which unsaturated compound is added, (B) photopolymerization initiator, (C) diluted monomer or oligomer 2. A curable resin composition containing the following (A), (B), (C) and (D) and soluble in a dilute alkaline aqueous solution. (A) Containing glycidyl methacrylate and alicyclic epoxy group in a part of carboxyl groups of a copolymer obtained from (meth) acrylic acid ester and a compound containing an unsaturated group and having at least one carboxyl group Modified copolymer to which unsaturated compound is added, (B) photopolymerization initiator, (C) diluted monomer or oligomer, (D) epoxy compound 3. The modified copolymer (A) has an acid value of 50 to 1.
It exists in the range of 50, The curable resin composition of Claim 1 or 2 characterized by the above-mentioned. 4. The addition ratio of glycidyl methacrylate and the alicyclic epoxy group-containing unsaturated compound constituting the modified copolymer (A) is 30/70 to 70/30 mol%. 4. The curable resin composition according to any one of 3 to 3. 5. The curable resin composition according to claim 1, wherein the unsaturated compound containing an alicyclic epoxy group is 3,4-epoxycyclohexylmethyl (meth) acrylate. 6. The photocurable resin composition according to claim 1, which is used as one component of a liquid resist and a dry film. 7. The thermosetting resin composition according to claim 1, which is used as one component of a liquid resist.