JPH08160616A - Manufacture of resist resin composition - Google Patents

Abstract

PURPOSE: To manufacture a resist resin composition excellent in photosensitivity, excellent in the alkali developing property of an unhardened film, excellent in the adhesiveness, electric insulation, solder heat resistance, solvent resistance, alkali resistance, acid resistance, plating resistance of an obtained hardened film, and excellent as a solder resist in particular. CONSTITUTION: A monomer having one or more ethylene unsaturated groups and one carboxyl group is additionally reacted with the epoxy group in a copolymer constituted of a (metha)acrylate having one epoxy group and one or more kinds of monomers having one ethylene unsaturated group other than the (metha)acrylate, then a bivalent carboxylic acid anhydride is additionally reacted with the hydroxyl group in an additional reaction product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resist resin which can be used in the production of printed wiring boards or precision metal processing, and more particularly to a method for producing a resist resin useful as a solder resist. The resist consisting of the resin obtained by can be applied to the surface of a substrate such as a printed wiring board without generating bubbles, and the film cured with active energy rays is excellent in heat resistance, electric insulation and solvent resistance. . In this specification, acrylate and / or methacrylate is referred to as (meth) acrylate, and acrylic acid and / or methacrylic acid is referred to as (meth) acrylic acid.

[0002]

2. Description of the Related Art A solder resist is applied to a printed circuit board or the like to form a heat-resistant and insulative film, and has a function of preventing bridges and stabilizing circuit insulation when soldering components to the printed circuit board. Is. Conventionally, solder resist has been used by the method of forming a pattern film by screen printing, but as the density of printed wiring boards becomes higher, circuit pattern exposure by patterning by screen printing (edge cuts) and unnecessary parts are unnecessary. Fogging on the face has become a problem.

In order to solve the above problem, a photo solder resist for forming a pattern film by a photoengraving method,
Alternatively, a dry film type solder resist has been developed. Among them, the method of using the photo solder resist is to apply a liquid resist material to the entire surface of the base material with a roll coater or the like, and then form a pattern of the cured film by photoengraving method. In addition, the embeddability between circuits is also good. For these reasons, the demand for photo solder resist has increased in recent years. In the photo solder resist, an uncured portion, that is, an unexposed portion is washed away with a developing solution, and an organic solvent or an alkaline aqueous solution is used as the developing solution, but the latter is safer and saves resources. Therefore, it is the mainstream.

[0004]

As an alkali developing type photo solder resist, a photo solder resist made of a resist resin obtained by adding an acid anhydride to novolak type epoxy acrylate is known (Japanese Patent Laid-Open No. 6-58242).
1-243869, JP-A-6-208224, etc.).
However, these photosolder resists have the following properties: alkali developability at low light exposure, adhesion of cured film to be obtained, electrical insulation, solder heat resistance, solvent resistance, alkali resistance, acid resistance and plating resistance. The overall balance of physical properties is not sufficient. The inventors of the present invention are resist resins having excellent photosensitivity, and the uncured film thereof has excellent alkali developability, and the resulting cured film has adhesion, electrical insulation, solder heat resistance, solvent resistance, and alkali resistance. In order to find out a method for producing a resin composition for resist which is excellent in acid resistance and plating resistance, particularly a method for producing a resin composition for resist which is excellent as a solder resist, the inventors conducted extensive studies.

[0005]

Means for Solving the Problems The inventors of the present invention have completed the present invention as a result of extensive studies to solve the above problems. That is, the first invention of the present invention comprises (meth) acrylate having one epoxy group and one or more kinds of monomers having one ethylenically unsaturated group other than the (meth) acrylate. After the addition reaction of a monomer having one or more ethylenically unsaturated groups and one carboxyl group to the epoxy group in the copolymer, the hydroxyl group in the addition reaction product is further A method for producing a resist resin composition, which comprises subjecting a divalent carboxylic anhydride to an addition reaction, and a second invention is a (meth) acrylate having one epoxy group and a method other than the (meth) acrylate. Weight average molecular weight of 3,000 to 150,0 consisting of at least one monomer having one ethylenically unsaturated group
After the addition reaction of the monomer having at least one ethylenically unsaturated group and one carboxyl group with the epoxy group in the copolymer of No. 00, the hydroxyl group in the addition reaction product is added. The method for producing a resist resin composition according to the first aspect of the invention is characterized by obtaining an addition product with an oxidation amount of 20 to 150 mgKOH / g by further performing an addition reaction with a divalent carboxylic acid anhydride. A photo solder resist comprising the resist resin composition obtained by the production method of the first invention or the second invention, and the fourth invention further contain an epoxy resin, an epoxy resin curing agent, a photopolymerization initiator and a diluent. It is a photo solder resist of the third invention. Hereinafter, the present invention will be described in detail.

In the production method of the present invention, as a copolymer serving as the skeleton of the resist resin, a (meth) acrylate having one epoxy group and a monomer having one ethylenically unsaturated group are used. A copolymer (hereinafter referred to as copolymer A) is used.

As the (meth) acrylate having one epoxy group, various ones can be used, for example, glycidyl (meth) acrylate, a compound represented by the following chemical formula 1 [as a commercial product, CYCLOMER A-200 manufactured by Daicel Chemical Co., Ltd.,
The same M-100 etc.] etc. are mentioned.

[0008]

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(In the chemical formula 1, R is hydrogen or a methyl group.)

As the monomer having one ethylenically unsaturated group, various monomers other than the above-mentioned (meth) acrylate having one epoxy group can be used.
Examples thereof include styrene, acrylonitrile, methacrylonitrile, vinyl acetate, and (meth) acrylates other than the (meth) acrylate having one epoxy group. Specific examples of the (meth) acrylate include alkyl (meth) acrylates having 1 to 12 carbon atoms,
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth )
Examples thereof include acrylate, 2-ethoxyethyl (meth) acrylate and isobornyl (meth) acrylate. The monomer having one ethylenically unsaturated group is preferably styrene and / or alkyl (meth) acrylate, and more preferably styrene and / or methyl (meth) acrylate, ethyl (meth) acrylate, butyl ( A lower alkyl (meth) acrylate such as (meth) acrylate or isobutyl (meth) acrylate.

In the copolymer A, the ratio of the (meth) acrylate having one epoxy group and the monomer having one ethylenically unsaturated group is 1 in the molecule based on the total amount of these. The (meth) acrylate having an epoxy group is preferably 2 to 80% by weight, more preferably 10 to 50% by weight. When this proportion is less than 2% by weight, the proportion of the epoxy groups introduced into the copolymer A is small and the proportion of carboxyl groups in the finally obtained resist resin composition is small, so that the alkali The solubility may become insufficient, or the ratio of (meth) acrylic groups in the resist resin composition may decrease, which may lower the sensitivity to active energy rays. The glass transition temperature of the cured product of the obtained composition may be too low, and tack may remain on the surface of the cured product of the resist resin composition.

The copolymer A is 3,000 to 150,000.
It is preferred to have a weight average molecular weight of 0. When the weight average molecular weight is less than 3,000, the sensitivity of the resulting resist resin composition to active energy rays,
Dispersion stability may not be sufficient, while 150,00
When it exceeds 0, the alkali solubility of the resulting resist resin composition may be insufficient.
In addition, in this invention, a weight average molecular weight means the weight average molecular weight of polystyrene conversion.

The copolymerization of the (meth) acrylate having one epoxy group and the monomer having one ethylenically unsaturated group can be carried out by various methods. For example,
A general polymerization method such as solution polymerization, which comprises heating in a polymerization solvent in the presence of a polymerization initiator, can be mentioned. Among these, 1
After heating a solution consisting of (meth) acrylate having one epoxy group, a monomer having one ethylenically unsaturated group, a polymerization solvent and a polymerization initiator to a predetermined temperature, and then adding to this solution, A method of dropping a solution consisting of a (meth) acrylate having one epoxy group, a monomer having one ethylenically unsaturated group, a polymerization solvent and a polymerization initiator suppresses the amount of unreacted monomer. However, the copolymerization ratio of the monomers in the obtained copolymer can be kept constant, which is preferable.
The reaction temperature is selected depending on the decomposition temperature and half-life of the polymerization initiator used, the boiling point of the polymerization solvent, and is usually 50.
A temperature of ~ 120 ° C is suitable. If the reaction temperature is less than 50 ° C, the reaction does not proceed sufficiently, while if it exceeds 120 ° C, the stability of the copolymer A obtained may be problematic. Various types of polymerization initiators can be used,
A general azonitrile-based polymerization initiator is preferred because it is easy to use. Examples of the azonitrile-based polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) and 2,2′-azobis (2,4-dimethyl). Valeronitrile) and the like. As a use ratio of the polymerization initiator, the total amount of the (meth) acrylate having one epoxy group and the monomer having one ethylenically unsaturated group is 10
It is preferably 0.1 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, based on 0 parts by weight. The polymerization solvent is
Various substances can be used as long as they can dissolve the produced copolymer A. For example, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, cellosolve acetate, acetic acid esters such as methyl propylene glycol acetate, carbitol acetate and ethyl carbitol acetate, and ketones such as acetone and methyl ethyl ketone. Is mentioned.

To the copolymer A, a monomer having at least one ethylenically unsaturated group and at least one carboxyl group is added to the epoxy group to undergo an addition reaction. Polymer B). Examples of the monomer include
(Meth) acrylic acid, crotonic acid, cinnamic acid, oligomers of dimers or more by Michael addition of (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate and amber Monohydroxyethyl acid (meth)
Acrylate etc. are mentioned. The addition reaction ratio of the copolymer A and the monomer having one or more ethylenically unsaturated groups and one carboxyl group is 1 or more ethylene per 1 mol of the epoxy group in the copolymer A. The proportion of the monomer having a polyunsaturated group and one carboxyl group is preferably 0.9 to 1.1 mol, more preferably the same amount. When the addition reaction ratio is less than 0.9 mol, the resulting copolymer B is obtained.
Since the unreacted epoxy group remains in the inside, crosslinking may occur between molecules in the reaction with the divalent carboxylic acid anhydride described below, which may cause gelation. If it exceeds the molar amount, a monomer having one or more ethylenically unsaturated groups and one carboxyl group is wasted, which is not economically advantageous.

The reaction of the copolymer A with a monomer having one or more ethylenically unsaturated groups and one carboxyl group is
The conditions usually used for the addition reaction of an epoxy group and a carboxyl group may be used, and examples thereof include a method of stirring and heating in the presence of a catalyst. Examples of the catalyst include tertiary amines such as N, N-dimethylbenzylamine, triethylamine and N, N-dimethylaniline, quaternary ammonium salts such as tetradiethylammonium chloride, tetrabutylammonium bromide and benzyltrimethylammonium chloride, diethylammonium chloride. And secondary amine hydrochlorides, and phosphorus compounds such as triphenylphosphine. A preferable ratio of the catalyst is a reaction solution 10 comprising the copolymer A and a monomer having one or more ethylenically unsaturated groups and one carboxyl group.
The amount is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, based on 0 parts by weight. The reaction temperature is preferably 70 to 140 ° C. If the reaction temperature is less than 70 ° C, the reaction does not proceed sufficiently, while if it exceeds 140 ° C, the stability of the copolymer B obtained may be problematic. When an amine is used as a catalyst, it is preferable to wash the reaction solution with an acidic aqueous solution after the reaction to extract and remove the amine, because the storage stability of the product can be further improved.

In the copolymer B, a divalent carboxylic acid anhydride is further added to the hydroxyl group formed by the reaction between the epoxy group and the carboxyl group. As the dicarboxylic acid anhydride, phthalic anhydride and its derivatives,
Examples thereof include tetrahydrophthalic anhydride and its derivative, hexahydrophthalic anhydride and its derivative, succinic anhydride, and maleic anhydride. The reaction amount of the divalent carboxylic acid anhydride in this reaction is such that the acid value of the resulting resist resin composition is 20 to 150 mgKOH / g.
The amount is preferably Oxidation is 20mgKOH
If it is less than 100 g / g, the alkali solubility of the cured film of the obtained resin composition is insufficient, while 150 mgKOH
If it exceeds / g, the water resistance and alkali resistance of the cured film of the obtained resin composition may be poor.

The addition reaction of the copolymer B and the divalent carboxylic acid anhydride may be carried out under the conditions usually carried out in the reaction of a hydroxyl group and a carboxyl group, and examples thereof include a method of stirring and heating in the presence of a catalyst. As the catalyst, the above-mentioned copolymer A
And those similar to those used in the reaction of the monomer having one or more ethylenically unsaturated groups with one carboxyl group. In the addition reaction, the catalyst used in the production of the copolymer B can be used as it is without further adding a catalyst to the reaction solution. The amount is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the reaction liquid containing the copolymer B and the divalent carboxylic acid anhydride. The reaction temperature is 70 ° C
140 ° C. is preferred. If the reaction temperature is less than 70 ° C, the reaction does not proceed sufficiently, while if it exceeds 140 ° C, the resulting resist resin may have a problem in stability. When an amine is used as the catalyst, washing the reaction solution with an acidic aqueous solution after the reaction to extract and remove the amine can further improve the storage stability of the product, and further mix with an epoxy resin described below. In that case, the storage stability of the composition can be greatly improved.

The resin composition obtained by the first or second invention of the present invention is used as a resist in many fields such as production of printed wiring boards or precision metal processing,
Particularly useful as the solder resist of the third invention,
In this case, a photopolymerization initiator and a diluent are usually added to the resin composition.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and other benzoins and their alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy. 2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1
Acetophenones such as-[4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone And the like anthraquinones; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4
Examples include thioxanthones such as diisopyrthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone or xanthones. These photopolymerization initiators can be used alone or in combination with a benzoic acid-based or amine-based light weight initiation promoter. The photopolymerization initiators can be used alone or in combination of two or more. The preferred amount of the photopolymerization initiator used is 0.2 to 20 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the resin composition obtained in the first invention.

As the diluent, an organic solvent and / or a UV-curable monomer described below with reference to specific examples can be used. The diluent is preferably used in an amount of 10 to 100 parts by weight per 100 parts by weight of the total amount of the resin composition and the photopolymerization initiator obtained in the first invention. When the amount of the diluent used is less than 10 parts by weight, the viscosity of the resulting resist is too high and the coating property is liable to be impaired. It becomes difficult to apply.

Examples of the organic solvent include acetic acid esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolve, cellosolve acetate and cellosolve such as butyl cellosolve, and Examples thereof include carbitols such as carbitol, carbitol acetate, butyl carbitol and ethyl carbitol acetate, and cellosolves or carbitols are preferable.

As the UV-curable monomer, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, mono- or di (meth) acrylate of ethylene glycol, Mono (di) (meth) acrylates of glycols, such as mono (meth) acrylates of methoxyethylene glycol, mono- or di (meth) acrylates of tetraethylene glycol, and mono- or di (meth) acrylates of tripropylene glycol, trimethylol Examples include triol or tetraol (meth) acrylic acid adducts such as propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate.

The resin composition obtained according to the first invention or the second invention is suitable as a resist by itself because it has a property of being cured by active energy rays and the cured coating film has excellent various physical properties. Although suitable as a photo solder resist, a composition comprising the resin composition obtained by the first or second invention, which is the fourth invention of the present invention, an epoxy resin, an epoxy resin curing agent, a photopolymerization initiator and a diluent. The thing is very suitable as a photo solder resist.

The epoxy resin used in the fourth invention is preferably a cresol novolac epoxy resin, a bisphenol A type epoxy resin, an epoxy resin having an isocyanuric acid skeleton, and the like. Specific examples of the epoxy resin are as follows. Cresol novolac epoxy resin: Sumi Epoxy ESCN220HH manufactured by Sumitomo Chemical Co., Ltd., Epototo YDCN704, Epotote YDP manufactured by Tohto Kasei Co., Ltd.
N638, DEN-431, DEN made by Dow Chemical Company
-438 etc. Bisphenol A type epoxy resin: Epi-coat 828, Epi-coat 1001 of Yuka Shell Epoxy Co., Ltd., Epotote YD128 of Toto Kasei Co., Ltd., etc. Epoxy resin having isocyanuric acid skeleton: TEPIC manufactured by Nissan Kagaku Co., Ltd. The preferred amount of the epoxy resin used is 10 to 100 parts by weight per 100 parts by weight of the resin obtained in the first invention.

Examples of the epoxy resin curing agent include dicyandiamide, melamine, benzoguanamine, acetoguanamine, 2-methylimidazole and their derivatives. The amount of curing agent used is 100
Appropriately 1 to 10 parts by weight per part by weight.

As the photopolymerization initiator, the same ones as described above can be used, and the preferable amount thereof is 0.2 to 20 parts by weight, more preferably 100 parts by weight of the resin composition obtained in the first invention. It is 1 to 10 parts by weight.

As the diluent, the same ones as described above can be used,
In this case, the preferable amount of use is 10 to 100 parts by weight per 100 parts by weight of the total amount of the resin composition obtained in the first invention, the epoxy resin, the curing agent for the resin and the photopolymerization initiator. When the amount of the diluent used is less than 10 parts by weight, the viscosity of the obtained photo solder resist is too high and the coating property is apt to be impaired. Etc. are difficult to apply.

The resist comprising the resin composition obtained by the first invention or the second invention further comprises, if necessary, a filler such as barium sulfate, silicon oxide, talc, clay or calcium carbonate, phthalocyanine blue, phthalocyanine. Coloring pigments such as green, titanium oxide or carbon black, various additives such as adhesion promoters or leveling agents, or hydroquinone, hydroquinone monomethyl ether, tertiary butyl catechol, phenothiazine or N-nitrosophenylhydroxylamine aluminum salt. A polymerization inhibitor may be added.

The method of using the resist resin composition obtained by the present invention may be a conventionally used method. Specifically, there are the following methods, for example. The resin composition obtained by the present invention is printed on a substrate by screen printing or the like, a resist pattern film is placed on the substrate, and the composition is cured by irradiation with active energy rays such as ultraviolet rays. The uncured portion is developed by dissolving it in an alkaline aqueous solution such as an aqueous sodium carbonate solution. When an epoxy resin is added to the composition, heating is further performed after development.

[0030]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. In each example, parts represent parts by weight, and the unit of acid value is mgKOH / g.

Example 1 Methyl methacrylate 60 parts, butyl methacrylate 2
A mixture of 3 parts and 17 parts of glycidyl methacrylate was used as a mixed monomer. In a four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen substitution and a stirrer, 15 parts of the mixed monomer and 15 toluene
0 parts and 1 part of 2,2′-azobisisobutyronitrile were added, and the temperature was raised to 90 ° C. while blowing nitrogen, and 85 parts of the mixed monomer and 25 parts of 2,2′-azobisisobutyronitrile were added to toluene. Initiator solution 31 in which 6 parts of ronitrile was dissolved
Parts were continuously dropped for 6 hours to carry out a polymerization reaction to obtain a solid content of 35% by weight and a styrene-converted weight average molecular weight of 7,000.
A copolymer solution (A-1) was obtained. Copolymer solution (A-
1) To 275 parts, 8.6 parts of acrylic acid, 1.3 parts of triethylamine and 0.06 part of hydroquinone were added, and the mixture was stirred at 110 ° C. for 6 hours while blowing air to obtain a liquid (B-1) having an acid value of 1. Obtained. To this liquid (B-1), 17.3 parts of tetrahydrophthalic anhydride was added and stirred at 80 ° C. for 4 hours. After cooling, the reaction mixture was charged with 120 parts of toluene, 75
Part of 10% ammonium sulfate aqueous solution was poured in, stirred for 30 minutes, transferred to a separatory funnel and allowed to stand to separate an oil layer and an aqueous layer, and then the aqueous layer was removed. The oil layer was transferred to the flask again, and the solvent was distilled off under reduced pressure.
g of ethyl carbitol acetate was added and dissolved,
250 parts of liquid (C-1) was obtained. The solid content of (C-1) was 52%, and the acid value was 26 (51 in terms of solid content). 100 parts of the above resin (C-1), dipentaerythritol hexaacrylate [Aronix M- manufactured by Toagosei Co., Ltd.
400] 10 parts, 25 parts as epoxy resin, TEPIC manufactured by Nissan Chemical Industries, Ltd., 2-methyl-1- as photoinitiator
[4- (methylthio) phenyl] -2-morpholino-
5 parts of propan-1-one [Irgacure 907 manufactured by Ciba-Geigy Co., Ltd.], ethyl carbitol acetate 10
, 1 part of phthalocyanine phosphorus, 40 parts of talc, 2 parts of Moderflow [manufactured by Monsanto Co., Ltd.] as a leveling agent, and 2 parts of melamine as an epoxy resin curing agent are kneaded with a three-roll mill to obtain a photo solder resist (D-1). Got

Evaluation The obtained photo solder resist (D-1) was screen-printed on a copper glass epoxy substrate, a through hole substrate and a printed wiring board on which a pattern was formed, and the temperature was set to 80 ° C.
It was dried for 30 minutes and used as a test piece. None of them touched with fingers. Of these test pieces, the copper glass epoxy board has a Kodak step tablet N
o. 2 (21 steps) are placed, the through-hole substrate is left as it is, and the resist pattern film is placed on the printed wiring board.
Irradiation was performed at mJ / cm ² . Next, after developing with a 1% sodium carbonate aqueous solution for 30 seconds, the mixture was heat-cured at 150 ° C. for 30 minutes. As a result, the photosensitivity of the copper glass epoxy substrate was 9 in the step tablet stage, the developability of the through-hole substrate was good and the holes were not filled, and the pencil hardness and the adhesion of the printed wiring board were evaluated. It was Further, heat resistance test in a solder bath at 260 ° C. for 30 seconds, three times, and in methylene chloride, 10% sodium hydroxide, 10% sulfuric acid, 1
A chemical resistance test was carried out by immersing in 0% hydrochloric acid for 1 hour. or,
Gold plating resistance and insulation resistance after moisture absorption were also evaluated. The results are shown in Tables 1 to 3.

Example 2 Methyl methacrylate 57 parts, butyl methacrylate 2
A mixture of 0 part and 23 parts of glycidyl methacrylate was used as a mixed monomer. In a four-necked flask similar to that of Example 1, 15 parts of the mixed monomer, 150 parts of toluene,
2,2'-azobis (2-methylbutyronitrile) was added to 1
30 parts of an initiator solution prepared by dissolving 5 parts of 2,2'-azobis (2-methylbutyronitrile) in 85 parts of the mixed monomer and 25 parts of toluene was added. Polymerization reaction was carried out by continuously dropping the mixture over time to obtain a copolymer solution (A-2) having a solid content of 35% by weight and a styrene-equivalent weight average molecular weight of 10,000. To 275 parts of the copolymer solution (A-2), 11.7 parts of acrylic acid,
Triethanolamine (1.3 parts) and hydroquinone monomethyl ether (0.06 parts) were added, and the mixture was stirred at 110 ° C for 6 hours while blowing air to obtain a liquid (B-2) having an acid value of 1. To this liquid (B-2), 17.3 parts of hexahydrophthalic anhydride was added and stirred at 80 ° C. for 4 hours. After cooling, the reaction solution was post-treated and separated in the same manner as in Example 1 except that 140 parts of toluene and 75 parts of 10% aqueous ammonium sulfate solution were used. After distilling off the solvent in the obtained oil layer under reduced pressure, 135 g of ethyl carbitol acetate was added and dissolved in the obtained resin to obtain 270 parts of liquid (C-2). The solid content of (C-2) is 49.
%, Acid value 33 (64 in terms of solid content), viscosity at 25 ° C. is 7
It was 10,000 cps. A solder resist (D-2) was produced by the same composition and method as in Example 1 except that 100 parts of (C-2) was used. The obtained solder resist (D-2) was evaluated in the same manner as in Example 1.
The results are shown in Tables 1 to 3.

Example 3 A mixture of 55 parts of isobornyl methacrylate, 15 parts of butyl methacrylate and 30 parts of glycidyl methacrylate was used as a mixed monomer. In a four-necked flask similar to that of Example 1, 15 parts of the mixed monomer and 15 parts of toluene
0 part, 1 part of 2,2'-azobisisobutyronitrile was added, the temperature was raised to 90 ° C while blowing nitrogen, and 2,2'-azo was added to 85 parts of the monomer (A-3) and 25 parts of toluene. 31 parts of an initiator solution containing 6 parts of bisisobutyronitrile was continuously added dropwise over 6 hours to carry out a polymerization reaction to obtain a copolymer solution having a solid content of 35% by weight and a styrene-equivalent weight average molecular weight of 8,000 (A- 3) was obtained. Copolymer solution (A-
3) To 275 parts, 15.2 parts of acrylic acid, 1.3 parts of triphenylphosphine and 0.06 part of hydroquinone were added, and the mixture was stirred at 110 ° C. for 6 hours while blowing air, and a liquid having an acid value of 2 (B-3). Got To this liquid (B-3), 20.1 parts of succinic anhydride was added, and the mixture was stirred at 80 ° C for 4 hours. After cooling, the reaction solution was post-treated and separated in the same manner as in Example 1 except that 140 parts of toluene and 75 parts of 10% aqueous ammonium sulfate solution were used. After the solvent in the obtained oil layer was distilled off under reduced pressure, the resin
g of ethyl carbitol was added and dissolved to obtain 270 parts of liquid (C-3). The solid content of (C-3) is 48%,
The acid value is 40 (83 in terms of solid content), the viscosity at 25 ° C is 90,
It was 000 cps. A solder resist (D-3) was produced by the same composition and method as in Example 1 except that 100 parts of (C-3) was used. The obtained solder resist (D-3) was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

Example 4 A mixture of 57 parts of styrene, 20 parts of butyl methacrylate and 23 parts of glycidyl methacrylate was used as a mixed monomer. In a four-necked flask similar to that of Example 1, 15 parts of the mixed monomer, 150 parts of toluene and 2,2′-
An initiator solution in which 1 part of azobisisobutyronitrile was added, the temperature was raised to 90 ° C. while blowing nitrogen, and 5 parts of 2,2′-azobisisobutyronitrile were dissolved in 85 parts of mixed monomer and 25 parts of toluene. Polymerization reaction was carried out by continuously dropping 30 parts over 6 hours to obtain a copolymer solution (A-4) having a solid content of 35% by weight and a styrene-equivalent weight average molecular weight of 7,000.
I got To 275 parts of the copolymer solution (A-4), 11.7 parts of acrylic acid, tetrabutylammonium bromide 1.
3 parts and phenothiazine 0.12 parts were added, and the mixture was stirred at 110 ° C. for 6 hours while blowing air, and a liquid having an acid value of 3 (B-
4) was obtained. 23.4 parts of tetrahydrophthalic anhydride was added to this liquid (B-4), and the mixture was stirred at 80 ° C. for 4 hours. After cooling, the reaction solution was post-treated and separated in the same manner as in Example 1 except that 140 parts of toluene and 75 parts of 10% aqueous ammonium sulfate solution were used. After the solvent in the obtained oil layer was distilled off under reduced pressure, the resin
g of diglyme was added and dissolved, and 270 parts of liquid (C
-4) was obtained. (C-4) has a solid content of 52% and an acid value of 3
3 (64 in solid content), 25 ° C viscosity is 50,000c
It was ps. (C-4) except that 100 parts were used
With the same composition and method as in Example 1, the solder resist (D
-4) was produced. The obtained solder resist (D-
4) was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

Example 5 60 parts of methyl methacrylate, butyl methacrylate 2
A mixture of 3 parts and 17 parts of glycidyl methacrylate was used as a mixed monomer. In a four-necked flask similar to that of Example 1, 20 parts of the mixed monomer, 180 parts of toluene and 1 part of 2,2′-azobisisobutyronitrile were put,
The temperature was raised to 90 ° C. while blowing nitrogen, and 27 parts of an initiator solution prepared by dissolving 2 parts of 2,2′-azobisisobutyronitrile in 80 parts of the mixed monomer and 25 parts of toluene was continuously added dropwise over 4 hours. A polymerization reaction was carried out to obtain a copolymer solution (A-5) having a solid content of 33% by weight and a styrene-equivalent weight average molecular weight of 50,000. Copolymer solution (A-5) 3
Acrylic acid (8.6 parts), triethanolamine (2.6 parts) and hydroquinone (0.06 parts) were added to 05 parts, and the mixture was stirred at 110 ° C for 6 hours while blowing air to obtain a liquid (B-5) having an acid value of 1. It was 17.3 parts of tetrahydrophthalic anhydride was added to this liquid (B-5), and the mixture was stirred at 80 ° C. for 4 hours. After cooling, the reaction solution was post-treated and separated in the same manner as in Example 1 except that 90 parts of toluene and 70 parts of 10% ammonium sulfate aqueous solution were used. After the solvent in the obtained oil layer was distilled off under reduced pressure, the resin
g of propylene glycol monomethyl ether acetate was added and dissolved to obtain 270 parts of liquid (C-5). The nonvolatile content of (C-5) was 45%, the acid value was 23 (51 in terms of solid content), and the viscosity at 25 ° C was 80,000 cps. Example 1 except that 100 parts of (C-5) was used.
A solder resist (D-5) was produced with the same composition and method as described above. The obtained solder resist (D-5) was evaluated in the same manner as in Example 1. The results are shown in Table 1.
~ Shown in 3 above.

Example 6 A mixture of 77 parts of methyl methacrylate and 23 parts of glycidyl methacrylate was used as a mixed monomer. In a four-neck flask similar to that used in Example 1, the mixed monomer 15 was added.
Parts, 150 parts of toluene and 1 part of 2,2′-azobis (2-methylbutyronitrile), while blowing nitrogen, the temperature was raised to 90 ° C., and 2,2 ′ was added to 85 parts of the mixed monomer and 25 parts of toluene. -30 parts of an initiator solution in which 5 parts of azobis (2-methylbutyronitrile) were dissolved was continuously added dropwise for 6 hours to carry out a polymerization reaction, and a solid content was 35% by weight, and a styrene-converted weight average molecular weight of 10,000 was a copolymer weight. A combined solution (A-6) was obtained. To 275 parts of the copolymer solution (A-6), 11.7 parts of acrylic acid, 1.3 parts of triethylamine and 0.06 part of hydroquinone were added, and the mixture was stirred at 110 ° C for 6 hours while blowing air, and a liquid having an acid value of 1 was added. (B-6)
I got To this liquid (B-6), 23.7 parts of hexahydrophthalic anhydride was added and stirred at 80 ° C for 4 hours. After cooling, the reaction solution was post-treated and separated in the same manner as in Example 1 except that 140 parts of toluene and 75 parts of 10% aqueous ammonium sulfate solution were used. After distilling off the solvent in the obtained oil layer under reduced pressure, 135 g of propylene glycol monomethyl ether acetate was added and dissolved in the obtained resin to obtain 270 parts of a liquid (C-6).
The solid content of (C-6) was 50%, the acid value 32 was (solid content conversion 64), and the viscosity at 25 ° C was 50,000 cps.
A solder resist (D-6) was produced in the same composition and method as in Example 1 except that 100 parts of (C-6) was used. The obtained solder resist (D-6) was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3
Shown in

Comparative Example 1 981 parts of cresol novolac type epoxy resin having an epoxy equivalent of 213 [YDCN704P manufactured by Tohto Kasei Co., Ltd.],
After 742 parts of ethyl carbitol acetate, 1.14 parts of phenothiazine and 22.5 parts of benzyldimethylamine were mixed and dissolved at 95 ° C., 338 parts of acrylic acid was added and the reaction was continued for 10 hours. To this, 340 parts (50 mol%) of phthalic anhydride was further added, and the mixture was reacted for 4 hours.
The solid content of the obtained reaction product was 68%, the acid value was 28 (solid content 55), and the viscosity at 25 ° C. was 23000 cps. Hereinafter, this resin is referred to as (A-7). (A-7) 10
A solder resist (D-7) was produced by the same composition and method as in Example 1 except that 0 part was used. The obtained solder resist (D-6) was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0039]

[Table 1]

Each physical property in Table 1 was evaluated by the following methods. a. Dryability: After coating the resist and drying at 80 ° C. for 30 minutes, the tack of the surface of the cured coating film was evaluated by touch with a finger. The results are indicated by the following symbols. ⊚: No tack, ○: Slight tack, Δ: Tack, ×: Remarkably tack. b. Photosensitivity ──── For the coating film coated on the copper glass epoxy substrate, Kodak Step Tablet No. Two
The number of stages evaluated by (21 stages). c. Developability ─── The through hole substrate was observed for hole filling after development. ⊚: No hole filling, ○: Slight hole filling, Δ: 10 to 50% hole filling, ×: Hole filling. d. Pencil hardness: According to the hand scraping method in the test method of JISK-5400. e. Adhesion: According to JIS D-0202 test method (cross-cut test).

[0041]

[Table 2]

The physical properties shown in Table 2 were evaluated by the following methods. f. Soldering heat resistance: According to the test method of JISC-6481, a 30 second float was repeated three times in a solder bath at 260 ° C, and then a peeling test was performed on the coating film with cellophane tape, and peeling of the coating film was observed. ⊚: Not peeled at all, ◯: Slightly peeled, Δ: About 10% peeled, ×: Whole peeled. g. Solvent resistance ─── Test piece in methylene chloride 2
After immersing at 0 ° C. for 1 hour, the coating film was subjected to a peeling test with cellophane tape, and the peeling of the coating film was observed. In the table, ⊚, ◯, Δ and × have the same meanings as f. h. Chemical resistance: The test piece was immersed in each chemical for 1 hour at 20 ° C., and then the coating film was subjected to a peeling test with cellophane tape to observe the peeling of the coating film. In the table, ⊚, ◯, Δ and × have the same meanings as f.

[0043]

[Table 3]

The insulation resistance in Table 3 is a value measured by the following measuring method. i. Insulation resistance --- According to JISZ-3197, insulation of test piece at room temperature (initial value), 55 ° C, 95%
RH, insulation after absorbing moisture for 96 hours (after moisture absorption) DC
Measured at -500V for 1 minute.

The insulation resistance of the solder resist cured coating film is
Usually, there is no problem if it is 1 × 10 ¹⁰ Ω or more. Therefore, as shown in Table 3, the solder resists of Examples 1 to 6 were
Both are at a sufficient level for insulation resistance.

[0046]

The resist resin obtained by the present invention can form a film with excellent adhesion to a substrate, has high sensitivity to active energy rays, and can form an uncured film in an alkaline aqueous solution easily. It is soluble, and the cured film has excellent hardness, adhesion, heat resistance, solvent resistance, chemical resistance, etc. Therefore, the photo solder resist made of the resin has an extremely excellent balance of physical properties as compared with the conventional photo solder resist.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location H05K 3/28 D (72) Inventor Hiroyuki Ota 1 East Toa, 1 Funami-cho, Minato-ku, Nagoya-shi, Aichi Synthetic Co., Ltd. Nagoya Research Institute

Claims (4)

[Claims] 1. A copolymer comprising a (meth) acrylate having one epoxy group and one or more kinds of monomers having one ethylenically unsaturated group other than the (meth) acrylate. After the addition reaction of a monomer having at least one ethylenically unsaturated group and one carboxyl group with the epoxy group, the hydroxyl group in the addition reaction product is further reacted with a dicarboxylic acid anhydride. A method for producing a resin composition for a resist, which comprises subjecting a product to an addition reaction. 2. A weight average molecular weight 3, comprising a (meth) acrylate having one epoxy group and one or more kinds of monomers having one ethylenically unsaturated group other than the (meth) acrylate. 000 to 150,000 epoxy groups in the copolymer are subjected to addition reaction with a monomer having at least one ethylenically unsaturated group and one carboxyl group, and then in the addition reaction product The method for producing a resist resin composition according to claim 1, wherein an addition product having an oxidation amount of 20 to 150 mgKOH / g is obtained by further subjecting the hydroxyl group of (1) to a divalent carboxylic acid anhydride. 3. A photo solder resist comprising the resin composition for resist obtained by the manufacturing method according to claim 1 or 2. 4. The photo solder resist according to claim 3, further comprising an epoxy resin, an epoxy resin curing agent, a photopolymerization initiator and a diluent.