JPH06263832A - Resin composition curable with active energy ray - Google Patents

Abstract

PURPOSE:To obtain a resin composition which gives a cured composition excellent in heat resistance, solvent resistance, chemical resistance, etc., has excellent alkali developability when in the state of an uncured film, and is useful especially as a liquid photo solder resist. CONSTITUTION:This resin composition comprises a (meth)acrylate having an acid group and an active energy ray-curable resin obtained by reacting a cresol- novolak epoxy resin with an unsaturated monocarboxylic acid and reacting this reactional product with a polybasic acid anhydride, the amount of the acid anhydride being 0.15-0.55mol per mol of the hydroxyl groups of the reactional product.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention can be applied to the surface of a material having fine irregularities without generating bubbles.
The present invention relates to an active energy ray curable resin composition that is easily cured by irradiation with active energy rays such as ultraviolet rays or electron beams, and a cured film of the resin composition has excellent heat resistance and electrical insulation. , Shows excellent corrosion resistance to acid, alkali or solvent treatment, and since the uncured film of the resin composition has dilute alkali developability, it can be used for manufacturing printed wiring boards, precision metal processing, etc., In particular, it is useful as a resin composition for a solder resist for printed wiring boards, and in addition to these, it can be used in various industries as a casting material, paint or molding material. still,
In the present specification, acrylate and / or methacrylate are referred to as (meth) acrylate, acrylic acid and / or methacrylic acid are referred to as (meth) acrylic acid, and acryloyl group and / or methacryloyl group are referred to as (meth) acryloyl group.

[0002]

2. Description of the Related Art Solder resist is a heat-resistant insulating coating material, which is cured by screen printing or photography to prevent bridges and stabilize circuit insulation when soldering components to a printed circuit board. Is to form. In the past, film formation by screen printing was the mainstream method, but with the recent lighter, thinner, shorter, and smaller electronic devices, the density of printed wiring boards has increased, exposing circuits (cutting edges) and fogging to unnecessary areas. (Bleaching) has become a problem, and at present, the formation of a cured film by a photographic method is predominant in printed wiring boards for high density and high mounting. Liquid solder resists used in photography include liquid photo solder resists and dry film type solder resists. In particular, liquid solder resists are liquid and easy to handle, resist coating is simple, and embedding between circuits is easy. Since it is also good, demand has been increasing in recent years.

The liquid photosolder resist is formed by applying the resist material on the entire surface by screen printing, a roll coater, a curtain coater or the like and forming a film by drying.
It is used by exposing on a negative film and then dissolving and developing the unexposed portion with a predetermined developing solution to form a pattern.
The liquid photo solder resist is a resin composition containing a curable resin as a main component, which is cured by ultraviolet rays or heat to form a cured product having excellent adhesion and heat resistance. Examples of such resin compositions include JP-A-60-208377 and JP-A-61-243.
As seen in Japanese Patent No. 869, etc., many of them are mainly composed of epoxy acrylate resin, and various properties can be exhibited by different types of epoxy resins, different acrylate conversion methods, introduction of different functional groups, etc. It is possible. For example, if the amount of (meth) acryloyl group is increased, the sensitivity to active energy rays such as ultraviolet rays is increased, and if the amount of epoxy group is increased, the thermosetting property is emphasized, and the cured film properties after heat curing become excellent. When a group is introduced to increase the acid value, the resin becomes a resin that dissolves in an alkaline aqueous solution and becomes an alkali developing type resin. Liquid photo-solder resists are classified into solvent-development type and alkali-development type depending on the developing method.However, solvent-development type resists are not used as a solvent because the cured film has insufficient solvent resistance and acid resistance. The chlorine-based organic solvents that are used are expensive and have a problem of air pollution. On the other hand, the alkali-development type is inexpensive and has recently been attracting attention because of no concern about air pollution. Alkali-developing liquid photosolder resist is generally made into a liquid by dissolving a solid resin as a main component in an organic solvent. The properties required for such an alkali-developable liquid photosolder resist are photosensitivity, developability, hardness, adhesion to a substrate, heat resistance,
Although solvent resistance, acid resistance and the like can be mentioned, developability with a dilute aqueous alkali solution is particularly important.

[0004]

The epoxy acrylate resin used as the resin which is the main component of the alkali-developable liquid photosolder resist generally has a high acid value in consideration of developability, and therefore has a high acid value. Although the addition ratio is increased, this causes a problem that the inherent properties of epoxy acrylate such as heat resistance, solvent resistance and chemical resistance are deteriorated. The present inventors do not have the above-mentioned drawbacks and do not impair the original properties of the resin, and the cured film has adhesiveness, electric insulation, solder heat resistance, solvent resistance, alkali resistance, acid resistance, and plating resistance. The inventors have made earnest studies to find an active energy ray-curable resin composition that has excellent properties and an uncured film has excellent alkali developability, and is particularly useful as a liquid photosolder resist.

[0005]

As a result of various studies, the present inventors have found that in order to solve the above-mentioned problems, hydroxyl group 1 in a reaction product of a cresol novolac type epoxy resin and an unsaturated monocarboxylic acid is Resin obtained by reacting a specific amount of polybasic acid anhydride per equivalent, and acid value (meth)
The present invention has been completed by finding that a composition comprising an acrylate is effective. That is, the present invention is an active energy obtained by reacting 0.15 to 0.55 mol of a polybasic acid anhydride per 1 mol of a hydroxyl group in a reaction product of a cresol novolac type epoxy resin and an unsaturated monocarboxylic acid. The present invention relates to an active energy ray curable resin composition composed of a ray curable resin and a (meth) acrylate having an acidic group. Hereinafter, the present invention will be described in detail.

Active energy ray curable resin The active energy ray curable resin constituting the resin composition of the present invention is a reaction product of a cresol novolac type epoxy resin and an unsaturated monocarboxylic acid, and a polybasic acid anhydride. It is obtained by reacting. As the cresol novolac type epoxy resin, a conventionally known one can be used, and a compound obtained by reacting cresol novolac resin with epichlorohydrin by a conventional method can be used. As the cresol novolac type epoxy resin, it is preferable to use one having a softening point of 80 ° C. or higher measured by a ring and ball method, and more preferably a softening point of 90 ° C. or higher. When the resin composition of the present invention is used as a solder resist, for example, by using a resin having a softening point of 80 ° C. or higher measured by a ring and ball method, the resist is applied on the entire surface of the substrate and then the solvent is removed by preliminary drying. The film thus formed has no tack, and is therefore convenient for exposing a negative film in close contact with the film, and the resolution of the fine pattern is improved. Cresol novolac type epoxy resin is commercially available. Specifically, Sumitomo Chemical Co., Ltd.'s Sumiepoxy ESCN2
20HH, ESCN195XH, Dainippon Ink and Chemicals, Inc. Epicolon N-695, Toto Kasei Co., Ltd. Epotote YDCN704P, YDCN703P, Nippon Kayaku Co., Ltd. EOCN-104S, Yuka Shell Epoxy Co., Ltd. 180S90, etc. Can be mentioned.

Specific examples of unsaturated monocarboxylic acids include:
(Meth) acrylic acid, crotonic acid, cinnamic acid, oligomer of dimer or more by Michael addition of (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, amber An acid monohydroxyethyl (meth) acrylate etc. are mentioned.

Specific examples of polybasic acid anhydrides include succinic anhydride, methylsuccinic anhydride, 2,3-dimethylsuccinic anhydride, ethylsuccinic anhydride, nonylsuccinic anhydride and maleic anhydride. , 3-Dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaccot anhydride, phthalic acid Anhydride, tetrahydrophthalic anhydride,
Dibasic acid anhydrides such as hexahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, trimetic anhydride, pyro Examples thereof include polybasic acid anhydrides such as mellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, and 5- (2,5-dioxotetrahydrofuryl) -3-cyclohexene-1,2-dicarboxylic acid anhydride. It is preferable to use succinic anhydride, phthalic anhydride or tetrahydrophthalic anhydride.

The active energy ray curable resin used in the present invention is usually obtained by sequentially reacting a cresol novolac type epoxy resin with an unsaturated monocarboxylic acid and a polybasic acid anhydride. As the amount of the unsaturated monocarboxylic acid at the time of producing the resin, it is preferable to use 0.8 to 1.2 mol of the unsaturated monocarboxylic acid with respect to 1 mol of the epoxy group of the cresol novolac type epoxy resin, More preferably, it is 1.0 to 1.1 mol. If the amount is less than 0.8 mol, the resin finally obtained may be thermally unstable, and thus the resin composition may be thermally unstable. The amount of the polybasic acid anhydride should be 0.15 to 0.55 mol, preferably 0.2 to 0.5 mol, per 1 mol of the hydroxyl group in the reaction product of the cresol novolac type epoxy resin and the unsaturated monocarboxylic acid. It is 0.4 mol. 0.1
When the amount is less than 5 mol, when the composition is used as a resist, the adhesion to the substrate and the alkali developability are deteriorated, while when it exceeds 0.55 mol, the heat resistance of the cured product of the composition is low. Properties, solvent resistance, chemical resistance, etc. deteriorate.

As a method for producing the above active energy ray curable resin, the cresol novolac type epoxy resin is dissolved in an organic solvent such as methyl cellosolve acetate, ethyl carbitol acetate, methyl ethyl ketone or the like to prepare hydroquinone, hydroquinone monomethyl ether or catechol. , Pyrogallol, phenothiazine, N-
A polymerization inhibitor such as nitrosophenylhydroxylamine aluminum salt and N, N-dimethylbenzylamine,
Tertiary amines such as triethylamine, N, N-dimethylaniline, quaternary ammonium salts such as tetradiethylammonium chloride, tetrabutylammonium bromide and benzyltrimethylammonium chloride, hydrochlorides of secondary amines such as diethylammonium chloride, triphenyl In the presence of a catalyst such as phosphorus compounds such as phosphine, the above unsaturated monocarboxylic acid is mixed, and the mixture is usually heated to 70 ° C.
Examples include a method in which a ring-opening esterification reaction is carried out by heating and stirring at ˜140 ° C., and subsequently a polybasic acid anhydride is added and the reaction is carried out at the same temperature.

(Meth) acrylate having an acid value The (meth) acrylate having an acid value is a (meth) acrylate-based monomer or oligomer which has an acid value and is cured by active energy rays. The (meth) acrylate having an acid value has an acidic group such as a carboxyl group, a sulfone group or a phosphoric acid group existing in the molecule. Even if there are a plurality of these acidic groups, two or more kinds of them exist. It may be. Specific examples of these are (meta)
Dimeric or higher oligomers obtained by Michael addition of acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, monohydroxymethacryl succinate (meth) acrylate, etc. , Pentaerythritol, dipentaerythritol, glycerin,
Trimethylolpropane, ditrimethylolpropane,
Polybasic acid ester and phosphoric acid ester of mono- or poly (meth) acrylate obtained by reaction of polyhydric alcohol such as sorbitol with (meth) acrylic acid and polybasic acid anhydride, polybasic acid, sulfuric acid, phosphorus pentoxide, etc. , Sulfonic acid esters, etc., and relatively low molecular weight bisphenol A
Examples thereof include polybasic acid esters, phosphoric acid esters, and sulfonic acid esters of polyfunctional epoxy mono- or poly (meth) acrylates such as epoxy resin, bisphenol F epoxy resin, and phenol novolac epoxy resin. Among these, especially a (meth) acryloyl group is 2
It is preferable to use poly (meth) acrylates having more than one since the hardness of the obtained cured product becomes high. As the polybasic acid anhydride, those already described as one of the raw materials for producing the active energy ray-curable resin in the present invention, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and the like can be used. As the polybasic acid, a polybasic acid corresponding to the above-mentioned polybasic acid anhydride, for example, succinic acid, maleic acid, tetrahydrophthalic acid or the like can be used.

In the composition of the present invention, the preferable amount of the (meth) acrylate having an acidic group is such that the acid value of the mixture of the two components of the active energy ray-curable resin and the (meth) acrylate having an acid value is the acid value. 20-150 mgK
OH / g, more preferably 40 to 120
The amount is mgKOH / g. 20 mg KO
When the amount is less than H / g, the developability and the hardness of the cured product are insufficient. On the other hand, when the amount is more than 150 mgKOH / g, the cured product has poor alkali resistance, solvent resistance and heat resistance. Not enough.

Other components The active energy ray-curable resin composition of the present invention is used as it is when it is cured by an electron beam, or when it is cured by ultraviolet rays, it is mixed with a photoinitiator and used for various purposes. can do. In any case, a diluent may be optionally used in the composition of the present invention. In the case of UV curing, photoinitiators that can be used 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,
Acetophenones such as 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one,
Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone, 2,4-dimethylthioxanthone, 2,
There are thioxanthones such as 4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopyrthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, and benzophenones such as benzophenone or xanthones. When the photoinitiator is used, the photoinitiator can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiation accelerator. The amount of the photoinitiator used is preferably 0.2 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the total of the active energy ray curable resin and the (meth) acrylate having an acid value. .

As the diluent, a usual organic solvent or an active energy ray-curable monomer is used as required. The organic solvent, methyl ethyl ketone, ketones such as cyclohexanone, toluene, aromatic hydrocarbons such as xylene, cellosolve, cellosolves such as butyl cellosolve, carbitol, carbitols such as butyl carbitol, ethyl acetate, butyl acetate, Acetic acid esters such as cellosolve acetate, ethyl propylene glycol acetate, carbitol acetate, ethyl carbitol acetate and the like can be mentioned. Examples of the active energy ray curable monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene glycol, methoxyethylene glycol, polyethylene glycol and propylene glycol. Mono- or di (meth) acrylates of glycols, N, N-
(Meth) acrylamides such as dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N
-Aminoalkyl (meth) acrylates such as vinylpyrrolidone, N, N dimethylaminoethyl (meth) acrylate, hexanediol, trimethylolpropane,
Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or polyhydric (meth) acrylates of adducts of ethylene oxide or propylene oxide, phenoxy (meth) acrylate, benzyl (meth) acrylate, etc. Aromatic (meth) acrylates of When a diluent is used, it is preferable to use 1 to 300 parts by weight, and more preferably 10 to 100 parts by weight, per 100 parts by weight of the mixture of the active energy ray curable resin and the (meth) acrylate having an acid value. is there.
Further, when the solvent is used in the production of the above-mentioned energy ray-curable resin, the diluent may be used as it is without separating it after the reaction.

The active energy ray-curable resin composition of the present invention has a wide variety of uses. When it is used as a photopolymerizable liquid resist ink composition, in addition to the above-mentioned components,
If necessary, barium sulfate, silicon oxide, talc,
Clay, filler such as calcium carbonate, phthalocyanine
Coloring pigments such as blue, phthalocyanine / green, titanium oxide and carbon black, various additives such as adhesion promoters or leveling agents, or hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, phenothiazine, N-nitrosophenyl. A polymerization inhibitor such as hydroxylamine aluminum salt may be added according to a conventional method. Further, in order to improve properties such as hardness, heat resistance and solvent resistance of the cured product,
If necessary, a thermosetting resin such as an epoxy resin, a phenol resin, a urea resin or a melamine resin may be blended.

[0016]

EXAMPLES The present invention will be described more specifically by showing Examples and Comparative Examples below. In the following, "part" means "part by weight". Example 1 981 parts of cresol novolac type epoxy resin (YDCN704P manufactured by Tohto Kasei Co., Ltd.) having an epoxy equivalent of 213, 742 parts of ethyl carbitol acetate, phenothiazine 1.
14 parts and benzyldimethylamine 22.5 parts at 95 ° C
Were mixed and dissolved in, and then 345 parts of acrylic acid was added.
After the addition, the reaction was continued at that temperature for 10 hours until the acid value was 0.5.
After confirming that the amount became less than mgKOH / g, 204 parts of phthalic anhydride (0.3 mol per 1 mol of hydroxyl group in the reaction product of cresol novolac type epoxy resin and acrylic acid) was added, and further reacted for 3 hours. Then, a solution of the active energy ray-curable resin was obtained. The nonvolatile content of the solution was 68%, the acid value was 37 mgKOH / g, and the viscosity at 25 ° C was 28700 cp.
It was s. Hereinafter, this resin solution is referred to as (A-1). 70 parts of (A-1) above was mixed with 30 parts of a 50% toluene solution of a phthalic anhydride modified product of pentaerythritol triacrylate as a (meth) acrylate having an acidic group, and the active energy ray-curable resin and acid value were mixed. A solution of a mixture of two components of (meth) acrylate having (hereinafter referred to as a two-component mixture) was obtained. The oxidation of a binary mixture is 6
9 mgKOH / g, the acid value of this solution is 43 mgK
It was OH / g. In 85 parts of the above two-component mixture solution, 5 parts of benzyl dimethyl ketal (Irgacure 651 manufactured by Ciba Geigy) as a photoinitiator, 1 part of phthalocyanine phosphorus as a color pigment, 30 parts of calcium carbonate as an extender pigment, 10 parts of talc, and a leveling agent. 2 parts of Modaflow (manufactured by Monsanto) and 4 parts of melamine as an epoxy curing agent were added and kneaded with a three-roll mill. In addition to this, cresol novolac type resin (YDCN704 manufactured by Tohto Kasei)
P) A mixture of 25 parts and 6 parts of ethyl carbitol acetate [referred to as component (B-1)] was mixed to obtain a resist ink. This resist ink was screen-printed on each of a copper glass epoxy substrate, a through-hole substrate and a printed wiring board on which a pattern was formed, and dried at 70 ° C. for 30 minutes to obtain a test piece. There was no tack on any touch.

Of these test pieces, a step tablet film was placed on the copper glass epoxy substrate, the through hole substrate was left as it was, and a resist pattern film was placed on the printed wiring board, and each was irradiated with ultraviolet rays by a 3 KW ultra-high pressure mercury lamp. did. After exposure at 500 mJ / cm ² , develop with 1% sodium carbonate aqueous solution for 30 seconds and
It was heat-cured at 50 ° C. for 30 minutes. The photosensitivity of the copper glass epoxy substrate was 8 in the number of step tablets. The developability on the through-hole substrate was good and no holes were filled.
The pencil hardness of the printed wiring board was 7H, and the adhesion was good. Furthermore, in a solder bath at 260 ° C for 30 seconds,
There is no abnormality in the heat resistance test three times, methylene chloride, 10%
The chemical resistance test of immersion in sodium hydroxide, 10% sulfuric acid, 10% hydrochloric acid for 1 hour showed no abnormality. Further, there was no problem in gold plating resistance and insulation resistance value after moisture absorption. The above results are shown in Tables 1 and 2.

[0018]

[Table 1]

[0019]

[Table 2]

The evaluation judgments of the respective performances shown in Tables 1 and 2 and Tables 3 and 4 below are as follows. -Drying property After applying the resist ink and drying at 70 ° C for 30 minutes, the tack was evaluated by touch with a finger. ⊚: No tack, ◯: Slight tack, Δ: Tack, ×: Remarkably tack. -Photosensitive step tablet The number of steps is shown.・ Developability It was confirmed by the hole filling property after development on the through-hole substrate. ⊚: No holes are filled, ◯: Holes are slightly filled, Δ: Holes are filled, ×: Holes are filled. -Pencil hardness It was performed by a hand-drawing method according to the test method of JISK-5400. -Adhesion property It carried out according to the test method of JISD-0202. The evaluation was performed by the number of remaining films in 100 grids of 1 mm. -Solder heat resistance According to the test method of JISC-6481, a solder bath at 260 ° C was floated three times for 30 seconds, and then a peeling test was performed on the coating film with cellophane tape to check the degree of peeling of the coating film. ⊚: Not peeled at all, ◯: Peeled slightly, Δ: 10
%: Peeled off, x: peeled off on the whole surface. -Solvent resistance After immersing the test piece in methylene chloride at 20 ° C for 1 hour, the coating film was subjected to a peeling test with a cellophane tape to check the degree of peeling of the coating film. ⊚: Not peeled at all, ◯: Peeled slightly, Δ: 10
%: Peeled off, x: peeled off on the whole surface. -Chemical resistance After immersing the test piece in each chemical at 20 ° C for 1 hour, the coating film was subjected to a peeling test with cellophane tape to check the degree of peeling of the coating film. ⊚: Not peeled at all, ◯: Peeled slightly, Δ: 10
%: Peeled off, x: peeled off on the whole surface. · A gold-plated test piece at a current density of 1A / dm ³ performs 12 minutes gilding performs peeling test by cellophane tape for the coating film, saw the degree of peeling of the coating film. ⊚: Not peeled at all, ◯: Peeled slightly, Δ: 10
% Peels off, x: peels off on the whole surface-Insulation resistance In accordance with JISZ-3197, the insulation property of the test piece at room temperature and the insulation property absorbed by 55 ° C, 95% RH, for 96 hours are measured at DC-500V for 1 minute. Measured as.

Example 2 1026 parts of cresol novolac type epoxy resin (180S90 manufactured by Yuka Shell Co., Ltd.) having an epoxy equivalent of 223, 775 parts of ethyl carbitol acetate, and 2.2 of hydroquinone.
9 parts of 7 parts and 22.5 parts of tetrabutylammonium bromide
It was mixed and dissolved at 5 ° C., and 345 parts of acrylic acid was added thereto. After addition, the reaction was continued at that temperature for 10 hours, and after confirming that the acid value was 0.5 mgKOH / g or less,
138 parts of succinic anhydride (0.3 mol with respect to 1 mol of hydroxyl group in the reaction product of cresol novolac type epoxy resin and acrylic acid) was added and further reacted for 3 hours to obtain a solution of an active energy ray-curable resin. The nonvolatile content of the solution is 6
6%, acid value 36 mgKOH / g, 25 ° C viscosity 200
It was 00 cps. . A phthalic anhydride-modified product of dipentaerythritol pentaacrylate as a (meth) acrylate having an acidic group in 80 parts of the above resin solution 20.
The parts were mixed to obtain a solution of a binary mixture. The acid value of the binary mixture is 73 mgKOH / g and the acid value of this solution is 5
It was 3 mgKOH / g. The above-mentioned binary mixture solution 85
Part, 5 parts of 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (Irgacure 907 manufactured by Ciba Geigy) as a photoinitiator, 1 part of phthalocyanine phosphorus, and barium sulfate 6 as an extender pigment.
0 part, 10 parts of talc, 1 part of AC-300 (manufactured by Kyoeisha Oil and Fats) as an antifoaming agent and 4 parts of melamine were added and kneaded with a three-roll mill, to which cresol novolac type resin (180S90 made by Yuka Shell) 25 Parts, ethyl carbitol acetate 5 parts, xylene 3 parts and polymerization initiator Perkmill D
A resist ink was obtained by mixing 1 part of the mixture [referred to as (B-2) component]. Using this resist ink, evaluation was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2 above.
Shown in.

Example 3 1003 parts of cresol novolac type epoxy resin (ESCN220HH manufactured by Sumitomo Chemical Co., Ltd.) having an epoxy equivalent of 218, 596 parts of ethyl propylene glycol acetate, 2.27 parts of hydroquinone and 1 part of tetraethylammonium chloride.
2.5 parts were mixed and dissolved at 95 ° C., and then acrylic acid 33
2 parts were added. After the addition, the reaction was continued at that temperature for 10 hours, and after confirming that the acid value was 0.5 mgKOH / g or less, 350 parts of tetrahydrophthalic anhydride (in the reaction product of cresol novolac type epoxy resin and acrylic acid) 0.5 mol) was added to 1 mol of the hydroxyl group and the reaction was continued for 3 hours to obtain a solution of the active energy ray-curable resin.
The solution has a nonvolatile content of 74% and an acid value of 58 mgKOH /
The viscosity at 25 ° C. was 49400 cps. To 60 parts of the above resin solution, as a (meth) acrylate having an acidic group, a toluene 50% solution of a tetrahydrophthalic anhydride modified product of dipentaerythritol pentaacrylate 4
0 parts were mixed to obtain a binary solution. The acid value of the binary mixture was 104 mgKOH / g, and the acid value of this solution was 67 mgKOH / g. 90 parts of a solution of the above binary mixture, 2 parts of 2,4-diethylthioxanthone as a photoinitiator, 2 parts of 2-dimethylaminobenzoate,
Phthalocyanine phosphorus 1 part, barium sulfate 60 parts, AC
-3001 parts and 4 parts of melamine were added and kneaded with a three-roll mill, and a mixture of 25 parts of cresol novolac type resin (ESCN220HH manufactured by Sumitomo Chemical Co., Ltd.) and 6 parts of ethyl propylene glycol acetate was mixed to obtain a resist ink. . Using this resist ink, evaluation was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2 above.

Example 4 966 parts of cresol novolac type epoxy resin (YDCN704P manufactured by Tohto Kasei) having an epoxy equivalent of 213, 413 parts of ethyl carbitol acetate, diglyme 213,
2.39 parts of hydroquinone and diethylamine hydrochloride 24
Parts were mixed and dissolved at 95 ° C., and then 331 parts of acrylic acid was added. After the addition, the reaction was continued at that temperature for 10 hours, and after confirming that the acid value became 0.5 mgKOH / g or less, 92 parts of succinic anhydride (the hydroxyl group in the reaction product of the cresol novolac type epoxy resin and acrylic acid was used). (0.2 mol relative to 1 mol) was added and reacted for 3 hours to obtain a solution of the active energy ray-curable resin. The nonvolatile content of the solution was 69%, the acid value was 25 mgKOH / g, and the viscosity at 25 ° C was 19%.
It was 200 cps. As a (meth) acrylate having an acidic group in 80 parts of the above resin solution, 20 parts of a modified dipentaerythritol pentaacrylate succinic acid was mixed to obtain a two-component mixture. The acid value of the binary mixture is 50m
gKOH / g, the oxidation of this solution is 38 mgKOH
/ G. 90 parts of a solution of the above-mentioned two-component mixture, 2 parts of 4,4′-tetraethylaminobenzophenone, 2 parts of benzophenone and 1 part of phthalocyanine phosphorus as a photoinitiator.
Part, 60 parts of barium sulfate, 1 part of Modaflow and 4 parts of melamine were added and kneaded with a triple roll, and cresol novolac type resin (YDCN704P manufactured by Toto Kasei) 25
Part, and a mixture of 4 parts of ethyl carbitol acetate were mixed to prepare a resist ink. Using this resist ink, evaluation was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2 above.

Example 5 1026 parts of a cresol novolac type epoxy resin (180S90 manufactured by Yuka Shell Co., Ltd.) having an epoxy equivalent of 223, 500 parts of diglyme, 2.27 parts of hydroquinone and 17.5 parts of triphenylphosphine were mixed and dissolved at 95 ° C. Then, 690 parts of acrylic acid dimer (Aronix M-5600 manufactured by Toagosei Chemical Industry Co., Ltd.) was added. After the addition, the reaction was continued at that temperature for 10 hours, and the acid value was 0.5 mgKOH / g.
After confirming that the amount was below, 127 parts of maleic anhydride (30 mol% based on all hydroxyl groups in the reaction product of cresol novolac type epoxy resin and acrylic acid) was added, and further reacted for 3 hours to cure with active energy rays. A solution of the functional resin was obtained. The nonvolatile content of the solution was 79% and the acid value was 35.9 mg.
KOH / g, 25 degreeC viscosity was 20000 cps.
70 parts of the resin solution was mixed with 30 parts of an acid-modified epoxy acrylate (SP-2600 manufactured by Showa High Polymer) as a (meth) acrylate having an acidic group to obtain a two-component mixture. The acid value of the binary mixture was 70 mg KOH / g and the oxidation of this solution was 59.6 mg KOH / g. To 90 parts of the above-mentioned two-component mixture, 4, as a photoinitiator,
2 parts of 4'-tetraethylaminobenzophenone, 2 parts of benzophenone, 1 part of phthalocyanine phosphorus, 60 parts of barium sulfate, 1 part of modaflow and 4 parts of melamine were added and kneaded with a three-roll mill, and cresol novolac resin (Toto Kasei Co., Ltd. YDCN704P) (30 parts) and ethyl carbitol acetate (6 parts) were mixed to obtain a resist ink. Using this resist ink, Example 1
It evaluated similarly to. The results are shown in Tables 1 and 2 above.

Comparative Example 1 In 85 parts of the resin (A-1) of Example 1, 5 parts of benzyl dimethyl ketal (Irgacure 651 manufactured by Ciba-Geigy) as a photoinitiator, 1 part of phthalocyanine phosphorus, 30 parts of calcium carbonate and 10 talc. Part, 2 parts of modoflow and 4 parts of melamine as an epoxy curing agent were added and kneaded with a three-roll mill, and the mixture (B-1) used in Example 1 was added thereto.
Were mixed to obtain a resist ink. Using this resist ink, evaluation was performed in the same manner as in Example 1. The results are shown in Tables 3 and 4.

[0026]

[Table 3]

[0027]

[Table 4]

Comparative Example 2 70 parts of the resin (A-1) of Example 1 was mixed with 30 parts of a 50% toluene solution of pentaerythritol tetraacrylate [Aronix M-450 manufactured by Toagosei Chemical Industry Co., Ltd.]. Benzyl dimethyl ketal (IRGACURE 6 manufactured by Ciba-Geigy) as a photoinitiator was added to 85 parts of the above mixture.
51) 5 parts, 1 part of phthalocyanine phosphorus, 30 parts of calcium carbonate, 10 parts of talc, 2 parts of modal flow and 4 parts of melamine were added and kneaded with a three-roll mill, and the mixture (B-1) used in Example 1 was added thereto. Were mixed to obtain a resist ink. Using this resist ink, evaluation was performed in the same manner as in Example 1. The results are shown in Tables 3 and 4 above.

Comparative Example 3 981 parts of a cresol novolac type epoxy resin (YDCN704P manufactured by Tohto Kasei Co., Ltd.) having an epoxy equivalent of 213, 742 parts of ethyl carbitol acetate, phenothiazine 1.
14 parts and benzyldimethylamine 22.5 parts at 95 ° C
Were mixed and dissolved in, and then 345 parts of acrylic acid was added.
After the addition, the reaction was continued at that temperature for 10 hours until the acid value was 0.5.
After confirming that the amount was less than mgKOH / g, 68 parts of phthalic anhydride (0.1 mol per 1 mol of hydroxyl group in the reaction product of cresol novolac type epoxy resin and acrylic acid) was added, and the reaction was continued for 3 hours. Thus, an active energy ray curable resin was obtained. The nonvolatile content of the solution is 66% and the acid value is 1.
The viscosity was 2500 cps at 2 mgKOH / g and 25 ° C. 70 parts of the above resin solution has an acidic group (meta)
As an acrylate, a solution of pentaerythritol triacrylate modified with phthalic anhydride in 50% toluene solution 30
The parts were mixed to obtain a binary solution. The acid value of the binary mixture is 41 mgKOH / g, the acid value of this solution is 25 m.
It was gKOH / g. 90 parts of the above two-component mixture,
2,4-Diethylthioxanthone (2 parts), 2-dimethylaminobenzoate (2 parts), phthalocyanine phosphorus (1 part), barium sulfate (60 parts), AC-3001 parts and melamine (4 parts) were added and kneaded with a three-roll mill. The mixture (B-1) used in was mixed to obtain a resist ink. Using this resist ink, evaluation was performed in the same manner as in Example 1. The results are shown in Tables 3 and 4 above.

Comparative Example 4 1026 parts of cresol novolac type epoxy resin (180S90 manufactured by Yuka Shell Co., Ltd.) having an epoxy equivalent of 223, 775 parts of ethyl carbitol acetate, and 2.2 of hydroquinone.
9 parts of 7 parts and 22.5 parts of tetrabutylammonium bromide
The mixture was mixed and dissolved at 5 ° C., and then 345 parts of acrylic acid was added. After the addition, the reaction was continued at that temperature for 10 hours, and after confirming that the acid value became 0.5 mgKOH / g or less, 276 parts of succinic anhydride (the total amount of cresol novolac type epoxy resin and acrylic acid in the reaction product was 60m to hydroxyl group
ol%) was added and the reaction was further continued for 3 hours to obtain an active energy ray-curable resin. The nonvolatile content of the solution was 68%, the acid value was 63 mgKOH / g, and the viscosity at 25 ° C was 51000 cps.
Met. As a (meth) acrylate having an acidic group in 80 parts of the resin solution, 20 parts of a modified phthalic anhydride of dipentaerythritol pentaacrylate is mixed,
A binary mixture was obtained. The acid value of the binary mixture is 83 mgK
OH / g, the oxidation of this solution is 61 mgKOH / g
Met. To 85 parts of the above binary mixture, 2-methyl-
[4- (methylthio) phenyl] -2-morpholino-1-propanone (Irgacure 9 manufactured by Ciba Geigy)
07) 5 parts, phthalocyanine phosphorus 1 part, barium sulfate 60 parts, talc 10 parts, AC-3001 parts and melamine 4 parts were added and kneaded with a three-roll mill, and the mixture used in Example 2 thereof (B-2 ) Was mixed to obtain a resist ink. Using this resist ink, evaluation was performed in the same manner as in Example 1. The results are shown in Tables 3 and 4 above.

[0031]

The active energy ray-curable resin composition of the present invention has a high degree of photosensitivity, and its cured film has hardness, adhesion, heat resistance, solvent resistance, chemical resistance, gold plating resistance, Since the uncured film has excellent alkali developability as well as excellent electrical characteristics, it is extremely useful as a photo solder resist.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H05K 3/28 D 7511-4E

Claims (1)

[Claims] 1. An active energy ray obtained by reacting 0.15 to 0.55 mol of a polybasic acid anhydride per 1 mol of a hydroxyl group in a reaction product of a cresol novolac type epoxy resin and an unsaturated monocarboxylic acid. An active energy ray curable resin composition comprising a curable resin and an acid group-containing (meth) acrylate.