JPH11258789A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin compsn. giving a cured body excellent in solvent resistance, heat resistance and flexibility and utilizable as an alkali- developable liq. resist compsn., a cover coating agent, an overcoating agent, an undercoating agent or an insulating coating agent. SOLUTION: The curable resin compsn. contains (A) the reaction product of a soap-free acrylic rubber dispersed epoxy resin with an ethylenically unsatd. monocarboxylic acid and a polybasic acid anhydride, (B) an epoxy resin and a UV-curing resin and (C) an epoxy curing agent and a photopolymn. initiator. The epoxy resin of the soap-free acrylic rubber dispersed epoxy resin is, e.g. of bisphenol A type, bisphenol AD type, bisphenol F type, phenol novolak type, cresol novolak type, octylphenol novolak type or terpene xylenol type.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable resin composition. In detail, the present invention is excellent in photo-curing and heat resistance, solvent resistance, acid resistance, alkali resistance, flexibility, electrical characteristics, etc., and is particularly suitable for manufacturing printed wiring boards, flexible circuit boards, etc. Curable resin composition developable with aqueous solution, liquid resist ink composition, cover coating agent,
It relates to an overcoat agent, an undercoat agent, and an insulation coat agent.

[0002]

2. Description of the Related Art Alkaline development type photo solder resists have been actively studied in recent years, and some compositions have been disclosed. JP-A-61-243869 discloses a liquid solder resist composition in which a reaction product obtained by adding a polybasic acid anhydride to phenol novolak type or cresol novolak type epoxy acrylate or the like is used as a base polymer and an aqueous alkali solution is used as a developing solution. ing. However, the solder resist film obtained from the above composition has a drawback that adhesion and flexibility are poor.

Japanese Patent Application Laid-Open No. 8-134331 discloses a liquid solder resist in which a reaction product obtained by adding a polybasic acid anhydride to rubber-modified epoxy acrylate or the like is used as a base polymer and an aqueous alkali solution is used as a developing solution. However, the solder resist film obtained with the above composition contains a polybutadiene skeleton in the main chain, is susceptible to air oxidation due to internal olefinic bonds, lacks long-term reliability of mechanical properties (such as tensile strength), and has dispersion polybutadiene particles. There is a drawback that the diameter is on the order of microns and the adhesion performance to the substrate is lacking.

Japanese Patent Application Laid-Open No. 9-40751 discloses a liquid solder resist using an acrylic rubber-dispersed epoxy resin and a polybasic acid anhydride-modified epoxy acrylate as a base polymer and an aqueous alkali solution as a developing solution. Compared with the technology described in JP-A-8-134331, the dispersed acrylic particle diameter is submicron, and although the adhesion performance and the flexibility performance to the base material are improved, when the acrylic rubber dispersion / epoxy is synthesized, the emulsification process is performed. There was a drawback that the emulsifier was contained and foaming was remarkable in the kneading and kneading step of the epoxy resin (e), the ultraviolet curable resin (f), the filler, and the like when used. The acrylic rubber dispersion / epoxy resin contains an epoxy group and is not modified with acrylic acid. For this reason, there was a disadvantage that the alkali resistance of the exposed portion was insufficient in the alkali developing step when using a liquid resist, and the alkali developability was insufficient due to lack of modification with a polybasic acid anhydride. .

[0005] In the above-mentioned alkali developing type photo solder resist, the dispersed acrylic particle diameter is submicron,
There has been a demand for adhesion performance and flexibility to a substrate, soap-free properties without an emulsifier, good alkali resistance in the alkali phenomena step, and good alkali developing performance.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a soap-free acrylic rubber-dispersed epoxy resin, an ethylenically unsaturated monocarboxylic acid, and a polybasic compound Reactants with acid anhydrides,
Further, by using a curable resin composition comprising an epoxy resin and an ultraviolet curing resin, and further comprising an epoxy curing agent and a photopolymerization initiator, the soap-free alkali developing step has good alkali resistance and good alkali developability, and after development. Curing resin composition, liquid resist ink composition, cover coating agent, overcoating agent, undercoating agent, insulating coating agent, which exhibited excellent adhesion and flexible performance by epoxy curing by heat treatment of It is intended to provide processed products.

[0007]

That is, the present invention provides:
(1) (A) Soap-free acrylic rubber dispersion / epoxy resin (a-1) and epoxy resin (a-2), ethylenically unsaturated monocarboxylic acid (b), and polybasic acid anhydride (c) And (B) an epoxy resin (e) and an ultraviolet curing resin (f), and (C) an epoxy curing agent (g) and a photopolymerization initiator (h). A curable resin composition characterized by the fact that (2) the epoxy resin (a-1) is a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, a cresol novolac type The curable resin composition according to (1), which is any one of epoxy resins, and (3) the epoxy resin (a-2) is a bisphenol F type epoxy resin. The curable resin composition according to any one of (1) to (2), which is any one of a resin, a bisphenol AD epoxy resin, a bisphenol A epoxy resin, a phenol novolak epoxy resin, and a cresol novolak epoxy resin. And (4) the epoxy resins (a-1) and (a-2) are each one of an octylphenol novolak type epoxy resin and a terpene xylenol type epoxy resin, respectively (1) to (3). The curable resin composition according to any one of (1) to (4), further comprising (5) an organic filler or an inorganic filler. The curable resin composition according to any one of (1) to (5) is applied to one of a metal, a plastic, a ceramic, and a circuit board and dried to form A workpiece comprising further (7) (A) soap free acrylic rubber dispersed epoxy resin (a-1), an ethylenically unsaturated monocarboxylic acid (b), and polybasic acid anhydride (c)
(D), (B) an epoxy resin (e) and an ultraviolet curing resin (f), and (C) an epoxy curing agent (g)
And a photopolymerization initiator (h).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the soap-free acrylic rubber dispersion / epoxy resin (a-1) used in the present invention, the acrylic rubber is grafted to the epoxy resin through a chemical bond. The particle size of acrylic rubber is dispersed and stabilized at submicron order. The acrylic rubber is chemically grafted with an epoxy resin and has a submicron particle size.
There is no operational problem such as separation and floating of the acrylic rubber.

In the case of thermosetting, a reactant (d), an epoxy resin (e) or an ultraviolet curable resin (f) described later becomes a sea phase, and the acrylic rubber becomes an island phase. The cured product has a sea / island two-phase structure by sea / island grafting. When an external stress is applied, the grafted island phase relaxes the stress and improves the adhesion performance and flexibility. At this time, an acrylic rubber-dispersed epoxy resin synthesized by emulsification in water has a sea / island two-phase structure and improves the adhesion performance and flexibility. However, an emulsifier is used. There was a problem that it was insufficient because it was performed in the presence of water.

On the other hand, the soap-free acrylic rubber-dispersed epoxy resin (a-1) used in the present invention does not use an emulsifier and is a so-called soap-free resin. ), And foaming during the compounding and kneading process of fillers and the like described below are suppressed, and the water resistance is also improved. As described above, in the present invention, soap-free means that no emulsifier is used when synthesizing the acrylic rubber dispersion / epoxy resin (a-1).

In order to obtain the soap-free acrylic rubber dispersion / epoxy resin (a-1) used in the present invention, an equimolar addition product of a methacrylic acid ester containing a hydroxyl group and a diisocyanate is prepared by a known method. Reaction with the hydroxyl group of 1). A methacryloyl group is grafted on the epoxy resin (a-1), and then an acrylic monomer is radically polymerized on the methacryloyl group. In this case, the acrylic monomer preferably has a Tg (glass transition temperature) of 25 ° C. or lower when polymerized. If the temperature is higher than 30 ° C., the cured product becomes hard, which is not preferable.

Known acrylic monomers can be used. Specifically, acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxy Methacrylic esters such as ethyl methacrylate, 2-hydroxypropyl methacrylate, and glycidyl methacrylate are exemplified. In use, a small amount of a hard component such as styrene, divinylbenzene or ethylene glycol diacrylate may be added to increase the solvent resistance of the acrylic rubber. The acrylic monomer is used singly or as a mixture of two or more such that the Tg of the island phase at the time of polymerization is 25 ° C. or less. Since the acrylic rubber has a function to relieve stress as an island phase, the acrylic rubber is polymerized so that the weight ratio of the acrylic rubber to the soap-free acrylic rubber dispersion / epoxy resin (a-1) is 5 wt% to 40 wt%. Is preferred. Further epoxy resin (a-2)
Acrylic rubber (e), ultraviolet curable resin (f), and the total weight of filler and acrylic rubber are 2 wt%
It is preferable to mix them in an amount of 20 wt%. 2wt%
If it is less than 10, stress relaxation is not exhibited as an island phase, which is not preferable in terms of adhesion and flexibility. If it exceeds 20% by weight, the heat resistance of the cured film is not preferable. The epoxy resin (a-1) used in the present invention is a liquid or solid epoxy resin at normal temperature (25 ° C.). Specific examples of the liquid epoxy resin include bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, and 1,4-butanediol diglycidyl. Ether, neopentyl glycol diglycidyl ether, 1,6 hexanediol diglycidyl ether and the like. Further, specific examples of the epoxy resin that is solid at room temperature (25 ° C.) include a phenol novolak epoxy resin, a cresol novolak epoxy resin,
Octylphenol novolak type epoxy resin, terpene xylenol type epoxy resin, naphthalene type epoxy resin, trisepoxypropyl isocyanurate and the like can be mentioned. As the epoxy resin (a-1), a resin containing a hydroxyl group is particularly preferable for grafting with the isocyanate adduct. When used, one or more of the above epoxy resins (a-1) are used.

The soap-free acrylic rubber dispersion / epoxy resin (a-1) used in the present invention can be synthesized by a known method as described above. Specifically, for example, when synthesizing a soap-free acrylic rubber dispersion / liquid epoxy resin, an equimolar adduct of hydroxyethyl methacrylate and tolylene diisocyanate is synthesized in advance. next,
The above equimolar adduct is added to and reacted with an epoxy resin (for example, Epicoat 828) containing a hydroxyl group previously dissolved and diluted with an organic solvent. Thereafter, a mixed solution of an acrylic monomer (for example, butyl acrylate, 2-ethylhexyl acrylate; ethylene glycol diacrylate as an acrylic rubber crosslinking agent) in which a radical polymerization initiator is dissolved is added continuously for a long time, and polymerized at a predetermined temperature. The acrylic rubber thus obtained and the epoxy resin are grafted, and the desired product is synthesized in a soap-free reaction system without using an emulsifier.

Also, when synthesizing a soap-free acrylic rubber dispersed / solid epoxy resin, for example, in the case of a phenol novolak type epoxy resin, the phenol novolak type epoxy resin previously dissolved in an organic solvent by heating and containing a hydroxyl group is added to the above resin. After reacting the equimolar adduct and introducing a methacryloyl group, a mixed solution of an acrylic monomer in which a radical polymerization initiator is dissolved is continuously added for a long time, and polymerized at a predetermined temperature. The acrylic rubber and epoxy resin thus obtained are grafted, and the desired product is synthesized in a soap-free reaction system without using an emulsifier.

The epoxy resin (a-2) used in the present invention
Specific examples include the epoxy resin (a-1) and the epoxy resin (e) described below. At the time of use, the epoxy resins (a-1) and (a-2) are used alone or as a mixture of two or more. The epoxy resins (a-1) and (a-2) are reacted with an ethylenically unsaturated monocarboxylic acid (b) and a polybasic acid anhydride (c) described below. Since the exposure is carried out by placing a photomask in the exposure step, the properties of the reactant (d) at this time are preferably solid properties. It is not preferable for liquid properties. When the property of the reactant (d) is liquid, it can be made solid by changing the mixing ratio of the epoxy resin (a-1) or (a-2).

Specific examples of the ethylenically unsaturated monocarboxylic acid (b) used in the present invention include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Acids are preferred.

The polybasic acid anhydride (c) used in the present invention is specifically maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 2-methyl Tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3,6-endomethylene-tetrahydrophthalic anhydride, 7-methyl-3,6-endomethylenetetrahydrophthalic anhydride and the like. . Tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferred from the viewpoint of electrolytic corrosion.

The reactant (d) used in the present invention may be the epoxy resin (a-1) alone or the epoxy resin (a-
It can be obtained by reacting 1) and an epoxy resin (a-2) with an ethylenically unsaturated monocarboxylic acid (b) and a polybasic acid anhydride (c).

The synthesis method includes: The epoxy resin (a-1) and the epoxy resin (a-
After dissolving 2) in a suitable organic solvent, an ethylenically unsaturated monocarboxylic acid (b) is reacted by a known method, and then a polybasic acid anhydride (c) is added to give an alkali developable resin acid value. 1. a method of reacting; After dissolving the epoxy resin (a-1) in a suitable organic solvent in advance, the ethylenically unsaturated monocarboxylic acid (b) is reacted by a known method, and the polybasic anhydride (c) is reacted with the reactant. After previously dissolving the epoxy resin (a-2) in an appropriate organic solvent, the reaction product is reacted with the ethylenically unsaturated monocarboxylic acid (b) by a known method, and reacted with the polybasic anhydride (c). 2. a method of mixing A method in which the epoxy resin (a-1) is dissolved in a suitable organic solvent in advance and then reacted with the ethylenically unsaturated monocarboxylic acid (b) and the polybasic anhydride (c) by a known method. Can be different.

The reactant (d) of the present invention can be obtained by the above-mentioned methods 1 to 3. Hereinafter, the first method will be described. When synthesizing the reactant (d) used in the present invention, specifically, a soap-free acrylic rubber dispersion / epoxy resin (a-1) and an epoxy resin (a-2) are mixed with a suitable organic solvent (cellosolve, Butyl cellosolve, a glycol derivative such as cellosolve acetate), and then add a predetermined amount of acrylic acid as an ethylenically unsaturated monocarboxylic acid (b), triphenylphosphine as a reaction catalyst, and hydroquinone monomethyl ether as a polymerization inhibitor. Resin acid value 10mg at reaction temperature 110 ° C or less
The reaction is carried out until the amount becomes KOH / g or less.

When reacting, the epoxy resin (a-
1), the number of equivalents (eq) of epoxy groups of the epoxy resin (a-2), and the number of moles of carboxyl groups of acrylic acid (mo)
l) (epoxy group / carboxyl group) is 0.7 to
It is preferably in the range of 1.5. If it is less than 0.7, unreacted acrylic acid remains in the reactant (d), and the coating film does not withstand alkali development after exposure. If it exceeds 1.5, the epoxy resins (a-1) and (a-2) remain in the reactant (d), and the coating film after heat curing is unfavorably soft.

The above epoxy resins (a-1) and (a-2)
A reaction product of the compound and acrylic acid contains a secondary hydroxyl group. Then, the polybasic acid anhydride (c) is added to obtain the reactant (d) used in the present invention under the above reaction conditions. When reacting the polybasic acid anhydride (c), the resin acid value is 50 to 1
The reaction is preferably performed so as to be 30 mgKOH / g. If the resin acid value exceeds 130 mgKOH / g, the coating film is not preferable because it does not withstand alkali in the alkali development step after exposure. When the resin acid value is less than 50 mgKOH / g, the coating film is insoluble in alkali in an alkali developing step after exposure, which is not preferable. As described above, the epoxy resin (a-1),
The reaction product (d) used in the present invention can be obtained by reacting (a-2) with the ethylenically unsaturated monocarboxylic acid (b) and the polybasic anhydride (c).

The epoxy resin (e) used in the present invention has a function of copolymerizing with the carboxyl group of the reactant (d) and a function of self-homopolymerizing. The epoxy resin (e) is already known, but specifically, the epoxy resins (a-1) and (a-2) and also Epicron 900 and Epicron 105 manufactured by Dainippon Ink and Yuka Shell Epoxy Co., Ltd. Epicoat 1001, epicoat 1004,
Phenoxy type epoxy resins such as YD134 manufactured by Toto Kasei, Epicron 1120 manufactured by Dainippon Ink, YL906 manufactured by Yuka Shell Epoxy, R232 and R234 manufactured by Mitsui Chemicals, Inc.
Epoxy resin such as TSR9 manufactured by Dainippon Ink and Chemicals, Inc.
30, rubber-modified epoxy resin such as Mitsui Chemicals SR35,
A dimer acid-modified epoxy resin such as Epototo YD172 manufactured by Toto Kasei Co., Ltd., a trihydroxyphenylmethane type epoxy resin such as YL933 manufactured by Yuka Shell Epoxy, a bisphenol S type epoxy resin such as EXA-1514 manufactured by Dainippon Ink and the like, and an oily shell. Epoxy Epicoat 60
Glycidylamine-type epoxy resin such as No. 4, a heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries, a hydantoin-type epoxy resin such as Araldite CY350 manufactured by Ciba-Geigy, and an alicyclic epoxy resin such as Araldite CY175 manufactured by Ciba-Geigy. . The epoxy resin (e) is used alone or as a mixture of two or more.

The ultraviolet curable resin (f) used in the present invention has a function of copolymerizing with the reactant (d) and a function of self-homogenizing. The ultraviolet curing resin (f) is already known. Specifically, a monofunctional oligomer containing one acryloyloxy group per molecule of the resin (f), a bifunctional oligomer containing two acryloyloxy groups per molecule of the resin (f), and an acryloyloxy group containing the resin (f) A) a trifunctional oligomer containing three per molecule, an acryloyloxy group containing four acryloyloxy groups per resin (f), a tetrafunctional oligomer containing four acryloyloxy groups per molecule, and a pentafunctional oligomer containing five acryloyloxy groups per molecule per molecule. It can be classified into a hexafunctional oligomer or the like containing six oxy groups per one molecule of the resin (f).

Examples of the monofunctional oligomer include acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, nonylphenoxypropyl acrylate and the like. Bifunctional oligomers include ethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6 hexanediol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, bisphenol F diglycidyl ether, 2 mol acrylic acid adduct , Bisphenol AD diglycidyl ether / 2 mol acrylic acid adduct, bisphenol A diglycidyl ether / 2 mol acrylic acid adduct, bisphenol S diglycidyl ether / 2 mol acrylic acid adduct, phenol novolak epoxy resin / 2 mol acrylic acid Adduct, cresol novolak epoxy resin, 2 mol acrylic acid adduct, octylphenol novolak epoxy resin, 2 mol Acrylic acid adduct, terpene xylenol-type epoxy resin, 2 moles acrylic acid adduct, a naphthalene type epoxy resin, 2 moles acrylic acid adduct, tris epoxypropyl isocyanurate 2 moles acrylic acid adduct, and the like.

Examples of the trifunctional oligomer include trimethylolpropane triacrylate, pentaerythritol triacrylate, glycerin triacrylate, M315 manufactured by Toagosei Co., Ltd., Techmore VG3101, 3 mol acrylic acid adduct, EPON 3 mol acrylic acid adduct, etc. Can be

As the tetrafunctional oligomer, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, sorbitol tetraacrylate,
Phenol novolak type epoxy resin / 4 mol acrylic acid adduct, cresol novolak type epoxy resin / 4 mol acrylic acid adduct and the like can be mentioned.

Examples of the pentafunctional oligomer include dipentaerythritol pentaacrylate, sorbitol pentaacrylate, an isophorone diisocyanate adduct of trimethylolpropane diacrylate and pentaerythritol triacrylate, and tolylene diisocyanate of trimethylolpropane diacrylate and pentaerythritol triacrylate. An adduct, a diphenylmethane diisocyanate adduct of trimethylolpropane diacrylate and pentaerythritol triacrylate, and the like can be given.

Examples of the hexafunctional oligomer include dipentaerythritol hexaacrylate, sorbitol hexaacrylate, pentaerythritol triacrylate 2 mol / isophorone diisocyanate 1 mol adduct, pentaerythritol triacrylate 2 mol / tolylene diisocyanate 1 mol adduct, pentaerythritol triacrylate Examples include an adduct of 2 mol of acrylate and 1 mol of diphenylmethane diisocyanate.

A methacrylate compound in which the acryloyloxy group is substituted with a methacryloyloxy group can also be mentioned. Also, an arylate compound in which the acryloyloxy group is substituted with an allyl ether group can be mentioned. . Also, a Michael type acrylate compound obtained by adding a primary amine to the above acrylate compound can be mentioned. Specifically, trimethylolpropane triacrylate / 1 mol ethanolamine adduct, pentaerythritol tetraacrylate / 1 mol ethanolamine adduct, dipentaerythritol tetraacrylate / 1
And a molar ethanolamine adduct.

The UV-curable resin (f) may be one kind or two
Mix and use more than one species. In this case, when the resin (f) is a monofunctional oligomer, the cured film is unfavorably soft.
The case of a bifunctional oligomer or more is preferable because the cured film is hard, the curing speed in the exposure step is high, and the film is resistant to the alkali solution in the development step.

The epoxy curing agent (g) used in the present invention is used when the carboxyl groups of the epoxy resins (a-1) and (a-2) are copolymerized with the epoxy resin (e), and when the epoxy resin (e) is used. It has a function as a catalyst in the self-homopolymerization of e). Specific examples of the curing agent (g) include imidazole derivatives, phenol derivatives, dicyandiamide, dicyandiamide derivatives, hydrazide derivatives, and acid anhydrides. The curing agent (g) is used alone or in combination of two or more. The amount of the curing agent used is preferably such that the active hydrogen amount of the curing agent (g) is 0.5 to 1.2 equivalents to the epoxy group of the epoxy resin.

The photopolymerization initiator (h) used in the present invention has a function of generating radicals upon exposure to ultraviolet light. Examples of the photopolymerization initiator (h) include known ones. Specifically, benzophenone, Michler's ketone, benzoin, benzoin ethyl ether, benzoin butyl ether, benzoin isobutyl ether,
2,2-dimethoxy-2-phenylacetophenone, 2
-Hydroxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-
4-isopropyl-2-methylpropiophenone, 2-
Ethyl anthraquinone, 2-t-butylanthraquinone, diethylthioxanthone, chlorothioxanthone,
Benzyl, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl benzoic acid,
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6 trimethylbenzoyldiphenylphosphine oxide, and the like.

Further, an equimolar addition product of benzoin and ethylene oxide, or a 2-fold to 4-fold molar addition product,
Equimolar addition of benzoin and propylene oxide or 2
4-fold molar addition product to 4-fold molar addition product, α-allylbenzoin, equimolar addition product of 1-hydroxycyclohexylphenyl ketone and ethylene oxide, 2-fold molar addition product to 4-fold molar addition product, 1-hydroxycyclohexylphenyl ketone and Equimolar addition product of propylene oxide, 2-fold to 4-fold mole addition product, benzoylbenzoic acid and ethylene glycol equimolar reactant, benzoylbenzoic acid and propylene glycol equimolar reactant, hydroxybenzophenone and ethylene oxide equimolar Adduct, 2-fold molar adduct to 4-fold molar adduct, equimolar adduct of hydroxybenzophenone and propylene oxide, 2-fold molar to 4-fold molar adduct, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 4- (2- Black oxy ethoxy) - phenyl -
(2-hydroxy-2-propyl) ketone, 4- (2-
(Hydroxyethoxy) phenyl- (2-hydroxy-2
-Propyl) ketone and ethylene oxide equimolar adduct, 2-fold to 4-fold molar adduct, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-
Propyl) ketone and propylene oxide equimolar adduct, 2-fold to 4-fold molar adduct, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4 -Decylphenyl) -2-
And hydroxy-2-methylpropan-1-one. These may be used alone or in combination of two or more.

A known photopolymerization initiation aid may be used in combination. Specific examples of these photopolymerization initiation aids include triethanolamine, diethanolamine, ethanolamine, tripropanolamine, dipropanolamine,
And propanolamine, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate. The photopolymerization initiation aid is used alone or in combination of two or more. The amount of the photopolymerization initiator (h) and the photopolymerization initiation aid used is the total amount of the reactant (d), the epoxy resin (e), and the ultraviolet curable resin (f) (dry base).
It is 1 to 15 parts by weight based on 100 parts by weight.

The filler used in the present invention is a known organic filler or inorganic filler. Until the organic filler becomes insoluble in the resin dissolving solvent, an epoxy resin, a melamine resin, a urea resin, a phenol resin, a polyimide resin, a Teflon resin, and a fine particle type filler obtained by polymerizing a polyamide resin, etc. Specifically. Examples of the inorganic filler include fine particles of a metal oxide such as alumina, antimony oxide, and ferrite, and fine particles of silicates such as talc, silica, mica, kaolin, and zeolite; barium sulfate; and calcium carbonate. The above fillers are used alone or in combination of two or more. The particle size of the filler is usually 10 μm or less. Preferably, they are fine particles of 5 μm or less.

In the present invention, when synthesizing the reactant (d),
An organic solvent is used for dissolving, diluting and mixing the epoxy resin (e), the ultraviolet curing resin (f), the epoxy curing agent (g), the photopolymerization initiator (h) and the filler. Examples of the organic solvent include acetates such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; ketones such as methyl ethyl ketone and cyclohexanone; cellosolve, butyl cellosolve Glycol ethers such as carbitol, butyl carbitol and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene and xylene; petroleum solvents such as petroleum ether and petroleum naphtha; amides such as dimethylformamide and dimethylacetamide. And used as desired.

In the curable resin composition of the present invention, known polymerization inhibitors, adhesion promoters, defoamers, leveling agents, flame retardants,
Color pigments such as phthalocyanine blue and phthalocyanine green, and thixotropic agents such as aerosil are used as desired. The curable resin composition of the present invention described above is a filler,
When mixing with a color pigment or the like, the dispersion is performed uniformly. The dispersion is performed by a known method, a polymerization inhibitor, an adhesion-imparting agent, a defoaming agent, a leveling agent, a curable resin composition containing a thixo agent, the filler, a coloring pigment, after rough kneading, for example, Kneading using three rolls or the like enables uniform dispersion. The curable resin composition thus obtained can be applied using a known screen printing, roll coater, curtain coater or the like.

After coating, the coating film is heated at 70 ° C. to 90 ° C. for 20 minutes to
It is dried using a hot air dryer or a far infrared dryer for 60 minutes to form a coating film. The thickness of the coating film is usually 30μ to 50μ.
If it is less than 30 μm, the insulation reliability is poor. If it exceeds 50 μm, the alkali development time is undesirably long.

The coating film thus obtained is exposed using a usual photomask. The active light source used at this time includes ultraviolet rays, electron beams and the like. Particularly, ultraviolet exposure is preferable. Examples of the light source at this time include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a halogen lamp. When a developer is used after exposure, an immersion method or a spray method is used. As the developing solution, an aqueous alkali solution such as sodium hydroxide or sodium carbonate is used. After the development, the film is washed with water, dried by heating, and thermally cured at 150 ° C. for 30 to 60 minutes. The cured film obtained by blending and kneading the curable resin composition of the present invention as described above, further drying and exposing, and further developing and thermally curing is soap-free and excellent in adhesion and flexibility.

[0041]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified below, “parts” means “parts by weight”. [Synthesis Example 1] (Synthesis of diisocyanate / HEMA) EP xylene 228 was placed in a 500 ml internal volume reaction vessel equipped with a thermometer, a stirrer, a cooler, and an air inlet.
Parts, 65 parts (0.50 mol) of hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) and 87 parts (0.50 mol) of tolylene diisocyanate (hereinafter abbreviated as TDI). After the addition of the catalyst, the reaction was carried out under the conditions of 80 ° C. × 3 hrs. A solid content of 40 wt% and an equimolar adduct of TDI / HEMA (hereinafter abbreviated as TDI / HEMA) were obtained.

[Synthesis Example 2] (Synthesis of soap-free acrylic rubber dispersion / epoxy resin) 38 parts of EP xylene, 190 parts (1 eq 0.50 mol) of Epicoat 828 manufactured by Yuka Shell Epoxy, 1.22 EP benzoic acid Parts (0.01 mol) and 0.95 parts of triphenylphosphine (hereinafter abbreviated as TPP) were charged into the reaction vessel used in Synthesis Example 1, and a carboxylic acid was reacted with the epoxy resin at 120 ° C. × 3 hrs. A hydroxyl group was introduced. After cooling to 90 ° C., while blowing in air, 0.090 parts of phenothiazine, TDI · HEMA 8.4 of Synthesis Example 1
A part (0.011 mol as isocyanate) and a known urethanation catalyst were added and reacted under the conditions of 90 ° C. × 10 hrs, and a methacryloyl group was introduced into a hydroxyl group of the epoxy resin to perform grafting. Then, the flow was switched to a nitrogen stream, and the reaction product was diluted with 15.0 parts of butycelloacetate at the same temperature. Next, azoisobutyronitrile (hereinafter referred to as AIB)
N) 0.6 part, butyceloacetate 15.0 parts,
60.0 parts of 2-ethylhexyl acrylate (hereinafter abbreviated as 2EHA), butyl acrylate (hereinafter abbreviated as BA)
16.9 parts of a uniform solution (91.9 parts in total) consisting of 14.0 parts, 1.3 parts of glycidyl methacrylate (hereinafter abbreviated as GMA), and 1.0 part of ethylene glycol diacrylate (hereinafter abbreviated as EGDA). Was added and polymerized over 2 hours. 75.0 parts of the remaining liquid was continuously dropped over 8 hours. After dropping, the remaining monomers are further polymerized for 2 hours, and a soap-free acrylic rubber dispersion / epoxy resin (hereinafter referred to as SAP-1) consisting of 80% by weight of solid content and 30% of island phase.
Abbreviated).

[Synthesis Example 3] (Synthesis of soap-free acrylic rubber dispersion / epoxy resin) EP xylene 53 parts, Yuka Shell Epoxy Epicoat 834 260 parts (1 eq 0.50 mol), phenothiazine 0.13 parts, TDI · HEMA of Synthesis Example 1
4 parts (0.011 mol as isocyanate) of a known urethanization catalyst were charged into the reaction vessel used in Synthesis Example 1, and reacted under the conditions of 95 ° C. × 5 hrs while blowing air to obtain a hydroxyl group contained in the epoxy resin. Then, a methacryloyl group was introduced into the resultant, and grafting was performed. Then, the flow was switched to a nitrogen stream, and the reaction product was treated with butycelloacetate 2
Diluted with 0.0 parts. Then 0.9 parts AIBN in advance,
Butycello acetate 20.0 parts, 2EHA 84.0 parts,
28.0 parts of a uniform solution (128 parts in total) consisting of 20.0 parts of BA, 1.6 parts of GMA and 1.5 parts of EGDA were added and polymerized for 2 hours. 100.0 parts of residual liquid to 8
The solution was continuously dropped over a period of hrs. After dropping, the remaining monomer is polymerized over 2 hours, and the solid content is 80 wt% and the island phase is 30%
And a soap-free acrylic rubber-dispersed epoxy resin (hereinafter abbreviated as SAP-2).

[Synthesis Example 4] (Synthesis of soap-free acrylic rubber dispersion / epoxy resin) 30 parts of EP xylene, Epicron 83 manufactured by Dainippon Ink and Chemicals, Inc.
0 150 parts (1 eq 0.50 mol), 1.22 parts (0.01 mol) of EP benzoic acid, and 0.75 part of TPP were charged into the reaction vessel used in Synthesis Example 1, and the conditions of 120 ° C. × 3 hrs were blown while blowing air. Was reacted. Then 90
Phenothiazine 0.0
80 parts, 8.4 parts of TDI / HEMA of Synthesis Example 1 (0.011 mol as isocyanate), and a known urethanization catalyst were added and reacted for 10 hours. Then, the mixture was switched to a nitrogen stream, and the reaction product was diluted with 12.0 parts of butycelloacetate at the same temperature. Then AIBN 0.5
Parts, butycello acetate 12.0 parts, 2EHA46.0
Parts, BA 11.2 parts, GMA 1.2 parts, EGDA 0.8
14.7 of a uniform solution (71.7 parts in total)
Was added and polymerized over 2 hours. 57.0 parts of the remaining liquid was continuously dropped over 8 hours. After dropping, the remaining monomer is polymerized over 2 hours, and the solid content is 80 wt%,
A soap-free acrylic rubber dispersion / epoxy resin (hereinafter abbreviated as SAP-3) consisting of 0% was obtained.

[Synthesis Example 5] (Synthesis of soap-free acrylic rubber dispersion / epoxy resin) 80 parts of EP xylene, 392 parts of EPON (octylphenol novolak type epoxy resin) manufactured by Mitsui Chemicals, Inc. (1e)
q, 0.22 mol), 1.83 parts (0.0
15 mol), 1.95 parts of TPP with an internal volume of 1000 ml
And reacted at 120 ° C. × 3 hrs. After cooling to 90 ° C., while blowing in air, 0.190 parts of phenothiazine, TDI HEMA1 of Synthesis Example 1
2.6 parts (0.0165 mol as isocyanate),
A known urethanation catalyst was added and reacted at 90 ° C. × 10 hrs. Then, the flow was switched to a nitrogen gas stream, and the reaction product was diluted with 30.0 parts of butycelloacetate at the same temperature. Next, 1.4 parts of AIBN, 30.0 parts of butycelloacetate, 123.0 parts of 2EHA, and 32.0 parts of BA
41.3 parts of a uniform solution (191.3 parts in total) consisting of 2.5 parts of GMA, 2.5 parts of GMA and 2.4 parts of EGDA were added.
Polymerization was performed over rs. 150.0 parts of the remaining liquid was continuously dropped over 8 hours. After dropping, the remaining monomer was further polymerized for 2 hours to obtain a soap-free acrylic rubber dispersion / epoxy resin (hereinafter abbreviated as SAP-4) composed of 80% by weight of solid content and 30% of island phase.

Synthesis Example 6 Synthesis of Reactant (d) 100 parts of SAP-1 of Synthesis Example 2 (0.295 eq as epoxy group), 56 parts (0.295 eq) of Epicoat 828 manufactured by Yuka Shell Epoxy, EP 43.3 parts (0.602 mol) of acrylic acid (hereinafter abbreviated as AA), 62 parts of butycelloacetate, 0.30 part of hydroquinone (hereinafter abbreviated as HQ), and 1.0 part of TPP were charged into a 500 ml reaction flask, and air was charged. 100 ℃ × 3 while blowing
The reaction was performed under the condition of 0 hrs. Then, 64.0 parts of tetrahydrophthalic anhydride (hereinafter abbreviated as THPA) (0.4
21 mol) and reacted for 5 hrs. A reaction product (d) (hereinafter abbreviated as EPA-1) having a resin acid value of 82 [mgKOH / g], a solid content of 75 wt%, and an island phase of 10.0 wt% (solid content basis) was obtained.

Synthesis Example 7 Synthesis of Reactant (d) 100 parts of SAP-2 of Synthesis Example 3 (0.215 eq as epoxy group), 56 parts of Epicoat 828 (0.2 part)
95eq), 37.4 parts (0.520 mol) of AA, 56.3 parts of butycelloacetate, 0.30 part of HQ, TP
The reaction was carried out under the same conditions as in Synthesis Example 6 except that 1.0 part of P and 55.3 parts (0.364 mol) of THPA were used. Resin acid value 78 [mgKOH / g], solid content 75w
As a result, a reaction product (d) (hereinafter abbreviated as EPA-2) having a content of 1% by weight and an island phase of 10.5 wt% (based on solid content) was obtained.

Synthesis Example 8 Synthesis of Reactant (d) 100 parts of SAP-3 of Synthesis Example 4 (0.373 eq as an epoxy group), 56 parts of cresol novolak type epoxy epiclone N665 (0.2 parts by 0.2)
71eq), 46.4 parts (0.644 mol) of AA, 64.0 parts of butycelloacetate, 0.30 part of HQ, TP
The reaction was carried out under the same conditions as in Synthesis Example 6 except that 1.0 part of P and 68.5 parts (0.451 mol) of THPA were used. Resin acid value 85 [mgKOH / g], solid content 75w
As a result, a reaction product (d) (hereinafter abbreviated as EPA-3) having a t% and an island phase of 9.5 wt% (solid content basis) was obtained.

Synthesis Example 9 Synthesis of Reactant (d) 100 parts of SAP-4 of Synthesis Example 5 (0.143 eq as epoxy group), 56 parts of octylphenol novolak type epoxy EPON manufactured by Mitsui Chemicals, Inc. (0.143 e)
q), 20.9 parts (0.290 mol) of AA, 47.0 parts of butycelloacetate, 0.25 part of HQ, TPP
The reaction was carried out under the same conditions as in Synthesis Example 6 except that 0.9 parts and 44.1 parts (0.290 mol) of THPA were used.
Resin acid value 70 [mgKOH / g], solid content 75 wt%,
Reactant (d) with 12.0 wt% of island phase (based on solid content)
[Hereinafter abbreviated as EPA-4].

[Synthesis Example 10] Cresol novolak type epoxy epiclone N665 112 manufactured by Dainippon Ink and Chemicals, Inc.
Part (0.542 eq), AA 39.0 parts (0.542
Mol), 70.0 parts of butycelloacetate, HQ 0.
The reaction was carried out under the same conditions as in Synthesis Example 6 except that 25 parts, 1.0 part of TPP, and 58.0 parts (0.381 mol) of THPA were used. Resin acid value 85 [mgKOH /
g] and a solid content of 75 wt% [abbreviated as EPA-5].
The curable resin composition of the present invention using the reactant (d) shown in the above synthesis example is shown in the following table.

[0051]

[Table 1] * 1 Dipentaerythritol hexaacrylate manufactured by Toa Gosei Co., Ltd. * 2 Trifunctional epoxy resin manufactured by Mitsui Chemicals, Inc. 211 g / eq * 3 Tris epoxypropyl isocyanurate manufactured by Nissan Chemical Co., Ltd. 100 g / q * 4 Photopolymerization initiator Irgacure 907 manufactured by Ciba Geigy * 5 Nippon Kayaku Co., Ltd. 2,4-diethylthioxanthone * 6 Nippon Aerosil Co., Ltd. thixotropic agent Aerosil 300 * 7 Monsanto Co., Ltd. Leveling agent The above curable composition is kneaded with 3 rolls and then mixed in 5 passes. Formulation was performed.

Next, the curable composition was screen-printed on a pre-degreased printed circuit board so as to have a dry film thickness of 30 μm to 35 μm. Then pre-dry 80
Exposure (300 mj / cm ² ) at 30 ° C. for 30 minutes
Was done. Next, alkali development was performed with 1% sodium carbonate at 30 ° C. × 2 minutes, and after washing with water, 150 ° C. × 30 minutes.
The thermosetting was performed under the conditions of minutes, and the cured product was evaluated. The evaluation results are shown below.

[0053]

[Table 2] ** 1 Method according to JIS K5405 ：: 100/100 adhesion ** 2 Method according to JIS K5405 ** 3 Observation of condition after immersion in various solvents for 1 hour at room temperature な し: No abnormality ** 4 JISC6481 at 260 ° C for 30 seconds x 3 cycles State observation ○: No abnormality ** 5 Erichsen extrusion distance mm according to JISK5400

Synthesis Example 11 Synthesis of Reactant (d) 200 parts of SAP-2 (0.430 eq as epoxy group), 31.7 parts of AA (0.440 mol), 44 parts of butycelloacetate of Synthesis Example 3, 0.30 parts of HQ,
1.0 part of TPP, 60.2 parts of THPA (0.396
(Mole) was used in the same manner as in Synthesis Example 6.
Resin acid value 74 [mgKOH / g], solid content 75 wt%,
A reaction product (d) (hereinafter abbreviated as EPA-6) having an island phase of 19 wt% (based on solid content) was obtained.

Synthesis Example 12 Synthesis of Reactant (d) 150 parts of SAP-3 of Synthesis Example 4 (0.560 eq as an epoxy group), 41.0 parts of AA (0.570 mol), 44 parts of butycelloacetate, 0.30 parts of HQ,
1.0 part of TPP, 60.7 parts of THPA (0.399
(Mole) was used in the same manner as in Synthesis Example 6.
Resin acid value 79 [mgKOH / g], solid content 75wt%,
A reaction product (d) (hereinafter abbreviated as EPA-7) having an island phase of 16 wt% (based on solid content) was obtained.

Synthesis Example 13 Synthesis of Reactant (d) 100 parts of SAP-1 of Synthesis Example 2 (0.295 eq as epoxy group) and 100 parts of SAP-4 of Synthesis Example 5 (0.143 eq as epoxy group) , AA 31.7
Part (0.44 mol), butycelloacetate 47 parts, HQ
The reaction was carried out in the same manner as in Synthesis Example 6 except that 0.3 part, 1.0 part of TPP, and 66.9 parts (0.440 mol) of THPA were used. A reaction product (d) (hereinafter abbreviated as EPA-8) having a resin acid value of 77 [mgKOH / g], a solid content of 75 wt%, and an island phase of 18 wt% (solid content basis) was obtained.

[0057]

[Table 3] * 1 Dipentaerythritol hexaacrylate manufactured by Toa Gosei Co., Ltd. * 2 Trifunctional epoxy resin manufactured by Mitsui Chemicals, Inc. 211 g / eq * 3 Tris epoxypropyl isocyanurate manufactured by Nissan Chemical Co., Ltd. 100 g / q * 4 Photopolymerization initiator Irgacure 907 manufactured by Ciba Geigy * 5 Nippon Kayaku Co., Ltd. 2,4-diethylthioxanthone * 6 Nippon Aerosil Co., Ltd. thixotropic agent Aerosil 300 * 7 Monsanto Co., Ltd. leveling agent

[0058]

[Table 4] ** 1 Method according to JISK5405 ：: 100/100 adhesion ** 2 Method according to JISK5405 ** 3 Observation of condition after immersion in various solvents for 1 hour at room temperature ：: No abnormality ** 4 Condition according to JISC6481 at 260 ° C for 30 seconds for 3 cycles Observation ○: No abnormality ** 5 Erichsen extrusion distance mm according to JISK5400

[0059]

According to the present invention, a cured product having excellent solvent resistance, heat resistance and flexibility can be obtained. The cured resin composition of the present invention can be used as a liquid resist composition, a cover coat agent, an overcoat agent, and an undercoat agent.

Claims (7)

[Claims] (A) A soap-free acrylic rubber dispersion.
Epoxy resin (a-1) and epoxy resin (a-2)
(D), (B) an epoxy resin (e) and an ultraviolet-curing resin (f), and (B) a reaction product of (b) an ethylenically unsaturated monocarboxylic acid (b), and a polybasic anhydride (c); C)
A curable resin composition comprising an epoxy curing agent (g) and a photopolymerization initiator (h). 2. The epoxy resin (a-1) is one of a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolak type epoxy resin. The curable resin composition according to claim 1, wherein 3. The epoxy resin (a-2) is one of a bisphenol F epoxy resin, a bisphenol AD epoxy resin, a bisphenol A epoxy resin, a phenol novolak epoxy resin, and a cresol novolak epoxy resin. Claim 1 to claim
3. The curable resin composition according to item 2. 4. Epoxy resins (a-1) and (a-2)
Is an octylphenol novolak type epoxy resin or a terpene xylenol type epoxy resin, respectively. 5. The curable resin composition according to claim 1, further comprising an organic filler or an inorganic filler. 6. A processed product formed by applying and drying the curable resin composition according to claim 1 on any one of a metal, a plastic, a ceramic, and a circuit board. 7. A soap-free acrylic rubber dispersion.
Reaction product (d) of epoxy resin (a-1), ethylenically unsaturated monocarboxylic acid (b), and polybasic anhydride (c), (B) epoxy resin (e) and ultraviolet curable resin A curable resin composition comprising (f) and (C) an epoxy curing agent (g) and a photopolymerization initiator (h).