TWI635109B - Method for manufacturing reactive epoxy carboxylate compound, resin composition and cured article thereof, article - Google Patents

Abstract

An object of the present invention is to provide a resin composition which provides a cured film excellent in curability, flexibility, toughness, and electrical reliability. The present invention is an epoxy resin (a) having at least two epoxy groups in one molecule, and a compound having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule ( b) and, if necessary, the production of a reactive epoxy carboxylate compound having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule (c) reacted in the presence of trimethylglycine method

Description

Method for producing reactive epoxy carboxylate compound, resin composition And hardened materials and articles

The present invention relates to a method for producing a reactive epoxy carboxylate compound using trimethylglycine as an esterification reaction catalyst, and a resin composition comprising the reactive epoxy carboxylate compound, comprising The resin composition of the reactive polycarboxylic acid compound of the acid modified product of the reactive epoxy carboxylate compound, and the cured product of these compositions.

As described in Patent Document 1 or Patent Document 2, various resin compositions containing a reactive epoxy carboxylate compound have been known.

Patent Document 1 describes an acid-modified epoxy acrylate compound having a polycyclic hydrocarbon group-containing epoxy resin as a basic skeleton and a cured product thereof, and is also known to have relatively high toughness after curing. Further, a solder resist using the above compound is also described.

Further, Patent Document 2 and the like disclose an epoxy carboxylate compound obtained by reacting an acrylic acid and a carboxylic acid compound having a hydroxyl group with a usual epoxy resin, and it is described that it has a low acid value and excellent developability. Further, it is described that the compound has resist ink fitness.

In Patent Document 1 or Patent Document 2, a tertiary amine or a tertiary phosphine is used as an esterification catalyst, and during storage of a resin solution (resin composition) containing an epoxy acrylate, there is a problem that the viscosity is temporally increased. Therefore, Patent Document 3 proposes a technique for losing the catalytic activity of a tertiary phosphine by performing epoxy acrylate synthesis under an oxygen atmosphere. However, in this technique, in order to ensure stability during synthesis or developability of an unexposed portion, it is necessary to strictly manage the temperature or time in the synthesis step or the catalyst deactivation step.

Further, in Patent Document 4, a quaternary phosphonium salt is used as the esterification catalyst, but bromide is used as a counter anion, and a large amount of halogen is contained in the final product, so that reliability is lowered.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 5-214048

[Patent Document 2] Japanese Patent Laid-Open No. Hei 6-324490

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-293876

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-341517

An object of the present invention is to provide a resin composition which is provided with a hardened film which is less in viscosity during storage and which is excellent in storage stability and excellent in developability, hardenability, and electrical reliability.

The present inventors have made an effort to solve the above problems, and as a result, it has been found that a resin composition having a specific reaction catalyst and composition can solve the above problems. The present invention has thus been completed.

That is, the present invention relates to: (1) a method for producing a reactive epoxy carboxylate compound, which comprises reacting an epoxy resin (a) and a compound (b) in the presence of trimethylglycine (trimethylglycine) A method for producing a reactive epoxy carboxylate compound (A), wherein the epoxy resin (a) has at least two or more epoxy groups in one molecule, and the compound (b) is in one molecule One or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups; (2) a method for producing a reactive epoxy carboxylate compound, which is an epoxy resin (a), a compound (b), And a method for producing a reactive epoxy carboxylate compound (A') wherein the compound (c) is reacted in the presence of trimethylglycine, wherein the epoxy resin (a) has at least two in one molecule More than one epoxy group, the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and the compound (c) having at least two or more in one molecule Hydroxyl group and more than one carboxyl group; (3) method for producing a reactive polycarboxylic acid compound Is a production of a reactive polycarboxylic acid compound (B) obtained by reacting a polybasic acid anhydride (d) with a reactive epoxy carboxylate compound (A) as described above in the presence of trimethylglycine. a method for producing a reactive polycarboxylic acid compound, which comprises reacting a polybasic acid anhydride (d) with a reactive epoxy carboxylate compound (A' as described above in the presence of trimethylglycine a method for producing a reactive polycarboxylic acid compound (B') obtained by the reaction; (5) a resin composition comprising the reactive epoxycarboxylic acid esterification as described above Compound (A) and/or reactive epoxy carboxylate compound (A') as described above; (6) a resin composition comprising the reactive polycarboxylic acid compound (B) as described above and/or The reactive polycarboxylic acid compound (B') as described above; (7) the resin composition as described above, further comprising the reactive compound (C); (8) the resin composition as described above, further comprising photopolymerization The initiator (D); (9) the resin composition as described above, further comprising trimethylglycine; (10) the resin composition as described above, which is a molding material; (11) as described above a resin composition which is a material for forming a film; (12) a resin composition as described above, which is a composition for a resist material; (13) a cured product which is as described above a cured product of a resin composition; (14) an article which is overcoated with a cured product of the resin composition as described above.

Since the resin composition of the present invention contains a reactive epoxy carboxylate compound and/or a reactive polycarboxylic acid compound synthesized using trimethylglycine as a main component, it does not increase in storage of the resin composition. Sticky and excellent in storage stability. In addition, the cured product obtained by curing the resin composition of the present invention by ultraviolet rays or the like can be preferably used for film formation having thermal toughness and mechanical toughness and further high temperature and high humidity resistance or thermal shock resistance. material.

The resin composition of the present invention can be used for a solder resist for a package board requiring a high reliability, and a printed wiring board. A solder resist, an interlayer insulating material for a multilayer printed wiring board, a solder resist for a flexible printed wiring board, a plating resist, or the like is used.

Hereinafter, the present invention will be described in detail.

Specific examples of the epoxy resin (a) having at least two or more epoxy groups in one molecule in the present invention include a phenol novolac type epoxy resin and a cresol novolak type epoxy resin. Trihydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy resin, bisphenol-A A novolak type epoxy resin, an epoxy resin containing a naphthalene skeleton, a glyoxal type epoxy resin, a heterocyclic epoxy resin, or the like.

Examples of the phenol novolac type epoxy resin include EPICLON N-770 (manufactured by Dainippon Ink and Chemical Industry Co., Ltd.), DEN438 (manufactured by Dow Chemical Co., Ltd.), and EPIKOTE 154. (manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN-201, RE-306 (manufactured by Nippon Kayaku Co., Ltd.), and the like. Examples of the cresol novolac type epoxy resin include EPICLON N-695 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), UVR -6650 (manufactured by Union Carbide), ESCN-195 (Sumitomo Chemical Industry Co., Ltd.) Ltd. manufactured) and so on.

Examples of the trihydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by The Dow Chemical Co., Ltd.), and EPIKOTE E1032H60 (oiled). Shell Epoxy Co., Ltd.) and so on. Examples of the dicyclopentadiene phenol type epoxy resin include XD-1000 (manufactured by Nippon Kayaku Co., Ltd.), EPICLON EXA-7200 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), and TACTIX-556 (Dow Chemical). Company manufacturing) and so on.

Examples of the bisphenol type epoxy resin include EPIKOTE 828, EPIKOTE 1001 (manufactured by Oiled Shell Epoxy), UVR-6410 (manufactured by Union Carbide Corporation), DER-331 (manufactured by The Dow Chemical Company), and YD-8125 ( Manufactured by Dongdu Chemical Co., Ltd., NER-1202, NER-1302 (manufactured by Nippon Kayaku Co., Ltd.), bisphenol-A epoxy resin, UVR-6490 (manufactured by Union Carbide Corporation), YDF-8170 (East Capital) bisphenol-F type epoxy resin, etc., such as Manufactured by Chemicals Co., Ltd., NER-7403, NER-7604 (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the biphenol-based epoxy resin include a biphenol type epoxy resin such as NC-3000, NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.), and YX-4000 (manufactured by Oiled Shell Epoxy Co., Ltd.). Ethylene glycol type epoxy resin, YL-6121 (manufactured by Oiled Shell Epoxy Co., Ltd.), and the like. Examples of the bisphenol A novolac type epoxy resin include EPICLON N-880 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), EPIKOTE E157S75 (manufactured by Oiled Shell Epoxy Co., Ltd.), and the like.

Examples of the epoxy resin containing a naphthalene skeleton include NC-7000, NC-7300, NC-7700 (manufactured by Nippon Kayaku Co., Ltd.), and EXA-4750 (manufactured by Dainippon Ink and Chemicals Co., Ltd.). Examples of the glyoxal type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Co., Ltd.). Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

The compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule in the present invention is used for an epoxy having at least two epoxy groups in one molecule. The resin (a) imparts reactivity to active energy ray. The ethylenically unsaturated group and the carboxyl group are not limited as long as they have one or more groups in the molecule. These compounds include a monocarboxylic acid compound and a polycarboxylic acid compound.

Examples of the monocarboxylic acid compound having one carboxyl group in one molecule include (meth)acrylic acid or crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a saturated dibasic acid or an unsaturated dibasic acid and A reactant of an unsaturated mono-monoglycidyl compound. Examples of the (meth)acrylic acid in the above may be (meth)acrylic acid, β-styrylacrylic acid, β-mercaptoacrylic acid, (meth)acrylic acid dimer, as a saturated dibasic acid anhydride or unsaturated second. a half ester of a monomoric reactant of a (meth) acrylate derivative having a hydroxyl group in one molecule, as a saturated dibasic acid or an unsaturated dibasic acid and monoglycidyl (meth)acrylate A half ester of an equimolar reactant such as an ester derivative.

Further, the polycarboxylic acid compound having two or more carboxyl groups in one molecule may, for example, be a saturated dibasic acid or an unsaturated dibasic acid and a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule. a half ester of a molar reactant, a half ester of a molar reaction such as a saturated dibasic acid or an unsaturated dibasic acid and a glycidyl (meth)acrylate derivative having a plurality of epoxy groups Wait.

Among these, in terms of sensitivity in the case of producing a resin composition, a reaction product of (meth)acrylic acid, (meth)acrylic acid and ε-caprolactone, or cinnamic acid can be preferably used. The compound (b) preferably has no hydroxyl group in the compound.

In the present invention, the compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule is used for introducing a hydroxyl group into the carboxylate compound. It is used as needed in the present invention.

Specific examples of the compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule include dimethylolpropionic acid, dimethylolbutyric acid, and dimethylol acetic acid. A polycarboxylic acid-containing monocarboxylic acid such as dimethylol valeric acid or dihydroxymethylhexanoic acid. More preferably, for example, dimethylolpropionic acid or the like.

Among these, in consideration of the stability of the reaction between the epoxy resin (a), the compound (b) and the compound (c), the compound (b) and the compound (c) are preferably a monocarboxylic acid, and are used in combination. In the case of a carboxylic acid and a polycarboxylic acid, the value expressed by the total mole amount of the monocarboxylic acid/the total molar amount of the polycarboxylic acid is preferably 15 or more.

The ratio of addition of the epoxy resin (a) to the total carboxylic acid of the compound (b) and the compound (c) in the reaction should be appropriately changed depending on the use. That is, in making all the rings When the oxy group is subjected to carboxylic acid esterification, since the unreacted epoxy group does not remain, the storage stability of the reactive epoxy carboxylic acid ester compound is high. In this case, only the reactivity generated by the introduced double bond is utilized.

On the other hand, by reducing the amount of the carboxylic acid compound added, the unreacted epoxy group remains, and the reactivity by the introduced unsaturated bond and the reaction with the remaining epoxy group can also be used in combination. For example, a polymerization reaction or a thermal polymerization reaction using a photocationic catalyst. However, in this case, attention should be paid to the storage of the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A') and the production conditions.

In the case of producing a reactive epoxy carboxylate compound (A) or a reactive epoxy carboxylate compound (A') having no epoxy group remaining, it is preferred that the total of the compound (b) and the compound (c) It is 90 equivalent % to 120 equivalent % with respect to 1 equivalent of the said epoxy resin (a). If it is this range, it can manufacture by the relatively stable conditions. When the total amount of the compound (b) and the compound (c) is more than the above range, the excess compound (b) and the compound (c) remain, which is not preferable.

Further, in the case of the residual epoxy group, the total of the compound (b) and the compound (c) is preferably 20 equivalent % to 90 equivalent % based on 1 equivalent of the epoxy resin (a). When it is out of this range, further reaction with an epoxy group cannot fully proceed. In this case, it is necessary to pay sufficient attention to gelatinizing in the reaction or the temporal stability of the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A').

Ratio of use of compound (b) to compound (c) relative to carboxylic acid The molar ratio compound (b): the compound (c) is preferably in the range of 100:0 to 5:95, more preferably 100:0 to 40:60. When the amount of the compound (c) used is 0, it is a reactive epoxy carboxylate compound (G), and when the amount of the compound (c) used is more than 0, it is a reactive epoxy carboxylate compound (G'). . If it is in this range, the sensitivity to the active energy ray is good, and it can be introduced to make the polybasic acid anhydride (d) and the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A' ) a sufficient hydroxyl group for the reaction.

The carboxylic acid esterification reaction can also be carried out without a solvent or by dilution with a solvent. The solvent which can be used herein is not particularly limited as long as it is an inert solvent for the carboxylic acid esterification reaction.

The amount of the solvent to be used is appropriately adjusted depending on the viscosity of the resin to be obtained or the intended use, and is preferably 90 parts by mass to 30 parts by mass based on the solid content, more preferably 80 parts by mass relative to the solid content. ~50 parts by mass.

Specific examples thereof include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, and aliphatic hydrocarbon solvents such as hexane, octane, and decane, and the like. Petroleum ether, white gasoline, solvent naphtha, etc. of the mixture, an ester solvent, an ether solvent, a ketone solvent, and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate; cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate and diethylene glycol alone. Methyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether Monoalkylene glycol monoalkyl ether monoacetate such as monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butanediol monomethyl ether acetate or A polyalkylene glycol monoester such as a monoalkyl ether monoacetate, a dialkyl glutarate, a dialkyl succinate or a dialkyl adipate.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethylbutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and triethylene glycol dimethyl ether. And glycol ethers such as triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone.

Further, it may be carried out in a separate or mixed organic solvent such as the reactive compound (C) described below. When the reactive compound (C) is used as a solvent, it can be used as it is in the form of the resin composition of the present invention, which is preferable.

In the production method of the present invention, trimethylglycine represented by the following formula (1) is used as a catalyst. The total amount of the reactant of the trimethylglycine is 100% with respect to the reactant, that is, the reactants to which the epoxy resin (a), the carboxylic acid compound (b), the compound (c), and optionally the solvent are added. The mass part is from 0.1 part by mass to 10 parts by mass. The reaction temperature at this time is from 60 ° C to 150 ° C, and the reaction time is preferably from 5 hours to 60 hours. Other catalysts may be used in combination, and specific examples of the usable catalyst include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyl. A known basic catalyst such as trimethylammonium iodide, triphenylphosphine, triphenylphosphonium, methyltriphenylphosphonium, chromium octylate or zirconium octylate is known.

When a catalyst is used, the catalyst in the resin composition of the present invention containing the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A') is not deactivated and remains. However, such a resin composition is also included in the present invention.

Further, the thermal polymerization inhibitor is preferably hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5. - Di-tert-butyl-4-hydroxytoluene and the like.

In the present reaction, sampling is appropriately performed, and the acid value of the sample is 5 mgKOH/g or less, preferably 3 mgKOH/g or less, and the end point is set as the end point.

The preferred molecular weight range of the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A') obtained in this manner is: gel permeation chromatography (GPC) The polystyrene-converted mass average molecular weight in the range of 1,000 to 50,000, more preferably 2,000 to 30,000.

When the molecular weight is less than the molecular weight, the toughness of the cured product cannot be sufficiently exhibited. Further, when the molecular weight is too large, the viscosity becomes high and coating or the like becomes difficult.

Next, the acid addition step will be described in detail. The acid addition step is carried out by introducing a carboxyl group into the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A') obtained in the above step to obtain a reactive polycarboxylic acid compound ( B) is carried out for the purpose. That is, a carboxyl group is introduced via an ester bond by subjecting a polybasic acid anhydride (d) to a hydroxyl group generated by an esterification reaction of a carboxylic acid.

The specific example of the polybasic acid anhydride (d) can be used as long as it is a compound having an acid anhydride structure in the molecule, but it is preferably an succinic anhydride or an o-benzene excellent in alkali developability, heat resistance, hydrolysis resistance, and the like. Dicarboxylic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, Trimellitic anhydride or maleic anhydride.

The reaction of adding the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the above carboxylic acid esterification reaction liquid. The amount of addition can be appropriately changed depending on the use.

In the case where the amount of the polybasic acid anhydride (d) to be added is, for example, when the reactive polycarboxylic acid compound (B) is to be used as the alkali-developing resist, it is preferred to add the finally obtained reactive polycarboxylic acid compound ( The solid content acid value of B) (according to JIS K5601-2-1:1999) is 40% KOH/g to 120 mgKOH/g, more preferably a polybasic acid anhydride (d) having a calculated value of 60 mgKOH/g to 120 mgKOH/g. When the solid content acid value at this time is in this range, the composition of the present invention exhibits good alkali aqueous developability. That is, good patterning and management of excessive development are also easy, and excess acid anhydride does not remain.

In the manufacturing method of the present invention, the three represented by the above formula (1) is used. Methylglycine is used as a catalyst. The amount of trimethylglycine used is different from the solvent to which the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A'), the polybasic acid anhydride (d), and optionally the solvent are added. The total amount of the reactants of the substance is 100 parts by mass to 0.1 parts by mass to 10 parts by mass. The reaction temperature at this time is from 60 ° C to 150 ° C, and the reaction time is preferably from 5 hours to 60 hours. Other catalysts may be used in combination, and specific examples of the usable catalyst include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyl. Trimethylammonium iodide, triphenylphosphine, triphenylphosphonium, methyltriphenylphosphonium, chromium octoate, zirconium octoate, and the like. Further, when trimethylglycine or other catalyst and solvent are used in the production of the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A'), the catalyst is not It is inactivated and remains in a solution of the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A'). When the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A') is not purified and used as a solution in the present acid addition step, it is also possible to add no further three. Methylglycine or other catalyst.

The acid addition reaction may be carried out without a solvent or may be carried out by diluting with a solvent. The solvent which can be used here is not particularly limited as long as it is an inert solvent for the acid addition reaction. Further, in the case of using a solvent in the carboxylic acid esterification reaction as the previous step, it may be directly supplied to the next step without removing the solvent under the conditions which are inert to the two reactions. Acid addition reaction. The solvent which can be used can be the same as the solvent which can be used in the esterification reaction of a carboxylic acid.

In the presence of a catalyst in the present acid addition reaction, including reactive poly The catalyst composition of the present invention in the resin composition of the carboxylic acid compound (B) or the reactive polycarboxylic acid compound (B') is not deactivated and remains, but such a resin composition is also included in the present invention. A resin composition which uses a catalyst in the carboxylic acid esterification reaction and directly uses the reaction liquid for the present acid addition reaction is also included in the present invention.

The amount of the solvent to be used is appropriately adjusted depending on the viscosity of the resin to be obtained or the intended use, and is preferably 90 parts by mass to 30 parts by mass based on the solid content, more preferably 80 parts by mass relative to the solid content. ~50 parts by mass.

Further, it may be carried out in a separate or mixed organic solvent such as the reactive compound (C). In this case, when it is used as a curable composition, it can be utilized as a composition, and it is preferable.

Further, as the thermal polymerization inhibitor or the like, it is preferred to use the same thermal polymerization inhibitor or the like as exemplified in the above-described carboxylic acid esterification reaction.

This reaction is an appropriate sampling, and the point at which the acid value of the reactant is within a range of plus or minus 10% of the set acid value is defined as the end point.

The preferred molecular weight range of the reactive polycarboxylic acid compound (B) is a polystyrene-converted mass average molecular weight in the GPC of from 1,000 to 50,000, more preferably from 2,000 to 30,000.

Specific examples of the reactive compound (C) which can be used in the present invention include a radical reaction type acrylate, a cationic reaction type other epoxy compound, and a vinyl compound which induces both of them. So-called reactive oligomers (oligomers).

Examples of the acrylate which can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

Examples of the monofunctional (meth) acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, and polyethylene glycol (A). Acrylate, (poly)ethylene glycol (meth) acrylate monomethyl ether, phenyl ethyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of the polyfunctional (meth) acrylate include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and decanediol II. (meth) acrylate, diol di(meth) acrylate, diethylene di (meth) acrylate, (poly) ethylene glycol di(meth) acrylate, different Tris(methyl) propylene methoxyacetate cyanurate, polypropylene glycol di(meth) acrylate, adipic acid epoxide di(meth) acrylate, bisphenol oxirane di(meth) acrylate , hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di(meth) acrylate, ε-caprolactone hydroxypivalate neopentyl glycol adduct di(meth)acrylic acid Poly(meth) acrylate of diester, dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth) acrylate, trimethylolpropane tri(meth) acrylate, trishydroxyethyl propane Tris(meth)acrylate, its ethylene oxide adduct, pentaerythritol tri(meth)acrylate, and its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate, dipentaerythritol Alcohol hexa(meth) acrylate, an ethylene oxide adduct thereof, and the like.

Examples of the vinyl compound which can be used include vinyl ether and styrene. Classes, other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrenes include styrene, methylstyrene, and ethylstyrene. Examples of the other vinyl compound include triallyl isocyanurate and trimethylallyl isocyanurate.

Further, the term "reactive oligomer" includes an urethane urethane having a functional group capable of inducing an active energy ray and a urethane bond in the same molecule, and the same molecule can be used in the same molecule. A polyester acrylate which induces a functional group of an active energy ray and an ester bond, an epoxy acrylate derived from another epoxy resin and having a functional group capable of inducing an active energy ray in the same molecule, and a reaction using the bond Oligomers and the like.

Further, the cationically reactive monomer is not particularly limited as long as it is a compound having an epoxy group. For example, glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3, 4-epoxy cyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester ("Cyracure UVR-6110" manufactured by Union Carbide Co., Ltd.), 3,4-epoxycyclohexylethyl 3,4-epoxycyclohexanecarboxylate, dioxide Vinyl cyclohexene ("ELR-4206" manufactured by Union Carbide Co., Ltd.), limonene dioxide ("Celloxide 3000" manufactured by Daicel Co., Ltd.), propylene oxide cyclohexene, 3, 4 -Epoxy-4-methylcyclohexyl-2-epoxypropane, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexanemethane , bis(3,4-epoxycyclohexyl) adipate ("Cyracure UVR-6128" manufactured by Union Carbide Co., Ltd.), bis(3,4-epoxycyclohexylmethyl) adipate, Bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxy ring) Hexyl) diethyl oxane and the like.

Among these, the reactive compound (C) is preferably a radical-curable acrylate. In the case of a cationic type, a carboxylic acid reacts with an epoxy, and therefore it is necessary to prepare a two-liquid mixing type.

Any one of the reactive epoxy carboxylate compound (A), the reactive epoxy carboxylate compound (A'), the reactive polycarboxylic acid compound (B), and the reactive polycarboxylic acid compound (B') The resin composition of the present invention is obtained by mixing with the other reactive compound (C). In this case, other components may be appropriately added depending on the application.

The resin composition of the present invention contains a reactive epoxy carboxylate compound (A), a reactive epoxy carboxylate compound (A') and/or a reactive polycarboxylic acid compound (B) in the composition, and reactivity The polycarboxylic acid compound (B') is 97 parts by mass to 5 parts by mass, preferably 87 parts by mass to 10 parts by mass, and further contains 3 parts by mass to 95 parts by mass, more preferably 3 parts by mass, of the other reactive compound (C). ~90 parts by mass. Other components may be contained in an amount of from 0 parts by mass to 80 parts by mass, as needed.

The carboxylate compound (A), the carboxylate compound (A'), the reactive polycarboxylic acid compound (B), and the reactive polycarboxylic acid compound (B') in the resin composition of the present invention can be used according to the use thereof. And use it appropriately. For example, even in the case of the solder resist application, a reactive epoxy is used in the case of forming a pattern by a printing method without development or a so-called solvent developing type in which an unreacted portion flows by a solvent or the like. The carboxylate compound (A) is a reactive polycarboxylic acid compound (B) in the case of development by alkaline water. In general, in view of the fact that the alkaline water developing type easily forms a fine pattern, in many cases, a reactive polycarboxylic acid is used for the purpose. Compound (B). Of course, there is no problem in using (A), (A'), (B) and (B') together.

The resin composition of the present invention is easily hardened by active energy rays. Specific examples of the active energy ray here include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays (γ rays), and laser rays, alpha rays (α rays), and beta rays (β rays). ), particle beams such as electron beams, and the like. In view of the preferred use of the present invention, among these, ultraviolet rays, laser rays, visible rays, or electron beams are preferred.

In the present invention, the material for molding refers to a material used for adding an uncured composition to a mold or pressing a mold to form an object, and then forming a hardening reaction by an active energy ray, or The uncured composition is formed by irradiating a focus light such as a laser to cause a hardening reaction.

Specific applications include the following materials: a sheet formed into a flat shape, a sealing material for protecting the element, and a finely formed "mold" for pressing the uncured composition to be finely formed. The nanoimprint materials, in particular, the light-emitting diodes such as light-emitting diodes and the peripheral sealing materials such as photoelectric conversion elements.

In the present invention, the material for forming a film refers to a material used for the purpose of covering the surface of the substrate. For specific applications, ink materials such as gravure inks, flexo inks, silk screen inks, offset inks, hard coats, Coating of top coat, overprint varnish, clear coat, etc. Materials, laminates, optical disks, other adhesives, adhesives, etc., resistants, etching resists, resists for micromachines, etc. The material conforms to the above-mentioned film forming material. Further, after the film forming material is temporarily applied to the release substrate and film-formed, a so-called dry film which is bonded to the original target substrate to form a film also conforms to the film forming material.

The present invention also includes a cured product obtained by irradiating the resin composition of the present invention with an active energy ray, and also comprising a multilayer material having a layer of the cured product.

Among these, by introducing a carboxyl group of the reactive polycarboxylic acid compound (B) or the reactive polycarboxylic acid compound (B') to improve the adhesion to the substrate, it is preferably used as a plastic substrate for coating. (plastic base), or the use of a metal substrate.

Further, the unreacted reactive polycarboxylic acid compound (B) or the unreacted reactive polycarboxylic acid compound (B') is effectively used as a characteristic of being soluble in an aqueous alkali solution, and is also preferably used as an alkaline water developing type resist. Agent material composition.

In the present invention, the resin composition for a resist material refers to a film layer on which a composition is formed on a substrate, and then partially irradiates an active energy ray such as ultraviolet rays, thereby utilizing physical properties of the irradiated portion and the unirradiated portion. The active energy ray-sensitive composition is depicted. Specifically, it is a composition used for the purpose of drawing the irradiation part or the non-irradiation part by dissolving it by a certain method, for example, by a solvent, etc., or an alkaline solution.

The resin composition for a resist material of the present invention can be adapted to be patternable Various materials, such as, for example, a solder resist material, an interlayer insulating material for a build up method, and can also be used as an optical waveguide for electrical wiring such as a printed wiring board, an optoelectronic substrate, or a light substrate. electronic. Light substrate, etc.

A particularly preferable use is a permanent resist application such as a solder resist, which can effectively utilize the properties of a cured product which can obtain toughness.

Patterning using the resin composition of the present invention can be carried out, for example, in the following manner. Using a screen print method, a spray method, a roll coat method, an electrostatic coating method, a curtain coat method, a spin coating method (Spin coat method) or the like, the composition of the present invention is applied onto a substrate at a film thickness of 0.1 μm to 200 μm, and the coating film is applied at a temperature of usually 50 ° C to 110 ° C, preferably 60 ° C to 100 ° C. Drying, whereby a coating film can be formed. Thereafter, the coating film can be directly or indirectly irradiated with high-energy rays such as ultraviolet rays at a strength of usually about 10 mJ/cm ² to 2000 mJ/cm ² via a photomask having an exposure pattern, and the developing solution described later can be used, for example, by using, for example, a photomask. Spray, vibration dipping, puddle, brushing, etc., to obtain a desired pattern.

The aqueous alkali solution used in the above development may be an aqueous solution of an inorganic alkali such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate or potassium phosphate or tetramethylammonium hydroxide or the like. An aqueous solution of an organic alkali such as ethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine or triethanolamine. The aqueous solution may further contain an organic solvent, a buffer, a binder, a dye or a pigment.

In addition, it can be used particularly as a hardening requiring active energy rays. Dry film use of mechanical strength before reaction. That is, since the balance of the hydroxyl group and the epoxy group of the epoxy resin (a) used in the present invention is within a specific range, even if the reactive carboxylate compound used in the present invention has a relatively high molecular weight. It also exerts good developability.

The method of forming the film is not particularly limited, and a gravure printing method such as a gravure, a relief printing method such as flexo printing, a stencil printing method such as a screen printing, a lithographic printing method such as a lithography, a roll coater, or the like, may be used arbitrarily. Various coating methods such as a knife coater, a die coater, a curtain coater, and a spin coater.

The article protected by the cured product of the present invention is a material obtained by forming at least two or more layers obtained by forming a film of the resin composition of the present invention on a substrate and then curing the film.

In addition, for the purpose of making the resin composition of the present invention suitable for various uses, it is also possible to add another component to the composition in an amount of 70 parts by mass. Other components include a photopolymerization initiator, other additives, a coloring material, and a volatile solvent added to adjust the viscosity to impart coating suitability and the like. The other ingredients that can be used are exemplified below.

The photopolymerization initiator (D) is capable of inducing an active energy ray to start polymerization of the reactive epoxy carboxylate compound (A), the reactive polycarboxylic acid compound (B), and the reactive compound (C). The active ingredient of the species. Examples of such a photopolymerization initiator (D) include a radical photopolymerization initiator, a cationic photopolymerization initiator, a Lewis acid sulfonium salt, and a salt compound.

Examples of the radical type photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and the like; acetophenone, 2,2-diethoxy-2-phenyl Acetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2- Acetophenones such as methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one; 2-ethylhydrazine, 2-tert-butylhydrazine, Anthraquinones such as 2-chloroindole and 2-pentylhydrazine; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; a ketal such as ketone dimethyl ketal or benzoin dimethyl ketal; benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4'-double Benzophenones such as methylaminobenzophenone; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene) A known conventional radical photoreaction initiator such as a phosphine oxide such as phenylphosphine oxide.

Further, examples of the cationic photopolymerization initiator include a diazonium salt of a Lewis acid, a phosphonium salt of a Lewis acid, a phosphonium salt of a Lewis acid, a phosphonium salt of a Lewis acid, other halides, a triazine-based initiator, and boric acid. a salt-based initiator, and other photoacid generators.

The diazonium salt of a Lewis acid may, for example, be p-methoxyphenyldiazonium fluorophosphonate or N,N-diethylaminophenyldiazonium hexafluorophosphonate (Sanxin Chemical Industry Co., Ltd. The sulfonium salt of Lewis acid, such as Sun Aid SI-60L/SI-80L/SI-100L manufactured by the company, etc., may be exemplified by diphenylphosphonium hexafluorophosphonate or diphenylphosphonium hexafluoroantimonate. Examples of the phosphonium salt of the Lewis acid include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide Co., Ltd.), and triphenylsulfonium For example, a fluoroantimonate (Cyracure UVI-6974 manufactured by Union Carbide Co., Ltd.) or the like, and a phosphonium salt of a Lewis acid may, for example, be triphenylsulfonium hexafluoroantimonate.

Other halides include 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanone (TrigonalPI, manufactured by Akzo), 2,2-two. Chloro-1-4-(phenoxyphenyl)ethanone (Sandray 1000, manufactured by Sandoz, etc.), α,α,α-tribromomethylphenylhydrazine (manufactured by Sumitomo Seika Co., Ltd.) BMPS, etc.). The triazine starting agent can be exemplified by 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine. (TriazineA manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (Triazine PMS manufactured by Panchim, etc.), 2, 4-trichloromethyl-(piperonyl)-6-triazine (TriazinePP, manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6- Triazine (Triazine B, manufactured by Panchim, etc.), 2[2'(5-methylfuranyl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (Sanwa Chemical) ), Ltd., etc.), 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd.), and the like.

Examples of the borate photopolymerization initiator include NK-3876 and NK-3881 manufactured by Japanese photosensitive pigments, and other photoacid generators include 9-phenyl acridine and 2,2'-bis(o-chlorobenzene). -4,4',5,5'-tetraphenyl-1,2-biimidazole (BIIMIDAZOLE, manufactured by Heijin Chemical Co., Ltd.), 2,2-azobis(2-amine Base-propane) dihydrochloride (V50 manufactured by Wako Pure Chemical Co., Ltd.), 2,2-azo Bis[2-(imidazolin-2-yl)propane]dihydrochloride (VA044, manufactured by Wako Pure Chemical Co., Ltd.), [η-5-2-4-(cyclopentadecyl) (1, 2) , 3,4,5,6,η)-(methylethyl)-benzene]iron(II) hexafluorophosphonate (Irgacure 261 manufactured by Ciba Geigy Co., Ltd.), double (y5-ring) Pentadienyl) bis[2,6-difluoro-3-(1H-pyridin-1-yl)phenyl]titanium (CGI-784, manufactured by Ciba Geigy Co., Ltd.) and the like.

In addition, an azo-based initiator such as azobisisobutyronitrile or a peroxide-based radical initiator which is inductive to heat such as benzoyl peroxide may be used in combination. Further, a radical-based or cationic-based initiator may be used in combination. The initiator may be used alone or in combination of two or more.

In the resin composition of the present invention, when the solid content of the composition of the present invention is 100% by mass, the amount of the photopolymerization initiator (D) used is 1% by mass or more and 20% by mass or less. It is preferably 1% by mass or more and 15% by mass or less.

As other additives, for example, a thermosetting catalyst such as melamine, a thixotropy-imparting agent such as Aerosil, an anthrone-based, a fluorine-based leveling agent or an antifoaming agent, hydroquinone, or the like may be used. A polymerization inhibitor such as hydroquinone monomethyl ether, a stabilizer, an antioxidant, and the like.

Further, as the other pigment material, for example, a so-called extender pigment which is not a material for coloring may be used. For example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, cerium oxide, clay, or the like can be mentioned.

In addition, resins that do not exhibit reactivity to active energy rays (so-called Inert polymer), for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone-based formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, Styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and modified products of these resins. These resins are preferably used in the resin composition in the range of up to 40 parts by mass.

In particular, when a reactive polycarboxylic acid compound (B) or a reactive polycarboxylic acid compound (B') is used for a solder resist application, it is preferred to use a resin which does not exhibit reactivity with an active energy ray. The usual epoxy resin. This is because the carboxyl group derived from (B) or (B') remains after being reacted by the active energy ray and hardened, and as a result, the cured product has poor water resistance or hydrolysis property. Therefore, the remaining carboxyl group is further carboxylated by using an epoxy resin, thereby forming a strong crosslinked structure. The above-mentioned cationically reactive monomer can be used in the conventionally known epoxy resin.

Further, in order to adjust the viscosity according to the purpose of use, a volatile solvent may be added in the resin composition in a range of at most 50 parts by mass, more preferably at most 35 parts by mass.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. In addition, in the examples, the parts represent parts by mass unless otherwise specified.

The acid value was measured under the following conditions.

1) Acid value: The measurement was carried out by the method according to JIS K0070:1992.

Example 1-1 to Example 1-4: Production of Reactive Epoxy Carboxylate Compound (A)

NC-3000H (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g/eq) and XD-1000 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent) as the epoxy resin (a) described in Table 1 were added. 254 g/eq), acrylic acid (abbreviated as AA, Mw=72) as the compound (b), and dimethylolpropionic acid (DMPA, Mw) as the compound (c) described in Table 1, in the amounts shown in Table 1. =134). 3 g of trimethylglycine (TMG) as a catalyst was added, and propylene glycol monomethyl ether monoacetate as a solvent was added so as to have a solid content of 80% by mass of the reaction liquid, and the reaction was carried out at 100 ° C for 24 hours. A solution of the reactive epoxy carboxylate compound (A) or the reactive epoxy carboxylate compound (A') is obtained. When the solid content acid value (AV: mgKOH/g) is 5 mgKOH/g or less, it is set as the reaction end point, and it progresses to the next reaction. The acid value was measured in the reaction solution and converted into an acid value as a solid component.

Comparative Example 1-1 to Comparative Example 1-3: Production of comparative reactive epoxy carboxylate compound

In the amount of the epoxy resin (a), NC-3000H (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g/eq), and the amount of acrylic acid as the compound (b) described in Table 1, were added. Tetramethylammonium chloride (abbreviated as TMAC), triphenylphosphine (TPP), and benzyltriphenylphosphonium bromide (TZP) 3 g as a catalyst, and the solid content is 80% by mass of the reaction liquid. In the manner of adding propylene glycol monomethyl ether monoacetate as a solvent, the reaction was carried out at 100 ° C for 24 hours to obtain a carboxylate compound solution. The solid content acid value (AV: mgKOH/g) was set to 5 mgKOH/g or less as the reaction end point.

Example 2-1 to Example 2-4: Preparation of Reactive Polycarboxylic Acid Compound (B)

To the solution of the reactive epoxy carboxylate compound (A) obtained in Example 1-1 to Example 1-4, tetrahydrophthalic anhydride as a polybasic acid anhydride (d) was added in an amount described in Table 2 ( Hydrylene glycol monomethyl ether monoacetate as a solvent is added so as to have a solid content of 65 parts by mass, and after heating to 100 ° C, an acid addition reaction is carried out to obtain a reactive polycarboxylic acid compound (B). A reactive polycarboxylic acid compound (B') solution. The solid component acid value (AV: mgKOH/g) is shown in Table 1.

Comparative Example 2-1 to Comparative Example 2-3: Preparation of Reactive Polycarboxylic Acid Compound

To the reactive epoxy carboxylate compound solution obtained in Comparative Example 1-1 to Comparative Example 1-3, THPA as a polybasic acid anhydride described in Table 2 was added, and the solid component was added in an amount of 65 parts by mass. The solvent propylene glycol monomethyl ether monoacetate was heated to 100 ° C, and then subjected to an acid addition reaction to obtain a comparative reactive polycarboxylic acid compound solution. The solid component acid value (AV: mgKOH/g) is shown in Table 2.

[Table 2]

Example 3 and Comparative Example 3: Preparation of dry film type resist composition

The reactive polycarboxylic acid compound (B) obtained in Example 2 or 54.44 g of the reactive polycarboxylic acid compound obtained in Comparative Example 2 and HX-220 as another reactive compound (C) were added (trade name: 3.54 g of diacrylate monomer manufactured by Nippon Kayaku Co., Ltd., Irgacure 907 (manufactured by Ciba Specialty Chemicals) as photopolymerization initiator (D), 4.72 g and Kayacure DETX-S (Japan) Chemicals Co., Ltd.) 0.47 g, GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) 14.83 g as a hardening component, 1.05 g of melamine as a thermosetting catalyst, and methyl ethyl ketone 20.95 as a concentration adjusting solvent g, kneading using a beads mill and uniformly dispersing to obtain a resist resin composition.

The obtained composition was uniformly applied onto a polyethylene terephthalate film to be a support film by a roll coating method, and passed through a hot air drying oven at a temperature of 70 ° C to form a resin layer having a thickness of 30 μm. Thereafter, a polyethylene film to be a protective film was attached to the resin layer to obtain a dry film. The obtained dry film was applied to a polyimide substrate (copper circuit thickness: 12 μm, polythene film thickness: 25 μm), and heating at a temperature of 80 ° C was used. A hot roll is attached to the entire surface of the substrate while peeling off the protective film.

Next, using an ultraviolet exposure apparatus (ORC MANUFACTURING Co., Ltd., model: HMW-680GW), a stage made by Kodak via a mask in which a circuit pattern is drawn and in order to estimate sensitivity The exposure meter (Step Tablet) No. 2 was irradiated with ultraviolet rays. Thereafter, the film on the dry film was peeled off and the peeled state was confirmed. Thereafter, spray development was carried out using a 1% sodium carbonate aqueous solution to remove the resin in the ultraviolet non-irradiated portion. After washing with water, the printed substrate was subjected to a heat curing reaction for 60 minutes using a hot air dryer at 150 ° C to obtain a cured film. The results of each evaluation are shown in Table 3.

Resistance to thermal shock resistance

The polyimide film of the cured film formed with the resist was subjected to a thermal shock test in the range of -65 ° C to 120 ° C. The test method is based on JISC5012-9.1:1993. After the test, a peel test using Cellophane Tape (registered trademark) was carried out.

○: no peeling

△: a little peeling

×: peeling

High temperature moisture resistance evaluation

The polyimide substrate on which the cured film of the resist was formed was placed in an autoclave at 120 ° C for 1 hour. The substrate was taken out, air-dried at room temperature, and a peel test using Cellophane Tape (registered trademark) was carried out.

○: no peeling

△: a little peeling

×: peeling

Sensitivity evaluation

The sensitivity is determined by the concentration portion remaining in the first few cells when the exposure portion of the stage exposure meter is developed. The larger the number of cells (value) is the rich portion of the exposure meter and is determined to be high sensitivity (unit: cell).

Development evaluation

The developability is the evaluation of the developability (unit: second) when the exposure portion that has passed through the pattern mask is developed, and the time until the pattern portion is completely developed, that is, the so-called break time.

Reliability evaluation (migration evaluation)

Each composition was applied to a ESPANEX M series (Sries) having a comb pattern of L/S = 25 μm / 25 μm by a screen printing method to a thickness of 25 μm (manufactured by Nippon Steel & Metal Co., Ltd. The coating film was dried by a hot air dryer at 80 ° C for 60 minutes on a substrate having a thickness of 25 μm and a thickness of Cu of 18 μm. Then, the entire surface of the coating film was hardened by irradiating ultraviolet rays with an ultraviolet exposure apparatus (manufactured by USHIO: 500 W Multi-Light). Next, development was carried out by using a 1% sodium carbonate aqueous solution (temperature: 30 ° C) as a developing solution for 120 seconds of spraying (spraying pressure: 0.2 MPa). After washing with water, heat treatment was performed for 60 minutes in a hot air dryer at 200 ° C to obtain a test substrate for evaluation of a High Accelerated Stress Tester (HAST). The electrode portion of the obtained substrate was connected by soldering, and placed in an environment of 120 ° C / 85% RH, and a voltage of 100 V was applied to measure the time until the resistance value became 10 ⁷ Ω or less.

○..250 hours or more

△..30 hours to 250 hours

×..30 hours or less

Sturability evaluation

The hardenability evaluation was expressed by the pencil hardness of the cured film after completion of heating at 150 °C. The evaluation method is based on JISK5600-5-4:1999.

From the above results, it is clear that the resist composition of the present invention has high electrical reliability. Further, it has good developability and sensitivity as a resist.

Example 4 and Comparative Example 4: Storage stability

The storage stability of the resin solutions obtained in Example 2 and Comparative Example 2 was evaluated, and the results are shown in Table 3. The storage stability was carried out by adding each resin solution to a 30 ml screw tube and storing it in a warm air dryer at 60 °C. The storage period was carried out at 60 ° C × 1 week, 60 ° C × 2 weeks, and 60 ° C × 4 weeks. Use E-type viscosity The viscosity was measured by time measurement, and the viscosity increase ratio (magnification) with respect to the initial viscosity (= 1.0) was evaluated. The results are shown in Table 4.

From the above results, it is clear that the resin composition of the present invention does not change in viscosity at 60 ° C for 2 weeks, and does not change slightly until it is stored for 4 weeks. On the other hand, when the reactive epoxy resin compound and the reactive polycarboxylic acid compound are produced, the resin composition of the comparative example in which trimethylglycine is not used is increased in viscosity after one week of storage, and thereafter Timeliness rises. Therefore, the resin composition obtained by the production method of the present invention using trimethylglycine as a catalyst is excellent in storage stability.

[Industrial availability]

The composition of the present invention is suitable for a resist material which is excellent in developability and storage stability, is excellent in curability and electrical reliability, and can be subjected to alkaline development. For example, it can be preferably used for a solder resist for a package substrate and a printed wiring. A solder resist for a board, an interlayer insulating material for a multilayer printed wiring board, a solder resist for a flexible printed wiring board, a plating resist, or the like.

Claims (13)

A method for producing a reactive epoxy carboxylate compound, which is a reactive epoxy carboxylate compound (A) in which an epoxy resin (a) and a compound (b) are reacted in the presence of trimethylglycine The method of producing the epoxy resin (a) having at least two or more epoxy groups in one molecule, and the compound (b) having one or more polymerizable ethylenically unsaturated groups in one molecule And one or more carboxyl groups, wherein the trimethylglycine is used as a catalyst. A method for producing a reactive epoxy carboxylate compound, which is a reactive epoxy carboxyl group which reacts an epoxy resin (a), a compound (b) and a compound (c) in the presence of trimethylglycine A method for producing an acid ester compound (A), wherein the epoxy resin (a) has at least two or more epoxy groups in one molecule, and the compound (b) has one or more polymerizable groups in one molecule The ethylenically unsaturated group has one or more carboxyl groups, and the compound (c) has at least two or more hydroxyl groups and one or more carboxyl groups in one molecule, wherein the trimethylglycine is used as a catalyst. A resin composition comprising the reactive epoxy carboxylate compound (A) produced by the method for producing a reactive epoxy carboxylate compound according to the first aspect of the invention. A resin composition comprising the reactive epoxy carboxylate compound (A') produced by the method for producing a reactive epoxy carboxylate compound according to the second aspect of the invention. A resin composition comprising a reaction of producing a polybasic acid anhydride (d) with a method for producing a reactive epoxy carboxylate compound as described in claim 1 The reactive polycarboxylic acid compound (B) obtained by reacting the epoxy carboxylic acid ester compound (A). A resin composition comprising a reaction of a polybasic acid anhydride (d) with a reactive epoxy carboxylate compound (A') produced by the method for producing a reactive epoxy carboxylate compound according to claim 2 The reactive polycarboxylic acid compound (B') obtained is obtained. The resin composition according to any one of claims 3 to 6, which comprises a reactive epoxy carboxylate compound (A), a reactive epoxy carboxylate compound (A'), and a reaction. The polycarboxylic acid compound (B), the reactive compound (C) other than the reactive polycarboxylic acid compound (B'), and the photopolymerization initiator (D). The resin composition according to any one of claims 3 to 6, which comprises trimethylglycine. The resin composition according to any one of claims 3 to 6, which is a material for molding. The resin composition according to any one of claims 3 to 6, which is a material for forming a film. The resin composition according to any one of claims 3 to 6, which is a composition for a resist material. A cured product which is a cured product of the resin composition according to any one of claims 3 to 8. An article coated with a cured product of a resin composition as described in claim 12 of the patent application.