KR20180089286A - Reactive polycarboxylic acid compound, active energy ray curable resin composition using same and cured product thereof, and use thereof - Google Patents

Abstract

The purpose of the present invention is to provide an active energy ray curable resin composition which gives a cured coating film having excellent heat resistance, thermal decomposition resistance, and developing properties. A reactive polycarboxylic acid compound of the present invention is obtained by making a reactive epoxy carboxylate compound (c) obtained by making an epoxy resin (a) represented by formula (1) react with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, and react with a polybasic acid anhydride (d) represented by formula (2) or (3). In formula (1), n denotes an average value, and denotes a value of 0 to 20. In formula (2), R_1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Description

REACTIVE POLYCARBOXYLIC ACID COMPOUND, ACTIVE ENERGY RAY CURABLE RESIN COMPOSITION USING SAME AND CURED PRODUCT THEREOF, AND USE THEREOF BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a novel reactive polycarboxylic acid compound, an active energy ray-curable resin composition containing them, a cured product thereof, and an overcoated article. In particular, the present invention relates to a novel reactive polycarboxylic acid compound suitable as a resist material applicable as a buildup layer of a printed wiring board, an active energy ray-curable resin composition containing the same, and a cured product thereof.

Generally, a thermosetting resin composition is used for a buildup layer such as a printed wiring board. In order to reduce the size and weight of a portable device and to improve the communication speed, wiring density is increasing due to miniaturization of the wiring and layering of the buildup layer.

On the other hand, in the outermost layer of the solder resist layer of the printed wiring board, a solder resist layer is formed by using a photosensitive resin composition in order to prevent deterioration of wiring. For example, Patent Document 1 discloses a photosensitive resin composition containing a binder resin obtained by reacting a reaction product of an epoxy resin having a triglycidyl ether structure and an unsaturated group-containing carboxylic acid with a polybasic acid anhydride.

Further, a photosensitive resin composition in which a phenol compound is blended as a thermosetting component with the intention of improving adhesion after a PCT test has been known (Patent Document 2). In addition, a photosensitive resin composition capable of developing alkali with good heat resistance and low dielectric tangent (positive tangent) has recently been developed for use as a material for a buildup layer (Patent Document 3).

JP-A-3-100009 International Publication No. 2010/026927 Japanese Laid-Open Patent Publication No. 2013-214057

However, the photosensitive resin composition described in Patent Document 1 has poor developability and thermal decomposability, and is not at a satisfactory level. The photosensitive resin composition of Patent Document 2 is limited in its use for a protective film, and its physical performance is not sufficient. In Patent Document 3, heat resistance and thermal decomposition resistance are still insufficient. Although the photosensitive resin composition is advantageous in that it is inexpensive and has a simple manufacturing process, its physical performance is not sufficient and it is difficult to apply it to a build-up layer.

It is therefore an object of the present invention to provide a novel reactive polycarboxylic acid compound suitable as a resist material which can be used as a build-up layer by improving the above-mentioned problems of the prior art and having heat resistance, heat decomposition resistance, fine alkali development, It is an object of the present invention to provide a resin composition.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies and, as a result, have found that a reaction product of an epoxy resin having a specific triglycidyl ether structure and an unsaturated group-containing carbonic acid is reacted with a specific polybasic acid anhydride, The present inventors have reached the present invention.

That is,

[1] A process for producing a reactive epoxy carboxylate compound (c) obtained by reacting an epoxy resin (a) represented by the following formula (1) with a carbonic acid compound (b) having an ethylenically unsaturated group capable of polymerization in one molecule and a carboxy group, A reactive polycarboxylic acid compound (A) obtained by reacting a polybasic acid anhydride (d) represented by the following formula (2) or (3)

(In the formula, n represents an average value and represents a value of 0 to 20.)

(In the formula (2), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

[2] An active energy ray-curable resin composition comprising the reactive polycarboxylic acid compound (A) described in [1]

[3] The active energy ray-curable resin composition according to [2], which further comprises a reactive compound (B) other than the reactive polycarboxylic acid compound (A)

[4] The active energy ray-curable resin composition according to [2] or [3], wherein the active energy ray-

[5] The active energy ray-curable resin composition according to any one of items [2] to [4], which comprises a thermosetting catalyst,

[6] The active energy ray-curable resin composition according to any one of items [2] to [5], which is a molding material,

[7] The active energy ray-curable resin composition according to any one of items [2] to [5]

[8] The active energy ray-curable resin composition according to any one of items [2] to [5], which is a resist material composition,

[9] A cured product of the active energy ray-curable resin composition according to any one of [2] to [8]

[10] An article overcoated with a cured product of the active energy ray-curable resin composition according to the item [9]

.

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention has not only a strong cured product but also excellent resin properties even when the solvent is dried. Further, the cured product obtained by curing the active energy ray-curable resin composition of the present invention with active energy rays such as ultraviolet rays or the like is suitable as a resist material which is heat-resistant, heat-decomposable, finely alkali-developable and applicable as a build-up layer.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

The reactive polycarboxylic acid compound (A) of the present invention is obtained by reacting an epoxy resin (a) having a structure represented by the following formula (1) with a carboxylic acid compound (b) having an ethylenically unsaturated group capable of polymerizing in one molecule and a carboxy group To obtain a reactive epoxy carboxylate compound (c). Can be obtained by reacting the polybasic acid anhydride (d) represented by the following formula (2) or (3).

(In the formula, n represents an average value and represents a value of 0 to 20.)

(In the formula (2), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

The epoxy resin (a) (hereinafter also referred to simply as " epoxy resin (a) ") represented by the above formula (1) used in the present invention is available under various trade names such as TECMORE, VG-3101 Seki Yukagaku Co., Ltd., trade name) and NC-6000 (manufactured by Nippon Kayaku Co., Ltd.).

In the present invention, the carbonic acid compound (b) (hereinafter also simply referred to as " carbonic acid compound (b) ") having both an ethylenically unsaturated group and a carboxyl group capable of being polymerized in one molecule, . The ethylenic unsaturated group and the carboxyl group are not limited as long as they have one or more ethylenic unsaturated groups and carboxyl groups, respectively.

Examples of the carbonic acid compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in the molecule include (meth) acrylic acid, crotonic acid,? -Cyanosinic acid, cinnamic acid or a saturated or unsaturated dibasic acid and unsaturated And a reaction product of a group-containing monoglycidyl compound. Examples of the (meth) acrylic acid in the above include (meth) acrylic acid,? -Styryl acrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, Acrylate derivatives and mono-carbonates containing a carboxyl group in one molecule such as semi-esters which are reaction products of mono-glycidyl (meth) acrylate and mono-glycidyl (meth) (Meth) acrylate derivatives having a plurality of hydroxyl groups in a molecule and half-esters of a bimolecular reactant, a bimodal reactant of a glycidyl (meth) acrylate derivative having a plurality of epoxy groups with a saturated or unsaturated dibasic acid And polycarboxylic acid compounds having a plurality of carboxyl groups in one molecule such as phosphorus acid esters and the like.

Among them, in consideration of the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), the carboxylic acid compound (b) is preferably a monocarbonic acid, and even when monocarboxylic acid and polycarboxylic acid are used in combination, It is preferable that the value represented by molar amount of carboxylic acid / molar amount of polycarboxylic acid is 15 or more.

Most preferred is a reaction product of (meth) acrylic acid, (meth) acrylic acid and? -Caprolactone or cinnamic acid from the viewpoint of sensitivity when the active energy ray-curable resin composition is used.

The carboxylation process for imparting reactivity to the carboxylate compound to obtain the reactive epoxycarboxylate compound (c) is described below.

The charging ratio of the epoxy resin (a) and the carboxylic acid compound (b) in this reaction should be appropriately changed depending on the application. That is, in the case of carboxylating all the epoxy groups, since the unreacted epoxy groups remain, the storage stability of the reactive epoxy carboxylate compound (c) is high. In this case, only the reactivity due to the introduced double bond is used.

On the other hand, by reducing the amount of the carboxylic acid compound (b) to leave an unreacted residual epoxy group, the reactivity by the introduced unsaturated bond and the reaction by the remaining epoxy group, for example, It is also possible to use a polymerization reaction in combination. In this case, however, attention should be paid to the preservation of the reactive epoxy carboxylate compound (c) and the examination of the production conditions.

In the case of producing the reactive epoxy carboxylate compound (c) which does not leave an epoxy group, it is preferable that the carboxylic acid compound (b) is 90 to 120 equivalent% based on 1 equivalent of the epoxy resin (a). Within this range, production under relatively stable conditions is possible. If the amount of the carbonic acid compound added is larger than this, the excess carboxylic acid compound (b) remains, which is not preferable.

When the epoxy group is left to remain, it is preferable that the carbonic acid compound (b) is 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). In the case of deviating from this range, the effect of complex curing is reduced. Of course, in this case, it is necessary to pay enough attention to the gelation during the reaction and the stability over time of the reactive epoxy carboxylate compound (c).

The carboxylation reaction may be carried out by reacting with a solvent or by diluting with a solvent. The solvent usable here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

The preferred amount of the solvent to be used should be appropriately adjusted depending on the viscosity and application of the resin to be obtained, but it is preferably used such that the solid content is 90 to 30 mass%, more preferably 80 to 50 mass%.

Specific examples thereof include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha Etc., ester solvents, ether solvents, ketone solvents and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as? -Butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol mono Mono or polyalkylene glycol monoalkyl ether monoacetates such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate; Polycarboxylic acid alkyl esters such as dialkyl glutaric acid, dialkyl glutaric acid, dialkyl succinate, and dialkyl adipate.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, Glycol ethers such as glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

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

In addition, it can be carried out alone or in a mixed organic solvent such as a reactive compound (B) other than the reactive polycarboxylic acid compound (A) to be described later (hereinafter, simply referred to as "reactive compound (B)"). In this case, when used as a curable resin composition, it is preferable because it can be directly used as a composition.

At the time of the reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst to be used can be appropriately selected depending on the amount of the reactant, that is, the reaction product of the epoxy resin (a), the carbonic acid compound (b) And 0.1 to 10 parts by mass based on 100 parts by mass of the total amount. The reaction temperature at that time is 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Boron, chromium octanoate, zirconium octanoate and the like, and the like.

A thermal polymerization inhibitor may also be used. As the thermal polymerization inhibitor, it is preferred to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene desirable.

The end point of this reaction is a time point at which the acid value of the sample becomes 5 mgKOH / g or less, preferably 3 mgKOH / g or less while appropriately sampling.

The preferable range of the molecular weight of the reactive epoxy carboxylate compound (c) thus obtained is that the weight average molecular weight in terms of polystyrene in GPC is in the range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1000 to 10000 to be.

If the molecular weight is smaller than the molecular weight, the hardness of the cured product is not sufficiently exhibited. If the molecular weight is too large, the viscosity becomes high and the coating becomes difficult.

Next, the acid addition process will be described in detail. The acid addition process is carried out for the purpose of obtaining a reactive polycarboxylic acid compound (A) by introducing a carboxyl group into the reactive epoxycarboxylate compound (c) obtained in the previous step, if necessary. Namely, the addition reaction of the polybasic acid anhydride (d) represented by the formula (2) or (3) (hereinafter also simply referred to as "polybasic acid anhydride (d)") to the hydroxyl group generated by the carboxylation reaction, Carboxyl groups are introduced.

The alkyl group having 1 to 10 carbon atoms in the formula (2) includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Preferably a hydrogen atom or a methyl group.

As the polybasic acid anhydride (d), a compound represented by the following formula (4) is preferable.

The reaction of adding the polybasic acid anhydride (d) can be carried out by adding a polybasic acid anhydride (d) to the carboxylation reaction solution. The addition amount should be appropriately changed depending on the application.

When the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkali aqueous solution-developing resist material, the amount of the polybasic acid anhydride (d) The solid acid value (in accordance with JIS K 5601-2-1: 1999) of the carboxylic acid compound (A) is preferably 40 to 120 mgKOH / g, more preferably 60 to 110 mgKOH / g It is preferable to input the calculated value. When the acid value of the solid at this time is in this range, the developability of the aqueous alkali solution of the active energy ray-curable resin composition of the present invention is satisfactory. That is, the patterning performance is good and the management of the (over) phenomenon is wide, and the excess acid anhydride does not remain.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction, and the amount of the catalyst to be used can be appropriately selected depending on the reactants, that is, the epoxy compound (a), the reactive epoxy carboxylate compound (c) obtained from the carbonic acid compound 0.1 to 10 parts by mass based on the total amount of the reaction product of the polybasic acid anhydride (d) and, if necessary, the solvent and others. The reaction temperature at that time is 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Boron, chromium octanoate, zirconium octanoate, and the like.

The acid addition reaction may be carried out by reacting with a solvent or by diluting with a solvent. The solvent usable here is not particularly limited as far as the acid addition reaction is an inert solvent. In the case where a solvent is used in the carboxylation reaction in the previous step, the solvent may be directly added to the acid addition reaction in the next step without removing the solvent, provided that the reaction is inert to both of the two reactions . The solvent that can be used is the same as that available in the carboxylation reaction.

The amount of the solvent to be used should be appropriately adjusted depending on the viscosity and application of the resin to be obtained, but is preferably such that the solid content is 90 to 30 mass%, more preferably 80 to 50 mass%.

In addition, it can be carried out alone or in a mixed organic solvent such as the above-mentioned reactive compound (B). In this case, when used as a curable resin composition, it is preferable because it can be directly used as a composition.

The thermal polymerization inhibitor and the like are preferably the same as those exemplified in the above carboxylation reaction.

This reaction is defined as the point where the acid value of the reactant is in the range of plus or minus 10% of the set acid value while sampling appropriately.

The preferred molecular weight range of the reactive polycarboxylic acid compound (A) thus obtained is in the range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1000 to 10000 in terms of polystyrene reduced weight average molecular weight in GPC to be.

If the molecular weight is smaller than the molecular weight, the hardness of the cured product is not sufficiently exhibited. If the molecular weight is too large, the viscosity becomes high and the coating becomes difficult.

Specific examples of the reactive compound (B) that can be used in the invention include so-called reactive oligomers such as radical reaction type acrylates, cationic reaction type other epoxy compounds, and vinyl compounds which are responsive to both .

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

Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (Meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like can be used. .

Examples of polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylenedi (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (Meth) acrylate of bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide di (meth) acrylate, bisphenol di (meth) acrylate, hydroxy bivalent neoprene glycol (Meth) acrylate of dipentaerythritol poly (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and epsilon -caprolactone, dipentaerythritol poly Trimethylolpropane tri (meth) acrylate, triethylolpropane tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol Tetra (meth) acrylate and ethylene oxide adduct thereof, dipentaerythritol hexa (meth) acrylate, and ethylene oxide adduct thereof.

Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and 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 styrene include styrene, methylstyrene, and ethylstyrene. Other examples of the vinyl compound include triallyl isocyanurate and trimethallyl isocyanurate.

Examples of the so-called reactive oligomers include urethane acrylate having a functional group sensitive to an active energy ray and a urethane bond in the same molecule, a polyester acrylate having a functional group sensitive to an active energy ray and an ester bond in the same molecule, Epoxy acrylates derived from an epoxy resin and having a functional group capable of reacting with an active energy ray in the same molecule, and reactive oligomers in which a combination of these is used.

The cationic reaction type monomer is not particularly limited as long as it is a compound having an epoxy group in general. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl- 4-epoxycyclohexanecarboxylate (manufactured by Union Carbide Co., Ltd., "Sylucker UVR-6110" and the like), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide 4-methylcyclohexyl-2-propylene oxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate Quot; UVR 6128 "), bis (3,4-epoxycyclohexylmethyl) Di-sulfates, and the like can be mentioned bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethyl siloxane.

Of these, the reactive compound (B) is most preferably a radical-curing acrylate. In the case of the cationic type, since the carbonic acid reacts with the epoxy group, it is necessary to prepare a two-liquid mixture type.

The active energy ray-curable resin composition of the present invention can be obtained by mixing the reactive polycarboxylic acid compound (A) of the present invention with the other reactive compound (B). At this time, other components may be appropriately added depending on the application.

The active energy ray-curable resin composition of the present invention contains 97 to 5 mass parts, preferably 87 to 10 mass parts, of the reactive polycarboxylic acid compound (A) in the composition, 3 to 95 mass parts of the reactive compound (B) More preferably 3 to 90 parts by mass. If necessary, other components may be contained in an amount of 0 to 80 parts by mass.

In addition, for the purpose of making the active energy ray-curable resin composition of the present invention suitable for various uses, other components may be added at an upper limit of 70 parts by weight in the composition. Other components include a photopolymerization initiator, other additives, a coloring material, or a volatile solvent added for adjusting the viscosity for the purpose of imparting a coating property or the like. Other components that can be used are illustrated below.

The active energy ray-curable resin composition of the present invention may further contain a photopolymerization initiator. As the photopolymerization initiator, a radical photopolymerization initiator and a cationic photopolymerization initiator are preferable.

Examples of the radical type photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1- Acetophenones such as hexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; Anthraquinones such as 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-chloro anthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 4,4'-bismethylaminobenzophenone; And 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; and the like. .

Examples of the cationic photopolymerization initiator include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine initiators, And other photo acid generators.

Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphate (manufactured by Sanskagakuko Co., Ltd., Adid SI-60L / SI-80L / SI-100L, etc.). Examples of the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and the like. (Cyracure UVI-6990 manufactured by Union Carbide Co., Ltd.), triphenylsulfonium hexafluoroantimonate (Cyracure UVI-6974 manufactured by Union Carbide Co., Ltd.) as the sulfonium salt of Lewis acid, triphenylsulfonium hexafluorophosphate And the like), and examples of the phosphonium salt of Lewis acid include triphenylphosphonium hexafluoroantimonate and the like.

Other halides include 2,2,2-trichloro- [1-4 '- (dimethylethyl) phenyl] ethanone (such as Trigonal PI manufactured by AKZO), 2,2-dichloro- (Sandray 1000 manufactured by Sandoz Co., Ltd.) and α, α, α-tribromomethylphenyl sulfone (BMPS manufactured by Seitetsukagaku Co., Ltd.). Examples of the triazine initiator include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine (Triazine A, (2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine (Triazine PMS manufactured by Panchim Co., (Triazine B manufactured by Panchim Corp.), 2 [2 '(5-methylfuryl) -6-triazine (Trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.), 2 (2'-furylethylidene) -4,6-bis (trichloromethyl) -s -Triazine (manufactured by Sanwa Chemical Co., Ltd.) and the like.

Examples of the photoacid generator include 9-phenylacridine, 2,2'-bis (o-chlorophenyl) norbornane, ) -4,4 ', 5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Guro Gene Chemical Industries, Ltd.), 2,2-azobis (2-amino-propane) dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd. and the like), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, (Cyclopentadecyl) (1,2,3,4,5,6, Eta) - (methylethyl) -benzene] iron (II) hexafluorophosphonate (Irgacure 261 manufactured by Ciba Geigy) (5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-pyryl-1-yl) phenyl] titanium (CGI-784 manufactured by Ciba Geigy).

In addition, an azo-based initiator such as azobisisobutyronitrile and a peroxide-based radical-type initiator that responds to heat such as benzoyl peroxide may be used together. Further, both of a radical-type and a cation-type photo-polymerization initiator may be used together. One type of photopolymerization initiator may be used alone, or two or more types may be used together.

Among them, a radical type photopolymerization initiator is particularly preferable in view of the characteristics of the reactive polycarboxylic acid compound (A) of the present invention.

In addition, the active energy ray-curable resin composition of the present invention may contain a coloring pigment. As the coloring pigment, for example, those not intended for coloring, so-called extender pigments may be used. Examples thereof include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, and clay.

In addition, the active energy ray-curable resin composition of the present invention may contain other additives as required. Examples of other additives include thermosetting catalysts such as melamine, thixotropic agents such as aerosil, polymerization inhibitors such as silicones, fluorine leveling agents and defoaming agents, hydroquinone and hydroquinone monomethyl ether, stabilizers, antioxidants Etc. may be used.

In addition, as a resin stream (so-called inner polymer) which does not show reactivity with an active energy ray, for example, other epoxy resin, phenol resin, urethane resin, polyester resin, ketone formaldehyde resin, cresol resin, Diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof. These are preferably used in the range of up to 40 mass% in the resin composition.

Particularly, when a reactive polycarboxylic acid compound (A) is to be used for the solder resist, it is preferable to use a known general epoxy resin as a resin which does not show reactivity with an active energy ray. This results in that the carboxyl group derived from the reactive polycarboxylic acid compound (A) remains after the reaction and curing by the active energy ray, and as a result, the cured product of the reactive polycarboxylic acid compound (A) is inferior in water resistance and hydrolytic ability. Therefore, by using an epoxy resin, the remaining carboxyl groups are further carboxylated to form a stronger crosslinked structure. The cationic reaction type monomer may be used in the epoxy resin of the general public.

Depending on the purpose of use, a volatile solvent may be added to the resin composition in an amount of up to 50% by mass, more preferably up to 35% by mass, for the purpose of adjusting the viscosity.

The active energy ray-curable resin composition of the present invention is easily cured by an active energy ray. Specific examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser beams, particle beams such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferable in view of the suitable use of the present invention.

The molding material used in the present invention refers to a material which is formed by putting an uncured composition into a mold frame or by pressing a mold frame to form an object and then causing a curing reaction by an active energy ray to form the composition, , And the like, and is used for a purpose of forming by causing a curing reaction.

Specific examples of applications include a sheet formed into a flat shape, a sealing material for protecting the element, a nanoimprint material which is pressed by pressing a " mold frame " A peripheral encapsulating material such as a light emitting diode, a photoelectric conversion element, or the like can be used as a suitable use.

In the present invention, the film-forming material is used for the purpose of covering the substrate surface. Specific applications include ink materials such as gravure ink, flexo ink, silk screen ink and offset ink, coating materials such as hard coating, top coating, overprint varnish and clear coating, various adhesives for laminating, , A resist material such as a solder resist, an etching resist, and a resist for a micromachine. Further, the so-called dry film coating film-forming material which forms a film by temporarily coating a film-forming material on a peelable base material and forming it into a film and bonding it to a base material intended for its original purpose.

The present invention also includes a cured product obtained by irradiating the above-mentioned photosensitive resin composition with active energy rays, and also includes a multi-layered material having a layer of the cured product.

Among them, the introduction of the carboxyl group of the reactive polycarboxylic acid compound (A) increases the adhesion to the base material, so that it is preferable to use the plastic base material or the metal base material for coating.

Furthermore, it is also preferable to use the unreacted reactive polycarboxylic acid compound (A) as an alkaline water-developing resist composition, taking advantage of its solubility in an aqueous alkali solution.

The resist composition used in the present invention means a composition in which a coating layer of the composition is formed on a substrate and then an active energy ray such as ultraviolet rays is partially irradiated to obtain an active region Energy ray-sensitive composition. Specifically, it is a composition used for the purpose of removing an irradiating unit or a non-irradiating unit by any method, for example, dissolving with a solvent or an alkali solution or the like to perform drawing.

The active energy ray-curable resin composition for resists of the present invention can be applied to various materials capable of being patterned, and is useful, for example, in an interlayer insulating material for a solder resist material or a build-up method, and more particularly, as an optical waveguide But also for electric, electronic, and optical substrates such as printed wiring boards, optical electronic boards, and optical substrates.

Particularly suitable applications include the use of insulating films such as photosensitive films, photosensitive films with a support, prepregs and the like, circuit boards (for laminate applications, multilayer printed circuit boards and the like), solder resists, underfill materials, A die-bonding material, a semiconductor encapsulant, a hole-filling resin, a part-filling resin, and the like. Among them, a resin composition for an insulating layer of a multilayer printed wiring board (a multilayer printed wiring board having a cured product of a photosensitive resin composition as an insulating layer), a resin composition for an interlayer insulating layer (a multilayer printed wiring board having a cured product of a photosensitive resin composition as an interlayer insulating layer) , And a resin composition for plating formation (a multilayer printed wiring board on which plating is formed on a cured product of a photosensitive resin composition).

In addition, good developability can be exhibited even at a high pigment concentration, and thus it can be suitably used for resist materials for color resists and color filters, particularly black matrix materials.

The patterning using the active energy ray-curable resin composition of the present invention can be performed, for example, as follows. The composition of the present invention is applied onto the substrate by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, or spin coating to a thickness of 0.1 to 200 m, Deg.] C, preferably 60 to 100 [deg.] C, to form a coating film. Thereafter, a high energy beam such as ultraviolet rays is directly or indirectly irradiated onto the coating film through a photomask having an exposure pattern formed thereon at an intensity of about 10 to 2000 mJ / cm 2, and using a developer to be described later, A desired pattern can be obtained by spraying, vibration immersion, puddle, brushing or the like.

Examples of the aqueous alkali solution used for the above development include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate and the like, An aqueous solution of an organic alkali such as hydrochloric acid, hydrobromic acid, sulfuric acid, sulfuric acid, sulfuric acid, sulfuric acid, and the like can be used. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

In addition, it is particularly suitably used as a dry film application in which mechanical strength before the curing reaction by an energy ray is required. That is, since the balance of the hydroxyl group and the epoxy group of the epoxy resin (a) used in the present invention falls within a specific range, the reactive epoxy carboxylate compound of the present invention exhibits good developability despite its relatively high molecular weight.

The method of forming the film is not particularly limited, and examples thereof include a concave printing method such as gravure printing, a convex printing method such as flexographic printing, a stencil printing method such as a silk screen, a flat printing method such as offset printing, a roll coater, a knife coater, Various coating methods such as coater, spin coater and the like can be arbitrarily adopted.

The cured product of the active energy ray-curable resin composition of the present invention means that the active energy ray-curable resin composition of the present invention is irradiated with active energy rays and cured.

The article overcoated with the active energy ray-curable resin composition of the present invention refers to a material composed of at least two layers obtained by forming a film on a substrate and curing the active energy ray-curable resin composition appearing in the present invention.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples, unless otherwise noted,% means% by mass.

The softening point, the epoxy equivalent, and the acid value were measured under the following conditions.

1) Epoxy equivalent: Measured by the method according to JIS K 7236: 2001.

2) Softening point: Measured by the method according to JIS K 7234: 1986.

3) Acid value: Measured by the method according to JIS K 0070: 1992.

4) The measurement conditions of GPC are as follows.

Model: TOSOH HLC-8220GPC

Column: Super HZM-N

Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40 < 0 > C

Detector: RI (differential refractometer)

Molecular weight standard: Polystyrene

(Synthesis Example 1): Synthesis of reactive epoxy carboxylate compound (c)

353 g of an epoxy resin having a triglycidyl ether structure (manufactured by Mitsui Mining and Smelting Co., Ltd., VG-3101, epoxy equivalent: 210) as the epoxy resin (a) 72, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added so as to have a solid content of 80% and reacted at 100 DEG C for 24 hours to obtain a reactive epoxy carboxylate compound (c1) solution.

(Synthesis Example 2)

353 g of an epoxy resin having a triglycidyl ether structure (manufactured by Mitsui Mining and Smelting Co., Ltd., VG-3101, epoxy equivalent: 210) as the epoxy resin (a) and 373 g of methacrylic acid (abbreviated as MAA, (Mw = 86), 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent so as to have a solid content of 80% and reacted at 100 DEG C for 24 hours to obtain a reactive epoxy carboxylate compound (c2) solution .

(Example 1, Comparative Example 1): Preparation of reactive polycarboxylic acid compound (A)

Propylene glycol monomethyl ether monoacetate was added to 593 g of the resulting reactive epoxy carboxylate compound (c) so as to have a solids content of 65% as a solvent and a compound (g) shown in Table 1 as a polybasic acid anhydride (d) After heating to 100 占 폚, acid addition reaction was carried out to obtain a solution of the reactive polycarboxylic acid compound (A). The solid acid value (AV: mgKOH / g) and the weight average molecular weight of the obtained reactive polycarboxylic acid compound (A) are shown in Table 1. Solid acid value (mg · KOH / g): The measurement was carried out as a solution and converted into a value in solid content.

(Example 2, Comparative Example 2): Preparation of resist material composition

54.44 g of the reactive polycarboxylic acid compound (A) obtained in Example 1, 3.54 g of HX-220 (trade name: diacrylate monomer manufactured by Nippon Kayaku Co., Ltd.) as the other reactive compound (B) 4.72 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals), 0.47 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 14.83 g of GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) 1.05 g of melamine as a curing catalyst and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent were added, kneaded in a viscometer, and uniformly dispersed to obtain a resist material resin composition.

The obtained composition was uniformly applied to a film of copper foil to be a support film by a roll coating method and passed through a hot air drying furnace at a temperature of 70 占 폚 to form a resin layer having a thickness of 30 占 퐉. Thereafter, spray development was carried out with a 1% aqueous solution of sodium carbonate to evaluate the developability (unit: second) with the time until complete development, that is, the break time.

From the above results, the resist material composition using the reactive polycarboxylic acid compound (A) of the present invention has good developability.

(Example 3 and Comparative Example 3): Evaluation of thermal decomposition resistance

24.8 g of the reactive polycarboxylic acid compound (A) obtained in Example 1, 0.5 g of Irgacure 184 as a photopolymerization initiator and 2.4 g of propylene glycol monomethyl ether monoacetate were added and uniformly applied to a polyimide film, A resin layer having a thickness of 20 占 퐉 was formed through a hot-air drying furnace at a temperature of 80 占 폚 to form a resin layer having a thickness of 20 占 퐉, followed by exposure to light with an ultraviolet exposure apparatus (Oak Seisakusho, Model HMW-680GW) to obtain a cured product. The produced cured product is cut into a width of 5 mm. Thereafter, it was set in the TA instruments manufactured viscoelasticity measuring device RSA-G2, and the tan δ was measured in an air atmosphere at a frequency of 10 Hz and a heating rate of 2 캜 / min., And the temperature at the maximum value of tan δ was defined as Tg.

Further, 3 mg of the prepared sample was measured at a temperature at which the weight was reduced by 5% by using TGA / DSC1 manufactured by METTLER in an air flow of 100 ml per minute.

From the above results, it can be seen that the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention is superior in heat resistance and thermal decomposition resistance to the comparative resin composition.

Claims (8)

A reactive epoxy carboxylate compound (c) obtained by reacting an epoxy resin (a) represented by the following formula (1) with a carbonic acid compound (b) having an ethylenically unsaturated group polymerizable in one molecule and a carboxy group, Reactive polycarboxylic acid compound (A) reacted with a polybasic acid anhydride (d) represented by the formula (2) or (3)

(Wherein n represents an average value and represents a value of 0 to 20);

(In the formula (2), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).  An active energy ray-curable resin composition comprising the reactive polycarboxylic acid compound (A) according to claim 1. 3. The method of claim 2,
(B) a reactive compound other than the reactive polycarboxylic acid compound (A), a photopolymerization initiator, and a thermosetting catalyst. The method according to claim 2 or 3,
Wherein the active energy ray-curable resin composition is a molding material. The method according to claim 2 or 3,
An active energy ray-curable resin composition which is a film-forming material. The method according to claim 2 or 3,
An active energy ray curable resin composition which is a resist material composition. A cured product of the active energy ray-curable resin composition according to claim 2 or 3. An article overcoated with a cured product of the active energy ray-curable resin composition according to claim 7.