KR20180138137A - 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 film having excellent heat resistance and developability. A reactive polycarboxylic acid compound (A) is formed by making a polybasic acid anhydride (e) represented by formula (2) or (3) react with a reactive epoxy carboxylate compound (d) which is obtained by making epoxy resin (a) represented by formula (1) react with a carbonic acid compound (b) having both a carboxyl group and an ethylenic unsaturated group capable of polymerizing in one molecule, and if necessary, with a compound (c) having a carboxyl group and a hydroxyl group in one molecule. In formula (1), R may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, a independently represents 1 to 3, and n represents an integer of 1 to 20 as an average value. In formula (2), R_1 independently represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and m represents an integer of 1 to 3.

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 (A), an active energy ray-curable resin composition containing the same, and a cured product thereof. In particular, the present invention relates to a novel reactive polycarboxylic acid compound suitable as a color resist, a resist material for a color filter, a resist material applicable as a black matrix material, an active energy ray-curable resin composition containing the same, and a cured product thereof.

The printed wiring board is required to have high accuracy and high density in order to reduce the size and weight of the portable device and to improve the communication speed. Accordingly, the demand for a solder resist for covering the circuit itself increases, There is a demand for performance that can withstand substrate adhesion, high insulation and electroless gold plating while maintaining heat resistance and thermal stability, and a film forming material having stronger curing properties is required.

As these materials, a carboxylate compound obtained by reacting a general epoxy resin with a compound having a carboxylic acid and a hydroxyl group together with acrylic acid is known as a material having a low acid value and excellent developability, and it is known that the compound has resist ink suitability (Patent Document 1).

On the other hand, an acid-modified epoxy acrylate having a basic skeleton of phenol aralkyl type epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku Co., Ltd.) is generally known as a material exhibiting high toughness after curing, The use as a resist has also been examined (Patent Document 2).

In addition, attempts have been made to apply carbon black or the like to an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton to apply it to a black matrix resist used for a liquid crystal display panel or the like (Patent Document 3). In addition, studies have been made so as to be applicable to black resists in other phenol-dicyclopentadiene skeletons, and it has been found that they have affinity with a good coloring pigment, and the resulting composition shows good developability even at a high pigment concentration And the like (Patent Document 4).

JP-A-06-324490 Japanese Patent Application Laid-Open No. 09-211860 Japanese Patent Application Laid-Open No. 2004-295094 Japanese Laid-Open Patent Publication No. 2009-102501

However, since acid-modified epoxy acrylates having an epoxy resin having a phenol-dicyclopentadiene skeleton as a basic skeleton have excellent compatibility with a resin such as carbon black, the pigment is dispersed, but since the developability is poor, It is necessary to have developability at a high pigment concentration.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide an acid-modified epoxy acrylate compound having excellent dispersibility such as a coloring pigment and having good developing properties even at a high pigment concentration, and an active energy ray- 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 conducted intensive studies and found that a reaction product of an epoxy resin having a phenol-dicyclopentadiene structure and an unsaturated group-containing carbonic acid, and a compound having a hydroxyl group and a carboxy group in one molecule, , A resin composition using a reaction product with a specific polybasic acid anhydride solves the above problems, and has reached the present invention.

That is,

[1] A process for producing a resin composition, which comprises adding to an epoxy resin (a) represented by the following formula (1) a carbonic acid compound (b) having an ethylenically unsaturated group capable of polymerizing in one molecule and a carboxy group (b), a compound having a hydroxyl group and a carboxy group (A) reacted with a polybasic acid anhydride (e) represented by the following formula (2) or (3) and a reactive polycarboxylic acid compound (d)

(Wherein R is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 4 carbon atoms, and a represents 1 to 3. n is an average value and represents an integer of 1 to 20)

(In the formula (2), R ₁ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m represents an integer of 1 to 3)

[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], further comprising 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 is a molding material,

[6] The active energy ray-curable resin composition according to any one of items [2] to [4], which is a film-forming material,

[7] The active energy ray-curable resin composition according to any one of items [2] to [4], which is a resist material composition,

[8] A cured product of the active energy ray-curable resin composition according to any one of items [2] to [7]

[9] An article overcoated with a cured product as described in [8]

.

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. The cured product obtained by curing the active energy ray-curable resin composition of the present invention with an active energy ray such as ultraviolet rays or the like is excellent in heat resistance and can be finely alkali developed, Lt; / RTI >

From the high affinity with the colored pigment, the reactive polycarboxylic acid-modified compound of the present invention and the active energy ray-curable resin composition containing the reactive polycarboxylic acid modified compound of the present invention exhibit good developability even at a high pigment concentration. And particularly, a black matrix material.

In addition, the active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention has excellent thermal and mechanical strength, good storage stability, high reliability against high temperature and high humidity, A solder resist for a printed wiring board requiring high reliability, an interlayer insulating material for a multilayer printed wiring board, a solder resist for a flexible printed wiring board, a plating resist, and a photosensitive optical waveguide.

(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 comprises an epoxy resin (a) having a structure represented by the following formula (1), a carboxylic acid compound (b) having an ethylenically unsaturated group capable of polymerizing in one molecule and a carboxy group, If necessary, the compound (c) having a hydroxyl group and a carboxy group in one molecule is reacted to obtain a reactive epoxy carboxylate compound (d). Next, it can be obtained by reacting a polybasic acid anhydride (e) represented by the following formula (2) or (3).

(Wherein R is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 4 carbon atoms, and a represents 1 to 3. n is an average value and represents an integer of 1 to 20)

(In the formula (2), R ₁ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m represents an integer of 1 to 3)

The hydrocarbon group having 1 to 4 carbon atoms in the formula (1) represents a saturated or unsaturated hydrocarbon group such as a methyl group, an ethyl group, an ethylene group, a propyl group, a propylene group, a butyl group or a butylene group.

First, the carboxylation process for imparting reactivity to a carboxylate compound to obtain a reactive epoxy carboxylate compound (d) will be described.

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 a product of various trade names such as XD-1000 (Manufactured by Sumitomo Chemical Co., Ltd.) and the like.

In the present invention, the carbonic acid compound (b) (hereinafter, simply referred to as " carbonic acid compound (b) ") having both an ethylenic unsaturated group capable of polymerizing in one molecule and a carboxy group, . The ethylenic unsaturated group and the carboxy group are not limited as long as they have at least one ethylenic unsaturated group and a carboxy group, respectively.

Examples of the carbonic acid compound (b) having a polymerizable ethylenically unsaturated group and a carboxy group in one 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 acids in the above include (meth) acrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, (Meth) acrylate derivatives having a hydroxyl group, and half-esters, which are reaction products of mono-glycidyl (meth) acrylate derivatives and saturated or unsaturated dibasic acids and monoglycidyl A monocarboxylic acid compound having one carboxyl group, and a half ester, which is a monohydric reactant with a (meth) acrylate derivative having a plurality of hydroxyl groups in a molecule, a glycidyl group having a saturated or unsaturated dibasic acid and a plurality of epoxy groups And polycarboxylic acid compounds having a plurality of carboxy groups in one molecule such as half esters, which are reaction products of monomers of (meth) acrylate derivatives.

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.

As the compound having at least one polymerizable ethylenic unsaturated group and at least one carboxy group in one molecule, it is preferable that the compound does not have a hydroxyl group in the compound.

The compound (c) (hereinafter also referred to simply as " compound (c) ") having both a hydroxyl group and a carboxy group in one molecule used in the present invention is reacted for the purpose of introducing a hydroxyl group into the carboxylate compound. These include a compound having one hydroxyl group and one carboxy group in one molecule, a compound having two or more hydroxyl groups and one carboxy group in one molecule, a compound having at least one hydroxyl group and at least two carboxy groups in one molecule .

Examples of the compound having one hydroxyl group and one carboxy group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, and hydroxystearic acid. Examples of the compound having two or more hydroxyl groups and one carboxy group in a molecule include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of the compound having at least one hydroxyl group and at least two carboxyl groups in a molecule include hydroxyphthalic acid and the like.

Among them, it is preferable that two or more hydroxyl groups are contained in one molecule in consideration of the effect of the present invention. The carboxy group is preferably one in one molecule in view of the stability of the carboxylation reaction. Most preferably, it has two hydroxyl groups and one carboxyl group in one molecule. Considering the availability of the raw materials, dimethylol propionic acid and dimethylol butanoic acid are particularly suitable.

As the compound having at least one hydroxyl group and at least one carboxyl group in one molecule, it is preferable that the compound does not have a polymerizable ethylenic unsaturated group.

The charging ratio of the epoxy resin (a), the carboxylic acid compound (b) and the compound (c) in the carboxylation reaction should be appropriately changed depending on the application. That is, when all the epoxy groups are carboxylated, unreacted epoxy groups do not remain, so that the storage stability of the reactive epoxy carboxylate compound (d) 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) and the amount of the compound (c) to leave an unreacted residual epoxy group, the reactivity by the introduced unsaturated bond and the reaction by the remaining epoxy group, It is also possible to use a combination of a polymerization reaction and a thermal polymerization reaction. In this case, however, attention should be paid to the preservation of the reactive epoxy carboxylate compound (d) and the examination of the production conditions.

It is preferable that the total amount of the carboxylic acid compound (b) and the compound (c) is 90 to 120 equivalent% based on 1 equivalent of the epoxy resin (a) when the reactive epoxy carboxylate compound (d) Do. Within this range, production under relatively stable conditions is possible. If the amount of the carbonic acid compound to be added is larger than this, the excess amount of the carboxylic acid compound (b) and the compound (c) remains undesirably.

When the epoxy group is left to remain, the total amount of the carboxylic acid compound (b) and the compound (c) is preferably 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 weakened. Of course, in this case, it is necessary to pay attention to the gelation during the reaction and the stability over time of the reactive epoxy carboxylate compound (d).

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

Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum ether, white gasoline, 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 ethers such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate and butylene glycol monomethyl ether acetate, Polycarboxylic acid alkyl esters such as monoacetates, dialkyl glutarates, dialkyl succinates, and dialkyl adipates; and the like.

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 also 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.

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, namely, the epoxy resin (a), the carbonic acid compound (b) and the compound (c) Is added in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of reactants. 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, and zirconium octanoate, 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.

In the carboxylation reaction, the point of time at which the acid value of the sample becomes 5 mgKOH / g or less, preferably 3 mgKOH / g or less, is appropriately sampled.

The preferable range of the molecular weight of the reactive epoxy carboxylate compound (d) thus obtained is in the range of 1,000 to 50,000, more preferably 2,000 to 30,000, in terms of polystyrene reduced weight average molecular weight in GPC.

When the molecular weight is smaller than the above-mentioned range, the hardness of the cured product is not sufficiently exhibited. When the molecular weight is too large, the viscosity becomes high and the coating becomes difficult.

Next, the acid addition step (hereinafter, simply referred to as " present acid addition reaction ") will be described in detail. The acid addition step is carried out for the purpose of obtaining a reactive polycarboxylic acid compound (A) by introducing a carboxy group into the reactive epoxy carboxylate compound (d) obtained in the previous step, if necessary. That is, the addition reaction of the polybasic acid anhydride (e) (hereinafter also simply referred to as "polybasic acid anhydride (e)") represented by the formula (2) or the formula (3) to the hydroxyl group generated by the carboxylation reaction, To introduce a carboxy group.

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. In the formula (2), R ₁ is preferably a hydrogen atom or a methyl group.

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

The reaction of adding the polybasic acid anhydride (e) can be carried out by adding a polybasic acid anhydride (e) 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 type resist material, the amount of the polybasic acid anhydride (e) to be added may be selected, for example, by adding the polybasic acid anhydride (e) The calculated acid value (based on JIS K5601-2-1: 1999) of the carboxylic acid compound (A) is preferably 20 to 120 mgKOH / g, more preferably 30 to 110 mgKOH / g . 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. In other words, the patterning performance is good and the management of the 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. The amount of the catalyst to be used is preferably in the range of 1 to 100 parts by weight per 100 parts by weight of the reactive epoxy carboxylate compound (a) obtained from the reaction product, that is, the epoxy compound (d) and the polybasic acid anhydride (e), 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 for the carboxylation reaction in the previous step, the solvent may be directly added to the acid addition reaction in the subsequent step without removing the solvent, provided that the reaction is inert to both of the two reactions . The solvent which can be used is the same as that which can be used in the carboxylation reaction.

The preferred amount of the solvent to be used is to be appropriately adjusted according to 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.

In the present acid addition reaction, the point where the acid value of the reactant is in the range of plus or minus 10% of the set acid value while appropriately sampling is regarded as the end point.

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.

When the molecular weight is smaller than the above-mentioned range, the hardness of the cured product is not sufficiently exhibited. When 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, dipentaerythritol poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, 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 acrylate 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-epoxycyclohexane carboxylate (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, 2-ethylhexyl-2-propylene oxide, etc.), limonene dioxide ("Cellxide 3000" manufactured by Daicel Chemical Industries, Ltd.) - (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate Cure UVR-6128 "), bis (3,4-epoxycyclohexylmethyl) adi Bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like.

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 to the composition at an upper limit of 70 parts by weight. Examples of the other components include a photopolymerization initiator, other additives, a coloring material, a curing accelerator, and a volatile solvent added for adjusting viscosity for the purpose of imparting coating properties. 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'-methyldiphenyl sulfide 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 photoacid generators other than these.

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 photo acid generator include 9-phenylacridine, 2,2'-bis (o-chloro (meth) acryloyloxy) Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2-biimidazole (such as imidazole from Kurogane Kasei), 2,2-azobis (2-amino-propane) dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd. and the like), 2,2-azobis [2- (imidazoline-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Hexyl fluorophosphonate (such as Irgacure 261 manufactured by Ciba Geigy), bis (y5-xylylene), bis (cyclopentadecyl) (1,2,3,4,5,6, (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 a range of up to 40 parts by 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 is because the carboxyl groups derived from the reactive polycarboxylic acid compound (A) remain after 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 hydrolysis. 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.

For the purpose of adjusting the viscosity, a volatile solvent may be added to the resin composition in a range of up to 50 parts by mass, more preferably up to 35 parts by mass, depending on the purpose of use.

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 molding material obtained by molding an uncured composition in a mold or pushing the mold to form an object and then causing the material to undergo a curing reaction with an active energy ray, Refers to a material that is used in applications in which focal light such as a laser is irradiated to cause a curing reaction to be molded.

Specific examples of applications include a sheet formed into a planar shape, a sealing material for protecting the element, a so-called nanoimprint material in which fine molding is performed by pressing a "frame" micro-machined to an uncured composition, Rigid light emitting diodes, peripheral encapsulation materials such as photoelectric conversion elements, and the like are suitable applications.

In the present invention, the film-forming material is used for the purpose of covering the substrate surface. Specific examples of the application include ink materials such as gravure ink, flexo ink, silkscreen ink and offset ink, coating materials such as hard coating, top coating, overprint varnish and clear coating, various adhesives for laminates, An adhesive material such as an adhesive, 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 is formed by temporarily coating a film-forming material on a peelable base material to form a film, and then adhering the film-forming material to a base material for the original purpose to form a film.

The present invention also includes a cured product obtained by irradiating the above-mentioned curable 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 carboxy group of the reactive polycarboxylic acid compound (A) enhances the adhesion to the substrate, and therefore, it is preferable to use it as a coating for covering a plastic substrate or a metal substrate.

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, and drawing.

The active energy ray-curable resin composition as the resist material composition 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 in particular, It is also used as a waveguide in electric / electronic / 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, Such as a die bonding material, a semiconductor encapsulant, a hole-filling resin, and a part-filling resin. In particular, it can be suitably used for a color resist, a resist material for a color filter, particularly, a black matrix material, because it can exhibit good developability even at a high pigment concentration.

The resin composition for an insulating layer of a multilayer printed wiring board (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is an insulating layer), a resin composition for an interlayer insulating layer (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is 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).

The patterning using the active energy ray-curable resin composition of the present invention can be performed, for example, as follows. The active energy ray-curable resin composition of the present invention is coated on the substrate by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, or spin coating to a film thickness of 0.1 to 200 m, At a temperature of usually 50 to 110 DEG C, preferably 60 to 100 DEG C, to form a coating film. Thereafter, a high energy beam such as ultraviolet rays is irradiated to the coating film directly or indirectly through a photomask having an exposure pattern formed thereon at an intensity of about 10 to 2000 mJ / cm 2, and the coating solution is sprayed, for example, Vibration dipping, puddling, brushing or the like, a desired pattern can be obtained.

Examples of the aqueous alkali solution used in the above development include inorganic alkali aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, and potassium phosphate, and aqueous solutions such as tetramethylammonium hydroxide and tetraethylammonium hydroxide , Tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine 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 requiring mechanical strength before curing reaction by an active energy ray. That is, since the balance of the hydroxyl groups and the epoxy groups of the epoxy resin (a) used in the present invention falls within a specific range, the reactive polycarboxylic acid compound (A) of the present invention exhibits good developing properties .

There are no particular restrictions on the method of forming the film, but it is possible to use various methods such as a concave printing method such as a gravure printing method, a convex printing method such as flexo printing, a plate printing method such as a silk screen, a flat printing method such as an offset printing method, a roll coater, Various coating methods such as a coater, a curtain coater, and a spin coater 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.

An article overcoated with the active energy ray-curable resin composition of the present invention refers to a material comprising at least two layers obtained by forming a film on a substrate and curing the active energy ray-curable resin composition of 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 K7236: 2001.

2) Softening point: Measured by the method according to JIS K7234: 1986.

3) Acid value: Measured by the method according to JISK0070: 1992.

4) The measurement conditions of GPC are as follows.

Model: TOSOH HLC-8220 GPC

Column: Super HZM-N

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

Detector: RI (differential refractometer)

Molecular weight standard: Polystyrene

(Synthesis Examples 1 to 3): Synthesis of reactive epoxy carboxylate compound (d)

(AA) or methacrylic acid (MAA) as the carbonic acid compound (b) in the amount shown in Table 1 as XD-1000 (softening point 74.8 ° C, epoxy equivalent 255 g / eq., Manufactured by Nippon Kayaku Co., , And dimethylolpropionic acid (hereinafter abbreviated as " DMPA ") as the compound (c). 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 mass% and reacted at 100 占 폚 for 24 hours to obtain a solution of a reactive epoxy carboxylate compound (d).

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

Propylene glycol monomethyl ether monoacetate was added to 200 g of the obtained reactive epoxy carboxylate compound (d) so that the amount of the compound (g) shown in Table 2 as the polybasic acid anhydride (e) and the solids content of the solvent as the content of 65% 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) of the obtained reactive polycarboxylic acid compound (A) is shown in Table 2. The solid acid value (mg · KOH / g) was measured as a solution and converted to a value in a solid content.

HTMA: 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd.

NTA: Norbornan tricarboxylic acid anhydride, see Japanese Patent 5532123 Synthesis

THPA: 1,2,3,6-tetrahydrophthalic anhydride, manufactured by Shin-Nihon Rika Co., Ltd.

SA: Ricaside SA Anhydrous succinic acid, manufactured by Shin-Nihon Rika Co., Ltd.

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

54.44 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative 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.) as a photo polymerization initiator, and NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) , 1.05 g of melamine as a curing accelerator, and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent were added and kneaded with a beads mill and uniformly dispersed to obtain a resist material resin composition.

The obtained composition was uniformly applied to a film of a 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 developability with a time until complete development (so-called break time) (unit: second). Table 3 shows the results.

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

8 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, 0.24 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and 0.24 g of Kayacure DETX-S (manufactured by Nippon Kayaku ), 0.403 g of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) as a curing agent component, 0.017 g of triphenylphosphine as a curing accelerator and 0.446 g of propylene glycol monomethyl ether monoacetate were added to the polyimide film And then passed through a hot air drying roll at a temperature of 80 DEG C to form a resin layer having a thickness of 20 mu m and then exposed with an ultraviolet ray exposure apparatus (manufactured by OXSYSAKUSHO Co., Ltd., model HMW-680GW) ≪ / RTI > The produced cured product is cut into a width of 5 mm. Thereafter, it was set in a TA instruments manufactured viscoelasticity measuring apparatus RSA-G2, and tan δ was measured in an air atmosphere at a frequency of 10 Hz and a heating rate of 2 ° C./min., And the temperature at the maximum value of tan δ was defined as Tg. Table 4 shows the results.

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 to the comparative resin composition.

(Example 4 and Comparative Example 4): Evaluation on pigment dispersibility

, 20 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, 5.0 g of DPHA (trade name: acrylate monomer manufactured by Nippon Kayaku Co., Ltd.) as the other reactive compound (B) 10 g of glycol monomethyl ether acetate and 15 g or 10 g of Mitsubishi carbon black MA-100 as a color pigment were added and stirred. In addition, 35 g of glass beads were added and dispersed for 1 hour with a paint shaker. The dispersion after completion of the dispersion was coated on a polyethylene terephthalate film with a wire bar coater # 2 and dried with a hot air dryer at 80 ° C for 10 minutes. The gloss of the surface of the coated film after completion of the drying was measured using a 60 ° reflection gloss system (Horiba Seisakusho IG-331 gloss system) to evaluate the dispersibility of the carbon black. Table 5 shows the results. The higher the gloss value, the better the pigment dispersion.

As is apparent from the above results, it was confirmed that the coating film obtained from the resin composition containing the reactive polycarboxylic acid compound (A) obtained in Example 1 had a high gloss value and excellent pigment dispersibility as compared with Comparative Examples . In addition, the resin composition containing the reactive polycarboxylic acid compound (A) of the present invention showed no change in the gloss value even when the content of the colored pigment was large. On the other hand, in the reactive polycarboxylic acid compound of the comparative example, the gloss decreases when the content of the colored pigment is increased, and the content dispersibility is low. Therefore, it can be confirmed that the pigment dispersibility of the reactive polycarboxylic acid compound (A) of the present invention does not depend on the content of the colored pigment and is excellent.

From the above, it can be seen that the cured product of the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention is excellent in heat resistance and can be finely alkali developed, Lt; / RTI > In particular, it is suitable for a color resist, a resist material for a color filter, particularly, a black matrix material, because it exhibits good developability even at a high pigment concentration.

Claims (9)

(B) a carbonic acid compound (b) having an ethylenically unsaturated group capable of polymerizing in one molecule and a carboxy group, and (c) a compound (c) having both a hydroxyl group and a carboxy group in one molecule, (D) reacted with a polybasic acid anhydride (e) represented by the following formula (2) or (3) to obtain a reactive polycarboxylic acid compound (A)

(Wherein R may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 4 carbon atoms, a represents 1 to 3, and n represents an average value of 1 to 20);

(In the formula (2), R ₁ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
m represents an integer of 1 to 3). An active energy ray-curable resin composition comprising the reactive polycarboxylic acid compound (A) according to claim 1. 3. The method of claim 2,
And a reactive compound (B) other than the reactive polycarboxylic acid compound (A). 3. The method of claim 2,
An active energy ray curable resin composition comprising a photo polymerization initiator. 5. The method according to any one of claims 2 to 4,
Wherein the active energy ray-curable resin composition is a molding material. 5. The method according to any one of claims 2 to 4,
An active energy ray-curable resin composition which is a film-forming material. 5. The method according to any one of claims 2 to 4,
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 any one of claims 2 to 4. An article overcoated with the cured article of claim 8.