TW201905022A - Reactive polycarboxylic acid compound, active energy ray-curable resin composition using the same, cured product of the composition, and use of the cured product - Google Patents

Abstract

An objective of the present invention is to provide an active energy ray curable resin composition which provides a cured film excellent in heat resistance and developability. The present invention provides a reactive polycarboxylic acid compound (A) which is formed by reacting an epoxy carboxylate compound (d) with a polybasic acid anhydride (e) represented by the following formula (2) or formula (3); wherein, the epoxy carboxylate compound (d) is obtained by reacting a carboxylic acid compound (b) having an ethylenically unsaturated group and a carboxy group polymerizable in one molecule with a compound (c), if necessary, having both a hydroxyl group and a carboxy group in one molecule, in an epoxy resin (a) represented by the following formula (1). In the formula, R may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, a represents 1 to 3, respectively; n represents an average value of 1 to 20. In the formula (2), R1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms; m represents an integer of 1 to 3.

Description

   Reactive polycarboxylic acid compound, active energy ray-curable resin composition using the same, hardened product of the composition, and use of the hardened product   

The present invention relates to a novel reactive polycarboxylic acid compound (A), an active energy ray-curable resin composition containing the compound (A), and a cured product of the composition. In particular, it is preferably a novel and reactive polycarboxylic acid compound that can also be used as a color resist, a resist material for a color filter, and a black matrix material, and an active energy ray hardener containing the compound. Type resin composition and hardened material of the composition.

Printed circuit boards are aimed at the miniaturization and lightweight of portable devices and the improvement of communication speed. They are required to have high precision and high density. Along with this, the requirements for solder resist covering the circuit itself have gradually increased. Compared with the previous requirements, it is required to maintain heat resistance and thermal stability, and at the same time to be able to provide substrate adhesion, high insulation, and ability to withstand electroless plating, and a film-forming material with stronger hardening properties. .

As for these materials, it is known that a carboxylic acid ester compound obtained by reacting a general epoxy resin with a compound having a carboxylic acid and a hydroxyl group and acrylic acid is a material having a low acid value and excellent developability. In addition, it is also known that this compound has suitability for a resist ink. (Patent Document 1).

On the other hand, the use of phenol aralkyl-type epoxy resins (such as NC-3000 manufactured by Nippon Kayaku Co., Ltd.) as the basic skeleton of acid-modified epoxy acrylates, which have high strength and toughness after hardening, has been It is generally known and the use of it as a solder resist has also been studied (Patent Document 2).

In addition, it is also known to disperse carbon black and the like in an acid-modified epoxy acrylate having a phenolaralkyl-type epoxy resin as a basic skeleton and to use it as a black matrix resist for a liquid crystal display panel (Patent Document 3). Furthermore, it was found that even other phenol-dicyclopentadiene skeletons can be applied to black resists, and have good affinity with colored pigments, and it has been found that the resulting composition can have good properties even with high pigment concentrations. Developable resistive materials and the like (Patent Document 4).

[Patent Document 1] Japanese Unexamined Patent Publication No. 06-324490

[Patent Document 2] Japanese Patent Laid-Open No. 09-211860

[Patent Document 3] Japanese Patent Laid-Open No. 2004-295094

[Patent Document 4] Japanese Patent Laid-Open No. 2009-102501

However, an acid-modified epoxy acrylate using an epoxy resin having a phenol-dicyclopentadiene skeleton as a basic skeleton, although colored pigments such as carbon black and the resin have good affinity and disperse the pigment, but because of poor developability, it is necessary It has developability at higher pigment concentration.

Therefore, an object of the present invention is to provide an acid-modified epoxy acrylate compound having improved dispersibility of a colored pigment, etc., and having good developing characteristics even if the pigment concentration is high, and to improve the problems of the above-mentioned conventional technology, and to contain the same. Active energy ray-curable resin composition of a compound.

In order to solve the aforementioned problems, the present inventors have worked hard to find out the results of the research, and found that the resin composition used was an epoxy resin having a phenol-dicyclopentadiene structure, an unsaturated carboxylic acid, and one as needed. When the reactant of a compound having both a hydroxyl group and a carboxyl group in the molecule is reacted with a specific polybasic acid anhydride, the aforementioned problems can be solved, and the present invention has been completed.

That is, the present invention relates to:

[1] A reactive polycarboxylic acid compound (A), in which an epoxy resin (a) represented by the following formula (1) and a carboxyl group having both a polymerizable ethylenically unsaturated group and a carboxyl group are combined. An acid compound (b) and a compound (c) having both a hydroxyl group and a carboxyl group in one molecule are reacted to obtain a reactive epoxy carboxylic acid ester compound (d), and the reactive epoxy carboxylic acid ester compound ( d) reacting with a polybasic acid anhydride (e) represented by the following formula (2) or formula (3);

In the formula, 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, and a represents 1 to 3 respectively; n represents an integer of 1 to 20;

In the formula (2), R ₁ independently represents a hydrogen atom, 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 containing the reactive polycarboxylic acid compound (A) according to the above [1].

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

[4] The active energy ray-curable resin composition according to the item [2] or [3], which contains a photopolymerization initiator.

[5] The active energy ray-curable resin composition according to any one of the above [2] to [4], which is a molding material.

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

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

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

[9] An article obtained by overcoating the hardened article according to the item [8].

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention not only obtains a tough hardened product, but also has excellent resin physical properties in a state where the solvent is dried. In addition, the hardened product obtained by hardening the active energy ray-curable resin composition of the present invention with active energy rays such as ultraviolet rays is excellent in heat resistance and can be finely alkali-developed. Therefore, it is suitable for forming materials and film formation. Materials, resist materials.

In addition, since the affinity with the coloring pigment is high, the reactive polycarboxylic acid-modified compound of the present invention and the active energy ray-curable resin composition containing the compound can exhibit good performance even at high pigment concentrations Developability, so it is suitable for color resists, resist materials for color filters, especially black matrix materials.

Furthermore, the active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention has thermal and mechanical toughness, good storage stability, and can withstand high temperature and humidity or High reliability due to hot and cold shocks, so it can also be used in soldering resists for printed circuit boards that require high reliability, interlayer insulation materials for multilayer printed circuit boards, solder resists for flexible printed circuit boards, plating resists, Applications such as photosensitive optical waveguides.

Hereinafter, the present invention will be described in detail.

The reactive polycarboxylic acid compound (A) of the present invention can be obtained by combining an epoxy resin (a) having a structure represented by the following formula (1) with a polymerizable compound in one molecule. The carboxylic acid compound (b) having an ethylenically unsaturated group and a carboxyl group is reacted with a compound (c) having both a hydroxyl group and a carboxyl group in one molecule as needed to obtain a reactive epoxy carboxylic acid ester compound (d). Then, the reactive epoxy carboxylic acid ester compound (d) is obtained by reacting a polybasic acid anhydride (e) represented by the following formula (2) or formula (3).

(In the formula, 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, and a represents 1 to 3 respectively; n represents an integer of 1 to 20)

(In the formula (2), R ₁ independently represents a hydrogen atom, 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 aforementioned formula (1) represents a saturated and unsaturated hydrocarbon group such as methyl, ethyl, ethylene, propyl, propyl, butyl, or butyl.

First, a carboxylic acid esterification step for imparting reactivity to a carboxylic acid ester compound to obtain a reactive epoxy carboxylic acid ester compound (d) will be described.

The epoxy resin (a) represented by the aforementioned formula (1) (hereinafter, also simply referred to as "epoxy resin (a)") used in the present invention is generally available in various trade names such as XD-1000 (Made by Nippon Kayaku Co., Ltd.), etc.

In the present invention, a carboxylic acid compound (b) (hereinafter also simply referred to as "carboxylic acid compound (b)") having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule is used to impart active energy to the compound. The reactivity of the line makes it a responder. The ethylenically unsaturated group and the carboxyl group are not limited as long as they each have one or more in the molecule.

Examples of the carboxylic acid compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule include (meth) acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or saturated or Reactants of an unsaturated dibasic acid with a monoglycidyl compound containing an unsaturated group, and the like. In the above, (meth) acrylics may be exemplified by (meth) acrylic acid, β-styrylacrylic acid, β-furan methacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride Half-esters, isomorphic reactants with (Meth) acrylate derivatives having one hydroxyl group in one molecule, saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives Mole reactants such as half-esters and other mono-molecular compounds containing one carboxyl group in one molecule, and other moire reactants with (meth) acrylate derivatives having a plurality of hydroxyl groups in one molecule Half-esters of isomers, such as half-esters, saturated or unsaturated dibasic acids, and glycidyl (meth) acrylate derivatives with multiple epoxy groups, etc., have multiple carboxyl groups in one molecule Polycarboxylic acid compounds.

Among these, if the reaction stability of the epoxy resin (a) and the carboxylic acid compound (b) is considered, the carboxylic acid compound (b) is preferably a monocarboxylic acid, and when a monocarboxylic acid and a polycarboxylic acid are used, It is preferable that the value shown by the molar amount of a monocarboxylic acid / the molar amount of a polycarboxylic acid is 15 or more.

In terms of sensitivity when the active energy ray-curable resin composition is used, the best examples include (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid.

The compound having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule is preferably one having no hydroxyl group in the compound.

The compound (c) having both a hydroxyl group and a carboxyl group in one molecule (hereinafter also referred to simply as "compound (c))" used in the present invention is a person who reacts with the purpose of introducing a hydroxyl group into a carboxylic acid ester compound. These are: compounds having one hydroxyl group and one carboxyl group in one molecule, compounds having two or more hydroxyl groups and one carboxyl group in one molecule, and one or more hydroxyl groups and two or more carboxyl groups in one molecule. compound of.

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

Among these, if the effect of the present invention is considered, it is preferred that it contains two or more hydroxyl groups in one molecule. Furthermore, if the stability of the carboxylic acid esterification reaction is considered, it is preferable to have one hydroxyl group in one molecule. The most preferred is one having two hydroxyl groups and one carboxyl group in one molecule. If considering the acquisition of raw materials, dimethylolpropionic acid and dimethylolbutyric acid are particularly suitable.

The compound having one or more hydroxyl groups and one or more carboxyl groups in one molecule is preferably one which does not have a polymerizable ethylenically unsaturated group in the compound.

The filling ratio of the epoxy resin (a) to the carboxylic acid compound (b) and the compound (c) in the carboxylic acid esterification reaction can be appropriately changed according to the application. That is, when all epoxy groups are esterified with a carboxylic acid, in order that the unreacted epoxy group does not remain, the storage stability as a reactive epoxy carboxylate compound (d) is high. In this case, only the reactivity caused by the introduced double bond is used.

On the other hand, it is also possible to reduce the loading amount of the carboxylic acid compound (b) and the compound (c) so that unreacted epoxy groups remain, thereby making use of the reactivity caused by the unsaturated bonds introduced in a complex manner, And the reaction caused by the residual epoxy group, for example, the polymerization reaction and the thermal polymerization reaction caused by the photo-cation catalyst are used in combination. However, at this time, it is necessary to pay attention to the research on storage and production conditions of the reactive epoxy carboxylic acid ester compound (d).

When producing a reactive epoxy carboxylic acid ester compound (d) which does not leave an epoxy group, the total of the carboxylic acid compound (b) and the compound (c) is preferably 90 to 1 equivalent to the epoxy resin (a). 120 equivalent%. Within this range, it can be manufactured under relatively stable conditions. If the loading amount of the carboxylic acid compound is more than this range, the excess carboxylic acid compound (b) and the compound (c) remain, which is not preferable.

When the epoxy group is left, 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). Beyond this range, the effect of compound hardening becomes worse. Of course, in this case, it is necessary to pay sufficient attention to the gelation during the reaction and the stability of the reactive epoxy carboxylic acid ester compound (d) with time.

The carboxylic acid esterification reaction can be performed without a solvent, or it can be diluted with a solvent and allowed to react. The solvent that can be used here is not particularly limited as long as it is a solvent that is inert to the carboxylic acid esterification reaction.

The use amount of the preferred solvent should be appropriately adjusted according to the viscosity of the obtained resin and the use, but it is more preferably that the solid content content is 90 to 30% by mass, and more preferably that it is used in a manner of 80 to 50% by mass.

Specific examples include 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, solvent naphtha, etc., ester solvents, ether solvents, ketone solvents, etc.

Examples of the ester-based solvent include ethyl acetate, alkyl acetates such as propyl acetate, butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, and diethyl ether. Glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as propylene glycol monomethyl ether monoacetate, butanediol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, Polycarboxylic acid alkyl esters such as dialkyl adipate.

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

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

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

During the reaction, in order to promote the reaction, it is better to use a catalyst. The amount of the catalyst used is relative to the reactant, that is, relative to the epoxy resin (a), the carboxylic acid compound (b), and the compound (c) and The total amount of the solvent and other reactants as necessary is 100 parts by mass, and is 0.1 to 10 parts by mass. The reaction temperature at this time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of usable catalysts include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethyl iodide. Ammonium, triphenylphosphine, triphenylstibine, methyltriphenyl , Known as general alkaline catalysts, such as chromium octoate and zirconium octoate.

A thermal polymerization inhibitor may be used. The thermal polymerization inhibitor is preferably a hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrin, diphenylamine, 3,5-di-third-butyl-4-hydroxyl. Toluene, etc.

The carboxylic acid esterification reaction system can appropriately take a sample while setting the acid value of the sample to 5 mgKOH / g or less, preferably 3 mgKOH / g or less as the end point.

The preferred molecular weight range of the reactive epoxy carboxylic acid ester compound (d) obtained in this way is a polystyrene equivalent weight average molecular weight in GPC in the range of 1,000 to 50,000, more preferably 2,000 to 30,000.

When the molecular weight is less than the above molecular weight, the toughness of the cured product cannot be fully exhibited. In addition, when the molecular weight is too large, the viscosity becomes high, and coating and the like become difficult.

Next, the acid addition step will be described in detail (hereinafter, also referred to simply as "the present acid addition reaction"). The purpose of performing the acid addition step is to introduce a carboxyl group into the reactive epoxy carboxylic acid ester compound (d) obtained in the previous step as necessary, and obtain a reactive polycarboxylic acid compound (A). That is, the hydroxyl group generated by the esterification reaction of the carboxylic acid is added to the polybasic acid anhydride (e) represented by the aforementioned formula (2) or formula (3) (hereinafter also simply referred to as "polybasic acid anhydride (e)"). It reacts to introduce a carboxyl group via an ester bond.

Examples of the alkyl group having 1 to 10 carbon atoms in the formula (2) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. R ₁ in the formula (2) is preferably a hydrogen atom or a methyl group.

The polybasic acid anhydride (e) is preferably a compound represented by the following formula (4).

The reaction for adding the polybasic acid anhydride (e) can be performed by adding the polybasic acid anhydride (e) to the carboxylic acid esterification reaction solution. The addition amount should be appropriately changed according to the application.

The amount of the polybasic acid anhydride (e) to be added, for example, when the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkaline aqueous solution development-type inhibitor material, it is preferred that the reactive polycarboxylic acid compound finally obtained is used. (A) The calculated value of the solid component acid value (according to JISK5601-2-1: 1999) becomes a preferable 20 to 120 mg‧KOH / g, and a more preferable 30 to 110 mg‧KOH / g to fill the polybasic acid anhydride ( e). When the solid component acid value at this time is within this range, it means that the developability of the alkaline aqueous solution of the active energy ray-curable resin composition of the present invention shows good developability. That is, the patterning property is good and the management of over-development is wide, and there is no excess acid anhydride remaining.

In the reaction, in order to promote the reaction, it is preferable to use a catalyst, which is relative to the reactant, that is, to the reactive epoxy carboxylic acid obtained from the epoxy compound (a), the carboxylic acid compound (b), and the compound (c). The total amount of the acid ester compound (d), the polybasic acid anhydride (e), and other reactants such as a solvent as needed, the catalyst is used in an amount of 0.1 to 10 parts by mass. The reaction temperature at this time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of usable catalysts include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethyliodide Ammonium, triphenylphosphine, triphenyl Methyltriphenyl , Chromium octoate, zirconium octoate, etc.

The present acid addition reaction system may be reacted without a solvent or may be diluted with a solvent to cause the reaction. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the acid addition reaction. In addition, when the carboxylic acid esterification reaction in the previous step is produced using a solvent, under conditions that are inert to these two reactions, it can be directly supplied to the acid addition reaction in the next step without removing the solvent. The solvent that can be used may be the same as that which can be used by the carboxylic acid esterification reaction.

The amount of the preferred solvent should be appropriately adjusted in accordance with the viscosity of the obtained resin and the use, but it is more preferably that the solid content content is 90 to 30% by mass, and more preferably 80 to 50% by mass.

Alternatively, it may be performed in a single or mixed organic solvent such as the aforementioned reactive compound (B). In this case, when it is used as a curable resin composition, it can be directly used as a composition, so it is preferable.

The thermal polymerization inhibitor and the like are preferably the same as those exemplified in the carboxylic acid esterification reaction.

In the present acid addition reaction, sampling is appropriately performed, and at the same time, the point at which the acid value of the reactant becomes a range of ± 10% of the set acid value is set as the end point.

The preferred molecular weight range of the reactive polycarboxylic acid compound (A) obtained in this way is a polystyrene-equivalent weight average molecular weight in GPC ranging from 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000. .

When the molecular weight is smaller than the above molecular weight, the toughness of the hardened material cannot be fully exerted. In addition, when the molecular weight is too large, the viscosity becomes high, and coating and the like become difficult.

Specific examples of the reactive compound (B) usable in the present invention include so-called free radical reactive acrylates, cation reactive other epoxy compounds, and ethylene compounds which are sensitive to both. Reactive oligomers.

Examples of usable acrylates 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, and polyethylene glycol (formaldehyde). Base) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, (formyl) Group) benzyl acrylate, tetrahydrofuran methyl (meth) acrylate, and the like.

Examples of polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and nonanediol di (Meth) acrylate, ethylene glycol di (meth) acrylate, divinyl di (meth) acrylate, polyethylene glycol di (meth) acrylate, ginsyl (meth) acryl fluorenyloxy Ethyl tripolyisocyanate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide Di (meth) acrylate, bisphenol di (meth) acrylate, bis- (meth) acrylate of ε-caprolactone adduct of neopentyl glycol of hydroxytrimethylacetate, dipentaerythritol Poly (meth) acrylates reacting with ε-caprolactone, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, trihydroxyethylpropane tri (Meth) acrylate and its ethylene oxide adduct, neopentaerythritol tri (meth) acrylate and its ethylene oxide adduct, neopentaerythritol tetra (meth) acrylate and its Ethylene oxide adduct, Dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct.

Usable vinyl compounds 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 styrenes include styrene, methylstyrene, and ethylstyrene. Examples of other ethylene compounds include triallyl trimer isocyanate, trimethylallyl trimer isocyanate, and the like.

Examples of the so-called reactive oligomers include urethane acrylate having both a functional group capable of functionalizing an active energy ray and a urethane bond in the same molecule, and having both urethane bonds in the same molecule. Similarly, for polyester acrylates whose active energy ray is a functionalizable functional group and an ester bond, epoxy acrylic acid which has both derived from other epoxy resins in the same molecule and which is a functional group functionalizable for active energy ray. Esters, reactive oligomers, and the like that can be used in combination.

The cation-reactive monomer is not particularly limited as long as it is a compound generally having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxy ring Hexylmethyl-3,4-epoxycyclohexane carboxylate ("CYRACURE UVR-6110" manufactured by UNION CARBIDE, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexane Carboxylic acid ester, ethylene cyclohexene diepoxide ("ELR-4206" manufactured by UNION CARBIDE, etc.), limonene diepoxide ("CELLOXIDE 3000" manufactured by DAICEL Chemical Industries, etc.), allyl cyclohexene di Epoxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy Cyclohexane-Meta Alkane, bis (3,4-epoxycyclohexyl) adipate ("CYRACURE UVR-6128" manufactured by UNION CARBIDE, etc.), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like.

Among these, the reactive compound (B) is preferably a radical curing type acrylate. When it is a cationic type, a carboxylic acid and an epoxy group react, so it must be a two-liquid mixed type.

The reactive polycarboxylic acid compound (A) of the present invention is mixed with other reactive compounds (B) to obtain an active energy ray-curable resin composition of the present invention. 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 parts by mass of the reactive polycarboxylic acid compound (A), preferably 87 to 10 parts by mass, and the other reactive compounds (B) from 3 to 95 parts by mass, more preferably 3 to 90 parts by mass. It may contain 0 to 80 mass parts of other components as needed.

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 with an upper limit of 70 parts by weight. Other components include a photopolymerization initiator, other additives, a coloring material, a hardening accelerator, and a volatile solvent added to adjust viscosity for the purpose of imparting suitable coating properties and the like. Other components that can be used are exemplified below.

The active energy ray-curable resin composition of the present invention may further contain a photopolymerization initiator. The photopolymerization initiator is preferably a radical photopolymerization initiator or a cationic photopolymerization initiator.

Examples of the radical-type photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether and the like; Toluene, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxy Acetophenones such as ethylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-propane-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-pentylanthraquinone; 2,4-diethylthioanthrone, 2-isopropyl Zanthrones such as thiaxanthone, 2-chlorothioxanthone; acetals such as acetophenone dimethyl acetal, benzyl dimethyl acetal; benzophenone, 4-benzoyl Benzophenones such as fluorenyl-4'-methyldiphenylsulfide, 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzylbenzophenone Well-known general radical photopolymerization initiators, such as phosphine oxides, phosphine oxides, such as bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide, and the like.

Examples of the cationic photopolymerization initiator include diazonium salts of Lewis acids, phosphonium salts of Lewis acids, phosphonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, and Based initiators, borate based initiators, and other photoacid generators.

Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazofluorophosphate, N, N-diethylaminophenyldiazohexafluorophosphate (Sunaid SI-60L / manufactured by Sanxin Chemical Industry Co., Ltd.) SI-80L / SI-100L, etc.), examples of phosphonium salts of Lewis acids include diphenyl sulfonium hexafluorophosphate, diphenyl sulfonium hexafluoroantimonate, etc., and examples of phosphonium salts of Lewis acid include triphenyl Samarium hexafluorophosphate (Cyracure UVI-6990, manufactured by Union Carbide, etc.), triphenyl samarium hexafluoroantimonate (Cyracure UVI-6974, manufactured by Union Carbide, etc.), etc. Examples of the phosphonium salts of Lewis acids include triphenyl鏻 Hexafluoroantimonate and so on.

Other halides include 2,2,2-trichloro- [1-4 '-(dimethylethyl) phenyl] ethanone (Trigonal PI, etc., manufactured by AKZO Corporation), and 2,2-dichloro- 1-4- (phenoxyphenyl) ethanone (Sandray1000, manufactured by Sandoz, etc.), α, α, α-tribromomethylphenylphosphonium (BMPS, etc. manufactured by Iron Chemicals Corporation), and the like. three Examples of system initiators: 2,4,6-ginseng (trichloromethyl) -tris , 2,4-trichloromethyl- (4'-methoxyphenyl) -6-tri (Triazine A, etc., manufactured by Panchim), 2,4-trichloromethyl- (4'-methoxystyryl) -6-tri (Triazine PMS, etc., manufactured by Panchim), 2,4-trichloromethyl- (piperyl) -6-tri (Triazine PP, etc., manufactured by Panchim), 2,4-trichloromethyl- (4'-methoxynaphthyl) -6-tri (Triazine B, etc., manufactured by Panchim), 2 [2 '(5-methylfuranyl) ethylene] -4,6-bis (trichloromethyl) -mesanthine (Manufactured by Sanwa Chemical Co., Ltd.), 2 (2'-furanylethylene) -4,6-bis (trichloromethyl) -mesan (Manufactured by Sanwa Chemical Co., Ltd.).

Examples of the borate-based photopolymerization initiator include NK-3876 and NK-3881 made by Japan Photosensitivity Pigment, and other photoacid generators include 9-phenylacridine, 2,2'-bis (ortho) (Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2-biimidazole (biimidazole produced by Kurojin Kasei Co., Ltd.), 2,2-azobis (2-amino-propane) Dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis [2- (imidazolin-2yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, etc.), [η- 5-2-4- (cyclopentadecyl) (1,2,3,4,5,6, η)-(methylethyl) -benzene] iron (II) hexafluorophosphate (manufactured by Ciba Geigy) Irgacure261, etc.), bis (y5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl] titanium (CGI-784, manufactured by Ciba Geigy, etc.) and the like.

In addition, an azo-based initiator such as azobisisobutyronitrile, a peroxide-based radical initiator such as benzamidine peroxide, and the like, which are thermally sensitive, may be used in combination. In addition, two types of photopolymerization initiators of a radical type and a cationic type may be used in combination. The photopolymerization initiator may be used singly or in combination of two or more kinds.

Among these, in consideration of the characteristics of the reactive polycarboxylic acid compound (A) of the present invention, a radical-type photopolymerization initiator is particularly preferred.

The active energy ray-curable resin composition of the present invention may contain a colored pigment. As the coloring pigment, for example, a so-called extender pigment that is not used for coloring can be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silicon dioxide, clay, and the like.

Furthermore, the active energy ray-curable resin composition of the present invention may contain other additives as necessary. Other additives can be used, for example, thermosetting catalysts such as melamine, shake-imparting agents such as Aerosil, polysiloxane-based, fluorine-based leveling agents and defoamers, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and the like. , Stabilizers, antioxidants, etc.

Other resins (so-called inert polymers) that do not show reactivity to the active energy ray can also use other epoxy resins, phenol resins, urethane resins, polyester resins, ketone-formaldehyde resins, cresol resins, Xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and modified products thereof. These are preferably used in the resin composition in a range of up to 40 parts by mass.

In particular, when a reactive polycarboxylic acid compound (A) is to be used for a solder resist application, it is preferable to use a known general epoxy resin as a resin which does not exhibit reactivity to active energy rays. The carboxyl group derived from the reactive polycarboxylic acid compound (A) remains after hardening by the reaction of the active energy ray, and as a result, the cured product is poor in water resistance and hydrolysis resistance. Therefore, by using an epoxy resin, the remaining carboxyl group is further carboxylated to form a stronger crosslinked structure. The known general epoxy resin can use the aforementioned cationic reactive monomer.

In addition, depending on the purpose of use, 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.

The active energy ray-curable resin composition of the present invention is easily hardened by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and laser rays, particle rays such as alpha rays, beta rays, and electron rays. In consideration of a suitable application of the present invention, among these, ultraviolet rays, laser rays, visible rays, or electron rays are preferred.

In the present invention, the material for molding refers to "the person who puts an unhardened composition into a mold, or press-fits the mold to shape an object, and causes a hardening reaction by active energy rays to shape it" or "the "Uncured composition is irradiated with focus light such as laser to cause curing reaction"

Specific applications include flat sheets, sealing materials to protect components, so-called nano-printing materials that are formed by pressing a non-hardened composition against a micro-molded "mold", and further forming a special shape. It is used for peripheral sealing materials such as light-emitting diodes, photoelectric conversion elements, etc., where thermal requirements are severe.

The material for forming a film in the present invention is applied for the purpose of covering the surface of a substrate. Specific uses can be used as: gravure printing ink, flexographic printing ink, screen printing ink, overprint printing ink and other printing materials; hard coating, top coating, overprint, transparent coating and other coating materials ; Adhesive materials for lamination and other various adhesives and adhesives for optical discs; resist materials such as solder resist, etching resist, micro-machine resist, etc. Further, a so-called dry film, which is formed by temporarily applying a film-forming material to a peelable substrate and forming a film, and then attaching it to the original substrate to form a film, can also be used as a film-forming material.

The present invention also includes a hardened material obtained by irradiating the hardened resin composition with active energy rays, and also includes a multilayer material having a layer of the hardened material.

Among these, the introduction of the carboxyl group of the reactive polycarboxylic acid compound (A) improves the adhesion to the substrate, and therefore it is preferably used for coating a plastic substrate or a metal substrate.

Furthermore, it is also preferable to use an unreacted reactive polycarboxylic acid compound (A) as an alkali aqueous development type resist material composition, which is soluble in an alkaline aqueous solution.

The term “resistive material composition” as used in the present invention refers to a film layer on which the composition is formed on a substrate, and thereafter, active energy rays such as ultraviolet rays are locally irradiated, and the physical properties of the irradiated portion and the unirradiated portion are used. An active energy ray-sensitive composition for drawing a difference. Specifically, it is a composition used for the purpose of rendering the irradiated part or unirradiated part by some methods, for example, dissolving it with a solvent or the like, an alkali solution, or the like, and drawing it.

The active energy ray-curable resin composition of the resist material composition of the present invention can be applied to various materials that can be patterned, for example, interlayer insulation materials used in solder resist materials and build-up methods It can also be used as an optical waveguide for electrical / electronic / optical substrates such as printed circuit boards, optoelectronic substrates, and optical substrates.

Particularly suitable applications are those that can make good use of heat resistance or developability, and are widely used for insulating resin sheets such as photosensitive films, photosensitive films with supports, prepregs, circuit boards (multilayer board applications, multilayer printing Circuit board applications, etc.), solder resist, underfill materials, die bonding materials, semiconductor packaging materials, caulking resins, component embedding resins and other applications that require resin compositions. Among them, since good developability can be exhibited even at a high pigment concentration, it can be suitably used for a color resist, a resist material for a color filter, and particularly a black matrix material.

Furthermore, a resin composition for an insulating layer of a multilayer printed circuit board (a multilayer printed circuit board using a cured product of a photosensitive resin composition as an insulating layer) and a resin composition for an interlayer insulating layer (with a photosensitive composition) can also be suitably used. A hardened body of the resin composition is a multilayer printed wiring board as an interlayer insulating layer), a resin composition for plating formation (a multilayered printed circuit board having a plating formed on a hardened body of the photosensitive resin composition), and the like.

Patterning using the active energy ray-curable resin composition of the present invention can be performed, for example, as follows. The active energy ray hardening type of the present invention is coated on a substrate by a screen printing method, a spray coating method, a roll coating method, an electrostatic coating method, a curtain coating method, a spin coating method and the like at a film thickness of 0.1 to 200 μm. The resin composition allows the coating film to be dried at a temperature of usually 50 to 110 ° C, preferably 60 to 100 ° C, thereby forming a coating film. Thereafter, the coating film is directly or indirectly irradiated with high-energy rays such as ultraviolet rays through the photomask formed with an exposure pattern at an intensity of usually about 10 to 2000 mJ / cm ^2, and a developing solution to be described later is used, for example, by spray coating or vibration immersion. , Puddle, brushing, etc. to obtain the desired pattern.

The alkali aqueous solution used for the above development can be used: potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate and other inorganic alkali aqueous solutions, tetramethylammonium hydroxide, hydrogen Aqueous organic bases such as tetraethylammonium oxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

In addition, it is particularly suitable for dry film applications that require mechanical strength before the hardening reaction caused by active energy rays. That is, since the balance between the hydroxyl group and the epoxy group of the epoxy resin (a) used in the present invention is in a specific range, the reactive polycarboxylic acid compound (A) of the present invention can still be used despite its relatively high molecular weight. Show good developability.

The method for forming a film is not particularly limited, but gravure printing methods such as gravure, letterpress printing methods such as flexographic printing, stencil printing methods such as screen printing, lithographic printing methods such as register, roll coater, doctor blade coating Various coating methods such as cloth applicators, die applicators, curtain applicators, and spin applicators.

The cured product of the active energy ray-curable resin composition of the present invention refers to an active energy ray-curable resin composition of the present invention which is irradiated with an active energy ray and hardened.

The article coated with the active energy ray-curable resin composition of the present invention means that the active energy ray-curable resin composition shown in the present invention is formed on a substrate and hardened to obtain at least two or more layers. Layered material.

[Example]

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

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

1) Epoxy equivalent: measured by a method according to JISK7236: 2001.

2) Softening point: Measured in accordance with JISK7234: 1986.

3) Acid value: Measured in accordance with JISK0070: 1992.

4) The measurement conditions of GPC are as follows.

Model: TOSOH HLC-8220GPC

Column: Super HZM-N

Eluate: THF (tetrahydrofuran); 0.35ml / min, 40 ° C

Detector: RI (differential refractometer)

Molecular weight standard: polystyrene

    (Synthesis Examples 1 to 3): Synthesis of Reactive Epoxycarboxylate Compound (d)    

Add XD-1000 (manufactured by Nippon Kayaku Co., Ltd., softening point 74.8 ° C, epoxy equivalent 255g / eq‧) 255g, acrylic acid (AA) or methacrylic acid (MAA) as the carboxylic acid compound (b) is shown in Table 1 The amount described in Table 1, and dimethylolpropionic acid (hereinafter, simply referred to as "DMPA") as the compound (c) is the amount described in Table 1. 3 g of triphenylphosphine as a catalyst was added, and propylene glycol monomethyl ether monoacetate was added as a solvent so that the solid content ratio became 80% by mass. The reaction was performed at 100 ° C for 24 hours to obtain a reactive epoxy carboxylate Ester compound (d) solution.

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

To 200 g of the obtained reactive epoxycarboxylic acid ester compound (d) solution, the compound described in Table 2 and the amount (g) were added as the polybasic acid anhydride (e), and the solid content content was added to 65%). The propylene glycol monomethyl ether monoacetate as a solvent was heated to 100 ° C, and then subjected to an acid addition reaction to obtain a solution of a reactive polycarboxylic acid compound (A). Table 2 shows the solid content acid value (AV: mgKOH / g) of the obtained reactive polycarboxylic acid compound (A). The solid content acid value (mg‧KOH / g) is measured by a solution and converted into a value of the solid content.

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

NTA: norbornane tricarboxylic anhydride, synthetic product with reference to Japanese Patent No. 5532123

THPA: 1,2,3,6-tetrahydrophthalic anhydride, manufactured by New Japan Physical and Chemical Co., Ltd.

SA: Rikacid SA succinic anhydride, made by New Japan Physical & Chemical Co., Ltd.

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

54.44 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1 and HX-220 (trade name: Diacrylate Monomer manufactured by Nippon Kayaku Co., Ltd.) were added as other reactive compounds (B). 3.54 g), Irgacure 907 (manufactured by Ciba Specialty Chemicals) 4.72 g and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) 0.47 g as a photopolymerization initiator 14.83 g, 1.05 g of melamine as a hardening accelerator, and 20.95 g of methyl ethyl ketone as a concentration-adjusting solvent were kneaded with a ball mill and uniformly dispersed to obtain a resin composition of a resist material.

The obtained composition was uniformly applied to a film of a copper foil as a support film by a roll coating method, and passed through a hot-air drying oven at a temperature of 70 ° C to form a resin layer having a thickness of 30 µm. Thereafter, spray development was performed with a 1% sodium carbonate aqueous solution, and the developability (unit: second) was evaluated in terms of the time until the complete development, the so-called break time. The results are shown in Table 3.

From the results described above, the resist material composition system 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, 0.2 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and Kayacure DETX-S (Nippon Kayaku Co., Ltd.) were added. (Manufactured) 0.01 g, NC-3000 (manufactured by Nippon Kayaku) 0.403 g as a hardener component, 0.017 g of triphenylphosphine as a hardening accelerator, and 0.446 g of propylene glycol monomethyl ether monoacetate, and uniformly applied to The polyimide film was passed through a hot air drying oven at a temperature of 80 ° C to form a resin layer having a thickness of 20 µm, and then exposed to an ultraviolet exposure device (OAK Manufacturing Co., Ltd., model HMW-680GW) to obtain a cured product. The produced hardened product was cut out with a width of 5 mm. Thereafter, it was set in a viscoelasticity measuring device RSA-G2 made by TA Instruments, and tan δ was measured at a frequency of 10 Hz and a heating rate of 2 ° C./min in an air environment, and the temperature of the maximum value of tan δ was set to Tg. The results are shown in Table 4.

From the results described above, it is understood that the active energy ray-curable resin composition system using the reactive polycarboxylic acid compound (A) of the present invention is superior in heat resistance compared to the resin composition for comparison.

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

20 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1 and 5.0 g of DPHA (trade name: acrylate monomer manufactured by Nippon Kayaku Co., Ltd.) as another reactive compound (B) were added, 10 g of propylene glycol monomethyl ether acetate as an organic solvent and 15 g or 10 g of Mitsubishi carbon black MA-100 as a coloring pigment were stirred. Furthermore, 35 g of glass beads were added, and dispersion was performed for 1 hour using a paint shaker. The dispersion liquid after the completion of the dispersion was coated on a polyethylene terephthalate film with a wire rod applicator # 2, and dried with a warm air dryer at 80 ° C for 10 minutes. The gloss of the coating film surface after the drying was terminated was measured using a 60 ° reflection gloss meter (Horiba IG-331 gloss meter) to evaluate the dispersibility of carbon black. The results are shown in Table 5. The higher the gloss value, the better the pigment dispersibility.

It is apparent from the above results that the coating film obtained from the resin composition containing the reactive polycarboxylic acid compound (A) obtained in Example 1 has a higher gloss value and superior pigment dispersibility than the comparative example. In addition, the resin composition containing the reactive polycarboxylic acid compound (A) of the present invention does not change the value of gloss even when the content of the colored pigment is large. On the other hand, it can be seen that when the reactive polycarboxylic acid compound of the comparative example increases the content of the coloring pigment, the gloss decreases and the content dispersibility is low. Therefore, it was confirmed that the pigment dispersibility of the reactive polycarboxylic acid compound (A) of the present invention is excellent in that it does not depend on the content of the colored pigment.

In summary, the hardened 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, so it is suitable for molding materials, Film forming material and resist material. In particular, good developability can be exhibited even at a high pigment concentration, so it can be suitably used as a color resist, a resist material for a color filter, especially a black matrix material.

Claims (9)

A reactive polycarboxylic acid compound (A) is an epoxy resin (a) represented by the following formula (1) and a carboxylic acid compound (b having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule) ), If necessary, a compound (c) having both a hydroxyl group and a carboxyl group in a molecule is reacted to obtain a reactive epoxy carboxylic acid ester compound (d), and the reactive epoxy carboxylic acid ester compound (d) is Respondents of the polybasic acid anhydride (e) represented by formula (2) or formula (3); In the formula, 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, and a represents 1 to 3 respectively; n represents an integer of 1 to 20; In the formula (2), R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and m represents an integer of 1 to 3.     An active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) described in item 1 of the patent application scope.         The active energy ray-curable resin composition according to item 2 of the scope of application for a patent, which comprises a reactive compound (B) other than the reactive polycarboxylic acid compound (A).         The active energy ray-curable resin composition according to item 2 or 3 of the scope of patent application, which comprises a photopolymerization initiator.         The active energy ray-curable resin composition according to any one of claims 2 to 4 of the scope of patent application, which is a molding material.         The active-energy-ray-curable resin composition according to any one of claims 2 to 4, which is a material for forming a film.         The active energy ray-curable resin composition according to any one of claims 2 to 4 of the scope of application for a patent, which is a resist material composition.         A hardened product is a hardened product of the active energy ray-curable resin composition according to any one of claims 2 to 7.         An article made of hardened material as described in item 8 of the scope of patent application.