JP7236813B2 - Reactive polycarboxylic acid compound, active energy ray-curable resin composition using the same, cured product thereof, and use thereof - Google Patents

Description

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

Printed wiring boards are required to have high precision and high density in order to reduce the size and weight of mobile devices and improve communication speed. Even more than the requirements, there is a demand for performance that can withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability. ing.

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

On the other hand, acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin (for example, Nippon Kayaku NC-3000) as a basic skeleton is generally known as a material that exhibits high toughness after curing, and a solder resist using this The use as is also being studied (Patent Document 2).

In addition, an attempt to disperse carbon black or the like in an acid-modified epoxy acrylate having a phenol aralkyl epoxy resin as a basic skeleton and apply it to a black matrix resist used in liquid crystal display panels and the like is also known (Patent Document 3).
In addition, a phenol aralkyl type acid-modified epoxy acrylate compound that has excellent dispersibility of color pigments and the like and has good development properties even at high pigment concentrations has been studied (Patent Document 4).

JP-A-06-324490 JP-A-09-211860 JP 2005-055814 A JP 2015-163368 A

However, although the acid-modified epoxy acrylate having a phenol aralkyl-type epoxy resin as a basic skeleton under study has a good affinity with a coloring pigment such as carbon black and disperses the pigment, it further improves the developability and further It is required to have high heat resistance.
Therefore, the present invention solves the above-mentioned problems of the prior art, and provides a highly heat-resistant acid-modified epoxy acrylate compound that is excellent in dispersibility of color pigments and the like and has good development characteristics even at high pigment concentrations, and It aims at providing the active-energy-ray-curable resin composition containing.

In order to solve the above problems, the present inventors have made intensive studies and found that an epoxy resin having a polycyclic hydrocarbon group, an unsaturated group-containing carboxylic acid, and, if necessary, a hydroxyl group and a carboxyl group in one molecule. The inventors have found that a resin composition using a reaction product with a specific polybasic acid anhydride as a reaction product with a compound having both of them solves the above-mentioned problems, and have arrived at the present invention.

That is, the present invention
[1] An epoxy resin (a) represented by the following formula (1), a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and, if necessary, in one molecule A reactive epoxy carboxylate compound (d) obtained by reacting a compound (c) having both a hydroxyl group and a carboxy group with a polybasic acid anhydride (e) represented by the following formula (2) or formula (3) a reactive polycarboxylic acid compound (A) reacted with

(In the formula, each Ar is independently either (I) or (II), and the molar ratio of (I) and (II) is (I)/(II) = 1 to 3. G is represents a glycidyl group, where n is the average number of repetitions and is a positive number of 0<n≦5.)

(In formula (2), each 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.)
[2] An active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) according to [1] above,
[3] The active energy ray-curable resin composition according to [2] above, which contains 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] above, which contains a photopolymerization initiator,
[5] The active energy ray-curable resin composition according to any one of [2] to [4] above, which is a molding material;
[6] The active energy ray-curable resin composition according to any one of [2] to [4] above, which is a film-forming material;
[7] The active energy ray-curable resin composition according to any one of [2] to [4] above, which is a resist material composition;
[8] A cured product of the active energy ray-curable resin composition according to any one of [2] to [7] above,
[9] An article overcoated with the cured product according to [8] above,
Regarding.

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention not only yields a tough cured product, but also has excellent resin physical properties even after the solvent has been dried. ing. In addition, 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 has excellent heat resistance and can be finely developed with an alkali. Suitable for forming materials and resist materials.
In addition, due to its high affinity with color pigments, the reactive polycarboxylic acid compound of the present invention and the active energy ray-curable resin composition containing the same exhibit good developability even at high pigment concentrations, and therefore, 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 further withstands high temperature and high humidity and thermal shock. Due to its high reliability, it is suitable for applications such as solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides that require particularly high reliability. is also used.

The present invention will be described in detail below.
The reactive polycarboxylic acid compound (A) of the present invention comprises an epoxy resin (a) having a structure represented by the following formula (1), and a polymerizable ethylenically unsaturated group and a carboxy group in one molecule. A carboxylic acid compound (b) having both of them is reacted with a compound (c) having both a hydroxyl group and a carboxy group in one molecule, if necessary, to obtain a reactive epoxy carboxylate compound (d). Alternatively, it can be obtained by reacting a polybasic acid anhydride (e) represented by formula (3).

(In the formula, each Ar is independently either (I) or (II), and the molar ratio of (I) and (II) is (I)/(II) = 1 to 3. G is represents a glycidyl group, where n is the average number of repetitions and is a positive number of 0<n≦5.)

(In formula (2), each 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.)

First, the carboxylation step for imparting reactivity to the carboxylate compound and obtaining the reactive epoxy carboxylate compound (d) will be described.

The epoxy resin (a) represented by the formula (1) (hereinafter also simply referred to as "epoxy resin (a)") used in the present invention has various trade names such as NC-3500 (Nippon Kayaku (manufactured by Co., Ltd.), etc., and is generally available.
Of Ar in the formula (1), (I) may be in the ortho-, meta-, or para-form. In the present invention, the meta isomer represented by the following formula (4) is preferred.

In the present invention, the carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule (hereinafter also simply referred to as "carboxylic acid compound (b)") is a compound that is exposed to active energy rays. It is made to react in order to impart reactivity. There are no restrictions as long as there are one or more ethylenically unsaturated groups and one or more carboxyl groups in the molecule.

Examples of the carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, saturated or unsaturated Examples thereof include reaction products of saturated dibasic acids and monoglycidyl compounds containing unsaturated groups. In the above, the (meth)acrylic acids include, for example, (meth)acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 Semi-esters that are equimolar reaction products with (meth)acrylate derivatives having one hydroxyl group in the molecule, and equimolar reaction products between saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives Monocarboxylic acid compounds containing one carboxyl group in one molecule such as half esters, and half esters which are equimolar reaction products with (meth)acrylate derivatives having multiple hydroxyl groups in one molecule, saturated or unsaturated Polycarboxylic acid compounds having multiple carboxy groups in one molecule such as half-esters, which are equimolar reaction products of dibasic acids and glycidyl (meth)acrylate derivatives having multiple epoxy groups, and the like.

Among these, considering the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), the carboxylic acid compound (b) is preferably a monocarboxylic acid. Even when they are used in combination, the value represented by the molar amount of monocarboxylic acid/molar amount of polycarboxylic acid is preferably 15 or more.
Most preferred are (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, and cinnamic acid in terms of sensitivity when used as an active energy ray-curable resin composition.
As a compound having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, a compound having no hydroxyl group is preferable.

The compound (c) having both a hydroxyl group and a carboxy group in one molecule (hereinafter also simply referred to as "compound (c)") used in the present invention is reacted for the purpose of introducing a hydroxyl group into the carboxylate compound. These include compounds with one hydroxyl group and one carboxy group in one molecule, compounds with two or more hydroxyl groups and one carboxy group in one molecule, and compounds with one or more hydroxyl groups in one molecule. and two or more carboxyl groups.
Examples of compounds having both one hydroxyl group and one carboxyl group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, hydroxystearic acid and the like. Compounds having two or more hydroxyl groups and one carboxyl group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid and the like. Examples of compounds having one or more hydroxyl groups and two or more carboxyl groups in one molecule include hydroxyphthalic acid and the like.
Among these, those containing two or more hydroxyl groups in one molecule are preferable in view of the effects of the present invention. Furthermore, it is preferable that one molecule has one carboxy group, considering the stability of the carboxylation reaction. Most preferably, one molecule has two hydroxyl groups and one carboxyl group. Considering availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferred.
As the compound having one or more hydroxyl groups and one or more carboxyl groups in one molecule, a compound having no polymerizable ethylenically unsaturated group is preferred.

The ratio of the epoxy resin (a), the carboxylic acid compound (b) and the compound (c) to be charged in this carboxylation reaction should be appropriately changed according to the application. That is, when all the epoxy groups are carboxylated, no unreacted epoxy groups remain, so that the reactive epoxy carboxylate compound (d) has high storage stability. In this case, only the reactivity due to the introduced double bond is utilized.

On the other hand, by reducing the amounts of the carboxylic acid compound (b) and the compound (c) charged and leaving unreacted residual epoxy groups, the reactivity due to the introduced unsaturated bonds and the reaction due to the residual epoxy groups, such as photocation It is also possible to use a combination of catalytic polymerization reaction and thermal polymerization reaction. However, in this case, attention should be paid to storage of the reactive epoxy carboxylate compound (d) and examination of manufacturing conditions.

When producing a reactive epoxy carboxylate compound (d) that does not leave epoxy groups, the total amount of the carboxylic acid compound (b) and the compound (c) is 90 to 120% by equivalent with respect to 1 equivalent of the epoxy resin (a). is preferred. Within this range, production under relatively stable conditions is possible. If the amount of the carboxylic acid compound charged is larger than this, excess carboxylic acid compound (b) and compound (c) remain, which is not preferable.

Further, when the epoxy group is to remain, the total amount of the carboxylic acid compound (b) and the compound (c) is preferably 20 to 90% by equivalent with respect to 1 equivalent of the epoxy resin (a). If it deviates from this range, the effect of composite hardening is reduced. Of course, in this case, sufficient attention must be paid to gelling during the reaction and to the stability of the reactive epoxy carboxylate compound (d) over time.

The carboxylation reaction can be carried out without a solvent or after dilution with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

The preferred amount of the solvent to be used should be appropriately adjusted depending on the viscosity of the resin to be obtained and the intended use. be done.

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 such as petroleum ether and white. Examples include gasoline, solvent naphtha, ester solvents, ether solvents, ketone solvents, and the like.

Ester-based solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, and triethylene. Mono or polyalkylene glycol monoalkyl ether monoacetates such as glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipic acid Examples thereof include polycarboxylic acid alkyl esters such as dialkyl.

Ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, glycols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether. Ethers, cyclic ethers such as tetrahydrofuran, and the like are included.

Ketone solvents include acetone, methyl ethyl ketone, cyclohexanone, isophorone, and the like.

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

During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is determined by the amount of the reactants, that is, the epoxy resin (a), the carboxylic acid compound (b) and the compound (c), and optionally the solvent. It is 0.1 to 10 parts by mass per 100 parts by mass of the total amount of reactants including other ingredients. The reaction temperature at that 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, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and octane. Known general basic catalysts such as zirconium oxide and the like can be mentioned.

A thermal polymerization inhibitor can also be used. Hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene and the like are preferably used as thermal polymerization inhibitors.

The carboxylation reaction is appropriately sampled, and the end point is when the acid value of the sample becomes 5 mgKOH/g or less, preferably 3 mgKOH/g or less.

As a preferred molecular weight range of the reactive epoxy carboxylate compound (d) thus obtained, the polystyrene equivalent weight average molecular weight in GPC is in the range of 500 to 50,000, more preferably 1,000 to 30,000. , particularly preferably 1,000 to 10,000.

If the molecular weight is smaller than this, the cured product will not exhibit sufficient toughness.

Next, the acid addition step (hereinafter also simply referred to as "acid addition reaction") will be described in detail. The acid addition step is performed 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 preceding step, if necessary. That is, the polybasic acid anhydride (e) represented by the formula (2) or (3) (hereinafter also simply referred to as "polybasic acid anhydride (e)") is added to the hydroxyl group produced by the carboxylation reaction. ) introduces a carboxy group via an ester bond.

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

A compound represented by the following formula (5) is preferable as the polybasic acid anhydride (e).

The reaction for adding the polybasic acid anhydride (e) can be performed by adding the polybasic acid anhydride (e) to the carboxylation reaction solution. The amount to be added should be appropriately changed depending on the application.

For example, when the reactive polycarboxylic acid compound (A) of the present invention is used as an alkali aqueous solution developable resist material, the amount of the polybasic acid anhydride (e) to be added is the polybasic acid anhydride (e ) The solid content acid value of the finally obtained reactive polycarboxylic acid compound (A) (in accordance with JISK5601-2-1: 1999) is preferably 20 to 120 mgKOH/g, more preferably 30 to 110 mgKOH/ It is preferable to provide a calculated value of g. When the solid content acid value at this time is within this range, the active energy ray-curable resin composition of the present invention exhibits good alkaline aqueous solution developability. In other words, it has good patterning properties and a wide range of control over overdevelopment, and no excess acid anhydride remains.

During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is the reaction obtained from the reactants, that is, the epoxy compound (a), the carboxylic acid compound (b) and the compound (c) epoxy carboxylate compound (d), polybasic acid anhydride (e), and if necessary, 0.1 to 10 parts by mass based on the total amount of reactants including a solvent and the like. The reaction temperature at that 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, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and octane. and zirconium oxide.

This acid addition reaction can be carried out without a solvent, or diluted with a solvent. 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 a solvent is used in the carboxylation reaction, which is the preceding step, it may be subjected directly to the acid addition reaction, which is the next step, without removing the solvent, provided that it is inert in both reactions. can. Solvents that can be used can be the same as those that can be used in the carboxylation reaction.

The preferred amount of the solvent to be used should be appropriately adjusted depending on the viscosity of the resin to be obtained and the intended use. be done.

In addition, the reactive compound (B) can be used alone or in a mixed organic solvent. In this case, when used as a curable resin composition, it can be used directly as a composition, which is preferable.

Moreover, it is preferable to use the same thermal polymerization inhibitor and the like as those exemplified in the carboxylation reaction.

The acid addition reaction is appropriately sampled, and the end point is reached when the acid value of the reaction product falls within the range of plus or minus 10% of the set acid value.

As a preferred molecular weight range of the reactive polycarboxylic acid compound (A) thus obtained, the weight average molecular weight in terms of polystyrene in GPC (gel permeation chromatography) measurement is in the range of 500 to 50,000, more preferably 1,000 to 30,000, particularly preferably 1,000 to 10,000.

If the molecular weight is smaller than this, the cured product will not exhibit sufficient toughness.

Specific examples of the reactive compound (B) that can be used in the present invention include radical reactive acrylates, cationic reactive epoxy compounds, and so-called reactive oligomers such as vinyl compounds sensitive to both of them. mentioned.

Usable acrylates include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

Monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and the like.

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 , diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipate epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, Hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of ε-caprolactone adduct of neoopene glycol hydroxybivalate, poly of reaction product of dipentaerythritol and ε-caprolactone (meth)acrylates, dipentaerythritol poly(meth)acrylates, trimethylolpropane tri(meth)acrylates, triethylolpropane tri(meth)acrylates and their ethylene oxide adducts, pentaerythritol tri(meth)acrylates and their ethylene Oxide adducts, pentaerythritol tetra(meth)acrylate and its ethylene oxide adducts, dipentaerythritol hexa(meth)acrylate and its ethylene oxide adducts, and the like.

Usable vinyl compounds include vinyl ethers, styrenes and other vinyl compounds. Vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether and the like. Styrenes include styrene, methylstyrene, ethylstyrene and the like. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

Furthermore, as so-called reactive oligomers, there are urethane acrylates having both a functional group sensitive to active energy rays and a urethane bond in the same molecule, and similarly a functional group sensitive to active energy rays and an ester bond in the same molecule. Examples include polyester acrylates having both of them, epoxy acrylates derived from other epoxy resins and having functional groups sensitive to active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination.

Moreover, the cationic reactive monomer is not particularly limited as long as it is generally a compound having an epoxy group. For example, glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ("Cyracure" manufactured by Union Carbide) UVR-6110", etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexene dioxide ("ELR-4206" manufactured by Union Carbide, etc.), limonene dioxide (Daisel Chemical Industries, Ltd. manufactured by "Celoxide 3000" etc.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy ) Cyclohexane-m-dioxane, 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, radical-curing acrylates are most preferable as the reactive compound (B). In the case of a cationic type, it is necessary to use a two-liquid mixed type because the carboxylic acid reacts with the epoxy group.

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 another reactive compound (B). At this time, other components may be added as appropriate depending on the application.

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

In addition, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various uses, other components may be added to the composition up to an upper limit of 70 parts by weight. Other components include photopolymerization initiators, other additives, coloring materials, curing accelerators, and volatile solvents added to adjust viscosity for the purpose of imparting coatability. Other ingredients that may be used are exemplified below.

The active energy ray-curable resin composition of the present invention can further contain a photopolymerization initiator. Radical photopolymerization initiators and cationic photopolymerization initiators are preferred as the photopolymerization initiator.
Examples of radical type photopolymerization initiators 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-dichloro Acetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1 -one and other acetophenones; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone and other anthraquinones; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc. thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone and other benzophenones; 2,4,6-trimethyl Known general radical type photopolymerization initiators such as phosphine oxides such as benzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide can be used.

Examples of cationic photopolymerization initiators 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, borate initiators, and other photoacid generators.

Examples of diazonium salts of Lewis acids include p-methoxyphenyldiazonium fluorophosphonate, N,N-diethylaminophenyldiazonium hexafluorophosphonate (San-Aid SI-60L/SI-80L/SI-100L manufactured by Sanshin Kagaku Kogyo Co., Ltd.) and the like. Lewis acid iodonium salts include diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate and the like, and Lewis acid sulfonium salts include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide, etc.). , triphenylsulfonium hexafluoroantimonate (Cyracure UVI-6974 manufactured by Union Carbide, etc.) and the like, and the phosphonium salts of Lewis acids include triphenylphosphonium hexafluoroantimonate and the like.

Other halides include 2,2,2-trichloro-[1-4′-(dimethylethyl)phenyl]ethanone (TrigonalPI manufactured by AKZO, etc.), 2,2-dichloro-1-4-(phenoxyphenyl) Examples thereof include ethanone (Sandoz Sandray 1000, etc.), α,α,α-tribromomethylphenyl sulfone (BMPS, etc. manufactured by Steel Chemical Co., Ltd.). Triazine-based initiators include 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4′-methoxyphenyl)-6-triazine (TriazineA manufactured by Panchim Co., etc.), 2,4 -trichloromethyl-(4′-methoxystyryl)-6-triazine (such as TriazinePMS manufactured by Panchim), 2,4-trichloromethyl-(pipronyl)-6-triazine (such as TriazinePP manufactured by Panchim), 2,4-trichloro Methyl-(4′-methoxynaphthyl)-6-triazine (TriazineB manufactured by Panchim, etc.), 2[2′(5-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (Sanwa Chemical Co., Ltd.), 2(2′-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd.), and the like.

Examples of borate-based photopolymerization initiators include NK-3876 and NK-3881 manufactured by Japan Photosensitive Color, and other photoacid generators such as 9-phenylacridine, 2,2′-bis(o-chlorophenyl )-4,4′,5,5′-tetraphenyl-1,2-biimidazole (such as biimidazole manufactured by Kurogane Kasei Co., Ltd.), 2,2-azobis(2-amino-propane) dihydrochloride (Wako Pure Chemical Industries, Ltd. V50, etc. manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis[2-(imidazolin-2yl)propane] dihydrochloride (VA044, etc. manufactured by Wako Pure Chemical Industries, Ltd.), [Eta-5-2-4-(cyclopentadecyl) (1 , 2,3,4,5,6, eta)-(methylethyl)-benzene]iron(II) hexafluorophosphonate (such as Irgacure 261 manufactured by CibaGeigy), bis(y5-cyclopentadienyl)bis[2,6 -difluoro-3-(1H-pyri-1-yl)phenyl]titanium (CGI-784 manufactured by CibaGeigy, etc.) and the like.

In addition, azo-based initiators such as azobisisobutyronitrile, heat-sensitive peroxide-based radical initiators such as benzoyl peroxide, and the like may be used together. Also, both radical and cationic photopolymerization initiators may be used together. A photoinitiator can also be used individually by 1 type, and can also collectively use two or more types.

Among these, the radical type photopolymerization initiator is particularly preferable in consideration of the properties of the reactive polycarboxylic acid compound (A) of the present invention.

Furthermore, the active energy ray-curable resin composition of the present invention can contain a coloring pigment. As the coloring pigment, for example, a so-called extender pigment, which is not intended for coloring, can also be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica and clay.

Furthermore, the active energy ray-curable resin composition of the present invention can contain other additives, if necessary. Other additives include, for example, thermosetting catalysts such as melamine, thixotropic agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, oxidation Inhibitors and the like can be used.

Other resins that do not show reactivity to active energy rays (so-called inert polymers) include, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, Styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the range of up to 40 parts by mass in the resin composition.

In particular, when the reactive polycarboxylic acid compound (A) is used for solder resist applications, it is preferable to use known general epoxy resins as resins that do not show reactivity to active energy rays. This is because carboxyl groups derived from the reactive polycarboxylic acid compound (A) remain even after reaction and curing by active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. Therefore, by using an epoxy resin, the remaining carboxyl groups are further carboxylated to form a stronger crosslinked structure. The above cationic reactive monomers can be used for the known general epoxy resins.

A volatile solvent can also be added to the resin composition in an amount of up to 50 parts by mass, more preferably up to 35 parts by mass, for the purpose of adjusting the viscosity according to 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 active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser beams, and particle beams such as alpha rays, beta rays and electron beams. Of these, ultraviolet light, laser light, visible light, or electron beams are preferred in view of the preferred application of the present invention.

In the present invention, the molding material refers to a material in which an uncured composition is put into a mold or pressed against the mold to mold an object, and then a curing reaction is caused by an active energy ray to be molded, or an uncured composition is used. It refers to a material used for molding by irradiating focused light such as a laser to cause a curing reaction.

Specific applications include a sheet molded into a flat surface, a sealing material for protecting an element, a so-called nanoimprint material that presses a microfabricated "mold" against an uncured composition to perform fine molding, Furthermore, it is suitable for use as a peripheral sealing material for light-emitting diodes, photoelectric conversion elements, etc., which have particularly strict thermal requirements.

In the present invention, the film-forming material is used for the purpose of coating the substrate surface. Specific applications include ink materials such as gravure ink, flexographic ink, silk screen ink, and offset ink; coating materials such as hard coats, top coats, overprint varnishes and clear coats; lamination, optical discs, and various other adhesives. This includes adhesive materials such as adhesives and adhesives, and resist materials such as solder resists, etching resists, micromachine resists, and the like. Furthermore, a so-called dry film, in which a film-forming material is temporarily applied to a peelable substrate to form a film and then laminated to the intended substrate to form a film, also corresponds to the film-forming material. .

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

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

Furthermore, it is also preferable to use the unreacted reactive polycarboxylic acid compound (A) as an alkaline water developable resist material composition, taking advantage of the feature of being soluble in an alkaline aqueous solution.

In the present invention, the resist material composition refers to forming a film layer of the composition on a substrate, then partially irradiating active energy rays such as ultraviolet rays, and determining the difference in physical properties between the irradiated portion and the non-irradiated portion. It refers to an active energy ray-sensitive composition that is to be drawn using. Specifically, it is a composition used for the purpose of drawing by removing an irradiated portion or an unirradiated portion by some method, for example, by dissolving it with a solvent or the like or an alkaline solution.

The active energy ray-curable resin composition, which is the resist material composition of the present invention, can be applied to various materials that can be patterned. Furthermore, it is also used as an optical waveguide in electrical/electronic/optical substrates such as printed wiring boards, optoelectronic substrates, and optical substrates.

Particularly suitable applications include photosensitive films, photosensitive films with supports, insulating resin sheets such as prepreg, circuit boards (laminated boards, multilayer printed wiring boards) Applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulation materials, hole-filling resins, component-embedding resins, and a wide range of other applications that require resin compositions. In particular, since good developability can be exhibited even at high pigment concentrations, it can be suitably used for color resists, resist materials for color filters, particularly black matrix materials, and the like.

Furthermore, a resin composition for an insulating layer of a multilayer printed wiring board (multilayer printed wiring board having a cured product of a photosensitive resin composition as an insulating layer), a resin composition for an interlayer insulating layer (a cured product of a photosensitive resin composition multilayer printed wiring board as an interlayer insulating layer), a resin composition for plating (multilayer printed wiring board in which plating is formed on a cured product of a 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 curable resin composition of the present invention is applied onto a substrate to a thickness of 0.1 to 200 μm by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, or spin coating. A coating film can be formed by drying the coating film at a temperature of usually 50 to 110°C, preferably 60 to 100°C. After that, the coating film is directly or indirectly irradiated with high energy rays such as ultraviolet rays at an intensity of about 10 to 2000 mJ/cm ² through a photomask having an exposure pattern formed thereon. A desired pattern can be obtained by vibration dipping, paddle, brushing, or the like.

Examples of alkaline aqueous solutions used for the development include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate and potassium phosphate, and tetramethylammonium hydroxide. , tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine and triethanolamine. This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

In addition, it is particularly suitable for dry film applications that require mechanical strength before curing reaction 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 within a specific range, the reactive polycarboxylic acid compound (A) of the present invention has a relatively high molecular weight. Therefore, good developability can be exhibited.

The method for forming the film is not particularly limited, but may be an intaglio printing method such as gravure, a letterpress printing method such as flexography, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, or the like. Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating the active energy ray-curable resin composition of the present invention with an active energy ray and curing it.

An article overcoated with the active energy ray-curable resin composition of the present invention means at least two or more layers obtained by forming and curing a film of the active energy ray-curable resin composition shown in the present invention on a substrate. shows a material comprising a layer of

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, % indicates mass % in the examples.
In addition, "Example 1-1" to "Example 1-3", "Example 2-1" to "Example 2-3", "Example 3-1" to "Example 3-3", "Example 4-1" to "Example 4-6" are respectively "Reference Example 1-1" to "Reference Example 1-3", "Reference Example 2-1" to "Reference Example 2-3", " Reference Example 3-1” to “Reference Example 3-3” and “Reference Example 4-1” to “Reference Example 4-6” shall be read.

The softening point, epoxy equivalent and acid value were measured under the following conditions.
1) Epoxy equivalent: Measured according to JISK7236:2001.
2) Softening point: Measured by a method according to JISK7234:1986.
3) Acid value: Measured according to JISK0070:1992.
4) The measurement conditions of GPC are as follows.
Model: TOSOH HLC-8220GPC
Column: Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml/min, 40°C
Detector: RI (differential refractometer)
Molecular weight standard: Polystyrene

(Synthesis Examples 1 to 3): Synthesis of reactive epoxy carboxylate compound (d) NC-3500 (manufactured by Nippon Kayaku Co., Ltd., softening point 70 ° C., epoxy equivalent 205 g / eq. Acrylic acid (AA) or methacrylic acid (MAA) was added in the amount described in Table 1 as b), and dimethylolpropionic acid (hereinafter abbreviated as "DMPA") was added in the amount described in Table 1 as compound (c). 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 80% by mass, and the mixture was reacted at 100° C. for 24 hours to obtain a reactive epoxy carboxylate compound (d) solution. .

(Example 1, Comparative Example 1): Preparation of reactive polycarboxylic acid compound (A) compound, the amount (g), and propylene glycol monomethyl ether monoacetate as a solvent so that the solid content is 65%, heated to 100 ° C., and then subjected to an acid addition reaction to obtain a reactive polycarboxylic acid compound (A) A solution was obtained. Table 2 shows the solid content acid value (AV: mgKOH/g) of the obtained reactive polycarboxylic acid compound (A). The solid content acid value (mgKOH/g) was measured as a solution and converted to a solid content value.

HTMA: 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, manufactured by Mitsubishi Gas Chemical Company, Inc.
NTA: Norbornanetricarboxylic anhydride, see Japanese Patent No. 5532123 Synthetic product THPA: 1,2,3,6-tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd. SA: Licacid SA succinic anhydride, Shin Nippon 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, and other reactive compounds (B) HX-220 (trade name: diacrylate monomer manufactured by Nippon Kayaku Co., Ltd.) 3.54 g, 4.72 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator and Kayacure DETX-S (Japan 0.47 g of Kayaku Co., Ltd.), 14.83 g of NC-3000 (manufactured by Nippon Kayaku) as a curing agent component, 1.05 g of melamine as a thermosetting catalyst, and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent. , kneaded in a bead mill, and uniformly dispersed to obtain a resist material resin composition.
The resulting composition was uniformly applied to a copper foil film serving 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. After that, spray development was carried out with a 1% sodium carbonate aqueous solution, and the developability was evaluated by the time required for complete development, the so-called break time (unit: seconds).

From the above results, the resist material composition using the reactive polycarboxylic acid compound (A) of the present invention exhibits better developability than the compositions using the comparative reactive polycarboxylic acid compounds. have.

(Example 3 and Comparative Example 3): Evaluation of heat resistance 8 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, Irgacure 907 (Ciba Specialty Chemicals) as a photopolymerization initiator 0.24 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.01 g of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) as a curing agent component, 0.403 g of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.), and triphenylphosphine as a heat curing catalyst. 0.017 g of and 0.446 g of propylene glycol monomethyl ether monoacetate are added, uniformly applied to a polyimide film, passed through a hot air drying oven at a temperature of 80 ° C. to form a resin layer with a thickness of 20 μm, and then an ultraviolet exposure device. (Oak Seisakusho Co., Ltd., model HMW-680GW) to obtain a cured product. The prepared cured product is cut into a width of 5 mm. After that, it was set in a viscoelasticity measuring device RSA-G2 manufactured by TA Instruments, in an air atmosphere, at a frequency of 10 Hz and a temperature increase rate of 2° C./min. was measured, and the temperature at the maximum value of tan δ was defined as Tg.

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 of Pigment Dispersibility 20 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, and DPHA (trade name) as the other reactive compound (B) : Nippon Kayaku Co., Ltd. acrylate monomer), 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 added and stirred. Further, 35 g of glass beads were added and dispersed with a paint shaker for 1 hour. After completion of dispersion, the dispersion was applied onto a polyethylene terephthalate film using wire bar coater #2 and dried for 10 minutes using a hot air dryer at 80°C. After drying, the glossiness of the coating film surface was measured using a 60° reflection gloss meter (Horiba IG-331 gloss meter) to evaluate the dispersibility of carbon black. Table 5 shows the results. The higher the gloss value, the better the pigment dispersibility.

From the above results, the coating film obtained from the resin composition containing the reactive polycarboxylic acid compound (A) obtained in Example 1 did not change in gloss even when the content of the coloring pigment was large. rice field. It can be confirmed that the pigment dispersibility of the reactive polycarboxylic acid compound (A) of the present invention is excellent regardless of the content of the coloring pigment, although the developability and heat resistance are improved.

As described above, the cured product of the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention has excellent heat resistance and can be finely developed with an alkali. Suitable for forming materials and resist materials. In particular, since it exhibits good developability even at high pigment concentrations, it is suitable for color resists, resist materials for color filters, particularly black matrix materials, and the like.

Claims (9)

An epoxy resin (a) represented by the following formula (1), a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, and optionally a hydroxyl group in one molecule. Active energy ray- reactive epoxy carboxylate compound (d) obtained by reacting compound (c) having a carboxy group with polybasic acid anhydride (e) represented by the following formula (3): Energy ray- reactive polycarboxylic acid compound (A).

(In the formula, each Ar is independently either (I) or (II), and the molar ratio of (I) and (II) is (I)/(II) = 1 to 3. G is represents a glycidyl group, where n is the average number of repetitions and is a positive number of 0<n≦5.)

An active energy ray -curable resin composition comprising the active energy ray-reactive polycarboxylic acid compound (A) according to claim 1 . The active energy ray- curable resin composition according to claim 2, further comprising an active energy ray- reactive compound (B) other than the active energy ray-reactive polycarboxylic acid compound (A). The active energy ray-curable resin composition according to claim 2 or 3, comprising a photopolymerization initiator. The active energy ray-curable resin composition according to any one of claims 2 to 4, which is a molding material. The active energy ray-curable resin composition according to any one of claims 2 to 4, which is a film-forming material. 5. The active energy ray-curable resin composition according to any one of claims 2 to 4, 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 7. An article overcoated with a cured product of the active energy ray-curable resin composition according to claim 8 .