JP2013108093A - Reactive carboxylate compound, active energy ray-curable resin composition using the same, and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant of a color pigment which provides an active energy ray-curable resin composition with good hardness and flame retardancy.SOLUTION: A reactive epoxy carboxylate compound (A) which is the dispersant of a color pigment, a reactive polycarboxylic acid compound thereof, and a resin composition including them are provided.

Description

The present invention relates to a compound (b) having at least one polymerizable ethylenically unsaturated group and one or more carboxyl groups in a molecule represented by acrylic acid or the like (b) in a phenol aralkyl type epoxy resin (a) having a biphenyl skeleton. ) reactivity obtained by reacting an epoxy carboxylate compound (a), and the reactive polycarboxylic acid compound is an acid-modified product relates (B). These reactive epoxycarboxylate compound (A) and reactive polycarboxylic acid compound (B) have good affinity for the pigment, and a tough cured product is obtained from the resin composition containing them. Can do.

  With the aim of reducing the size and weight of portable devices and improving communication speed, printed wiring boards are required to have high precision and high density. With this, the demand for solder resists that cover the circuit itself has become increasingly sophisticated. Performance that can withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability is required more than required, and a film forming material with tougher cured material properties is required. It was.

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

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

In addition, an attempt to apply a black matrix resist used in liquid crystal display panels by dispersing carbon black or the like in an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin (eg, Nippon Kayaku NC-3000) as a basic skeleton. Are known. (Patent Document 3)
In this application, when coloring pigments such as carbon black are blended at a high concentration, the pigment has good affinity with the resin and the pigment is dispersed, so that good developability can be obtained even when the pigment is present at a high concentration. As shown, there is no pigment residue and development is possible. Conventional acid-modified epoxy acrylates, particularly acid-modified epoxy acrylates having a biphenyl skeleton, exhibit relatively good dispersibility, but have been required to have developability at a higher pigment concentration, that is, higher pigment dispersibility. However, since the affinity with the good pigment and the skeleton have a rigid structure, when the pigment dispersion is made, the dispersion liquid is pseudo-aggregated and the stability is not good. there were.

  In addition, the epoxy resin (a) used in this invention is already well-known (patent document 4).

Japanese Patent Laid-Open No. 06-324490 JP-A-11-140144 JP 2005-55814 A Japanese Patent No. 2952094

Although the curable resin composition using the phenol aralkyl type epoxy resin can obtain a relatively tough cured product, there is a demand for further toughened cured material properties that can withstand bending of the substrate.
Furthermore, there is a need for acid-modified epoxy acrylates that have higher dispersion in colored pigments, especially carbon black, and that have good development characteristics even at high pigment concentrations. At this time, a material having a relatively high molecular weight and appropriate developability is required.
By using the reactive epoxycarboxylate compound of the present invention, it is cured by active energy rays such as ultraviolet rays, has good storage stability, and also has good flame retardancy and further folding resistance. A tough film with excellent resistance can be obtained.
In addition, when a colored resist composition is used, good development characteristics can be obtained even at a high pigment concentration.

Since the present inventors to solve the problems described above, the epoxy resin having a specific structure, reacted the compound having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule (b) It has been found that the reactive epoxycarboxylate compound obtained in this way, and the reactive polycarboxylic acid compound obtained by reacting it with the polybasic acid anhydride (d) have particularly excellent resin properties.
Furthermore, it has been found that it has a particularly good affinity with colored pigments and can be a resist material having good developability even at a high pigment concentration.
That is, the present invention
Colored pigments obtained by reacting the compound (b) to the epoxy resin (a) in one molecule both a one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups represented by the following general formula (1) It is related with the reactive epoxy carboxylate compound (A) which is a dispersing agent of this .

Wherein R ₁ is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, m is an integer of 1 to 4, and n is a positive number of 1 to 10 on average. Respectively.)
Furthermore, it is related with the reactive polycarboxylic acid compound (B) which is a dispersing agent of the coloring pigment obtained by making the carboxylate compound (A) obtained above react with a polybasic acid anhydride (d).
Furthermore, the present invention relates to an active energy ray-curable resin composition comprising the carboxylate compound (A) and / or a reactive polycarboxylic acid compound (B).
Furthermore, the present invention relates to an active energy ray-curable resin composition comprising a reactive compound (C) other than (A) and (B).
Furthermore, the present invention relates to an active energy ray-curable resin composition characterized by containing a coloring pigment in the active energy ray-curable resin composition.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a molding material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a film forming material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a resist material composition.
Furthermore, it is related with the hardened | cured material of the said active energy ray curable resin composition.
Further, the present invention relates to an article overcoated with the active energy ray-curable resin composition.

The active energy ray-curable resin composition containing an epoxy resin having a specific structure of the present invention has excellent resin properties not only in obtaining a tough cured product but also in a state where the solvent is only dried. The cured product obtained from the active energy ray-curable resin composition of the present invention can be suitably used as a film-forming material that requires thermal and mechanical toughness.
More preferably, it can be used for applications requiring particularly high characteristics 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.
Furthermore, since it has high affinity with colored pigments such as carbon black, it can exhibit good developability even at high pigment concentrations, so that resist materials for color resists and color filters, particularly It can be suitably used for a black matrix material or the like.

The reactive epoxycarboxylate compound (A) of the present invention can be polymerized with one or more polymers in the molecule in order to impart reactivity to the epoxy resin (a) represented by the following formula (1) having a characteristic biphenyl skeleton. It reacted ethylenically unsaturated group and a compound having both one or more carboxyl groups (b) is obtained.

That is, the feature of the present invention is exhibited by simultaneously introducing an ethylenically unsaturated group and a hydroxyl group into a molecular chain by epoxy carboxylation.

It is essential that the epoxy resin (a) represented by the general formula (1) used in the present invention has a specific structure having a biphenyl skeleton. In the formula, R ₁ is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms. The halogen atom shown here represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Moreover, a C1-C4 hydrocarbon group shows saturated and unsaturated hydrocarbon groups, such as a methyl group, an ethyl group, ethylene group, a propyl group, a propylene group, a butyl group, butylene group.
Furthermore, in General formula (1), m shows the integer of 1-4 and shows the number of functional groups introduce | transduced. n is an average value and represents a positive number of 1 to 10, preferably 1 to 6, respectively. If the value of n is less than 10, preferably less than 6, a suitable viscosity range is obtained.

Of the epoxy resins (a) represented by the general formula (1), those in which R ₁ is all hydrogen atoms are preferred because they are available at low cost.
Furthermore, these production methods and the like are known and described in detail in Patent Document 4. Generally, commercial products are available from Nippon Kayaku as NC-3000 series.
In the NC-3000 series, in the above formula, all R ₁ are hydrogen atoms, and n is an average value of 1 to 10 positive numbers. In the present invention, a suitable one of the series grades can be appropriately selected.

  The compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule used in the present invention is reacted in order to impart reactivity to active energy rays. is there. These include monocarboxylic acid compounds and polycarboxylic acid compounds.

  Examples of monocarboxylic acid compounds containing one carboxyl group in one molecule include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or saturated or unsaturated dibasic acid and unsaturated group-containing monoglycidyl. A reaction product with a compound is mentioned. In the above, examples of the acrylic acid include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and one molecule. (Meth) acrylate derivatives having a single hydroxyl group and half-esters that are equimolar reactants, half-esters that are equimolar reactants of saturated or unsaturated dibasic acid and monoglycidyl (meth) acrylate derivatives, etc. Can be mentioned.

  Furthermore, as a polycarboxylic acid compound having a plurality of carboxyl groups in one molecule, a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule and a half ester, a saturated or unsaturated dibasic acid as an equimolar reaction product, and And half-esters which are equimolar reaction products with glycidyl (meth) acrylate derivatives having a plurality of epoxy groups.

Of these, most preferable are (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid in terms of sensitivity when an active energy ray-curable resin composition is used.
As the compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule, those having no hydroxyl group in the compound are preferable.

  The compound (c) having one or more hydroxyl groups and one or more carboxyl groups in one molecule used in the present invention is reacted for the purpose of introducing hydroxyl groups into the carboxylate compound. These include compounds having one hydroxyl group in one molecule and one carboxyl group, compounds having two or more hydroxyl groups and one carboxyl group in one molecule, one or more hydroxyl groups in one molecule and two There are compounds having both of the above carboxyl groups.

Examples of the compound having one hydroxyl group and one carboxyl group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, hydroxystearic acid and the like.
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.

Among these, those having two or more hydroxyl groups in one molecule are preferable in view of the effects of the present invention. Furthermore, it is preferable that the carboxyl group is one in one molecule in view of the stability of the carboxylation reaction. Most preferably, it has two hydroxyl groups and one carboxyl group in one molecule. Considering the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable.
As the compound (c) having both one or more hydroxyl groups and one or more carboxyl groups in one molecule, those having no polymerizable ethylenically unsaturated group in the compound are preferable.

  Among these, considering the stability of the reaction between the epoxy resin (a) and the carboxylic acid compounds (b) and (c), it is preferable that (b) and (c) are monocarboxylic acids. Even when the acid and the polycarboxylic acid are used in combination, the value represented by the total molar amount of the monocarboxylic acid / the total molar amount of the polycarboxylic acid is preferably 15 or more.

  The charge ratio of the total carboxylic acid of the epoxy resin (a) and the carboxylic acid compounds (b) and (c) in this reaction should be appropriately changed according to the application. That is, when all the epoxy groups are carboxylated, unreacted epoxy groups do not remain, so that the storage stability as a reactive carboxylate compound is high. In this case, only the reactivity due to the introduced double bond is used.

  On the other hand, by deliberately reducing the charged amount of the carboxylic acid compound and leaving an unreacted residual epoxy group, the reactivity due to the introduced unsaturated bond and the reaction due to the remaining epoxy group, for example, a polymerization reaction or heat caused by a photocationic catalyst, It is also possible to use the polymerization reaction in combination. In this case, however, attention should be paid to the storage of the reactive carboxylate compound and the examination of the production conditions.

  When producing the reactive carboxylate compound (A) that does not leave an epoxy group, the total amount of the carboxylic acid compounds (b) and (c) is 90 to 120 equivalent% with respect to 1 equivalent of the epoxy resin (a). Is preferred. Within this range, it is possible to manufacture under relatively stable conditions. When the amount of the carboxylic acid compound charged is larger than this, an excess of the carboxylic acid compound (b) remains, which is not preferable.

  Moreover, when leaving an epoxy group intentionally, it is preferable that the total of carboxylic acid compound (b) and (c) is 20-90 equivalent% with respect to 1 equivalent of said epoxy resin (a). When deviating from this range, the effect of the composite curing is reduced. Of course, in this case, sufficient attention must be paid to gelation during the reaction and stability with time of the carboxylate compound (A).

  The use ratio of the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups and the compound (c) having one or more hydroxyl groups and one or more carboxyl groups is the molar ratio to the carboxylic acid. (B) :( c) is preferably in the range of 9: 1 to 1: 9, more preferably 4: 6 to 8: 2. If it is this range, the fall of the sensitivity when (b) is too few can be prevented, and the effect of (c) when (c) is too little can be prevented from becoming diluted.

This carboxylation 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 carboxylation reaction.
The preferred amount of solvent used should be adjusted as appropriate depending on the viscosity and intended use of the resulting resin, but is preferably 90 to 30% by weight, more preferably 80 to 50% by weight as the solid content. Use a solvent.

Specific examples of what can be used as the above solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and Examples thereof include petroleum ether, white gasoline, and solvent naphtha.
Examples of ester 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, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.
Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, 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. Glycol ethers, and cyclic ethers such as tetrahydrofuran.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  In addition, it can carry out in single or mixed organic solvents, such as reactive compounds (C) other than (A) and (B). In this case, when it is used as a curable composition, it can be used directly as a composition, which is preferable.

  During the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of the catalyst used is the reaction product, that is, the epoxy compound (a), the carboxylic acid compound (b), and optionally a solvent or the like. 0.1 to 10% by weight based on the total amount of reactants. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, Examples include known general basic catalysts such as zirconium octoate.

  Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like as a thermal polymerization inhibitor.

  The end point of this reaction is the time when the acid value of the sample is 5 mgKOH / g or less, preferably 2 mgKOH / g or less, while sampling appropriately.

As a preferable molecular weight range of the reactive carboxylate compound (A) thus obtained, the polystyrene-equivalent weight average molecular weight in GPC is in the range of 1,000 to 30,000, more preferably 1,500 to 20,000. is there.
When the molecular weight is smaller than this, the toughness of the cured product is not sufficiently exhibited, and when it is larger than this, the viscosity becomes high and coating or the like becomes difficult.

Next, the acid addition step will be described in detail. The acid addition step is performed for the purpose of obtaining a reactive polycarboxylic acid (B) by introducing a carboxyl group into the reactive carboxylate compound (A) obtained in the previous step as necessary. Reasons for introducing a carboxyl group include, for example, in applications where resist patterning or the like is required, imparting solubility in alkaline water to active energy ray non-irradiated parts, and imparting adhesion to metals, inorganic substances, etc. It is introduced with the purpose of.
Specifically, the carboxyl group is introduced through an ester bond by addition reaction of the polybasic acid anhydride (d) to the hydroxyl group generated by the carboxylation reaction.

  As specific examples of the polybasic acid anhydride (d), for example, any compound having an acid anhydride structure in one molecule can be used. For example, it can be used in alkaline aqueous solution developability, heat resistance, and hydrolysis resistance. Excellent succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride Acid is particularly preferred.

  The reaction for adding the polybasic acid anhydride (d) can be performed by adding the polybasic acid anhydride (d) to the carboxylation reaction solution. The amount added should be changed as appropriate according to the application.

  However, when the polycarboxylic acid compound (B) of the present invention is to be used as an alkali development resist, the polybasic acid anhydride (d) is finally obtained from the reactive polycarboxylic acid compound (B). It is preferable to charge a calculated value such that the solid content acid value (based on JIS K5601-2-1: 1999) is 30 to 120 mg · KOH / g, more preferably 40 to 105 mg · KOH / g. When the solid content acid value at this time is within this range, the developability of the aqueous alkaline solution developability of the active energy ray-curable resin composition of the present invention is good. That is, good patternability and a wide control range for over-development are possible, and no excess acid anhydride remains.

  In the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is a reaction product, that is, a carboxy obtained from the epoxy compound (a), the carboxylic acid compound (b) and (c). It is 0.1 to 10% by weight with respect to the total amount of the reaction product including the rate compound and other basic acid anhydride (d), and optionally 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 the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, Examples include zirconium octoate.

The acid addition reaction can be performed 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, in the case of producing using a solvent in the carboxylation reaction that is the previous step, it may be subjected directly to the acid addition reaction that is the next step without removing the solvent, provided that both reactions are inert. it can.
The preferred amount of solvent to be used should be appropriately adjusted depending on the viscosity and use of the resin obtained, but preferably 90 to 30% by weight, more preferably 80 to 50% by weight as the solid content. Use.

Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum ether, white Examples include gasoline and solvent naphtha.
Examples of ester 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, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.
Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, 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. Glycol ethers, and cyclic ethers such as tetrahydrofuran.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  In addition, the reaction can be performed in a single or mixed organic solvent such as a reactive compound (C) described later. In this case, when it is used as a curable composition, it can be used directly as a composition, which is preferable.

  Moreover, it is preferable to use the thing similar to the illustration in the said carboxylation reaction as a thermal-polymerization inhibitor.

  In this reaction, the end point is determined when the acid value of the reaction product is within a range of plus or minus 10% of the set acid value while appropriately sampling.

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

  Examples of acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other 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, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogen Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( (Meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct, etc. Is mentioned.

  Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

Furthermore, as so-called reactive oligomers, urethane acrylate having a functional group capable of acting on active energy rays and a urethane bond in the same molecule, and similarly a functional group capable of acting on active energy rays and an ester bond in the same molecule. Polyester acrylate,
Other examples include epoxy acrylates derived from epoxy resins and having functional groups capable of acting on active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination.

  The cation 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, -epoxycyclohexanecarboxylate (manufactured by Union Carbide) "Syracure UVR-6110" etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide), limonene dioxide (Daicel Chemical) “Celoxide 3000” manufactured by Kogyo Co., Ltd.), allyl cyclohexylene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxy) Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3,4 -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane and the like.

  Of these, the reactive compound (C) is most preferably an acrylate that is radically curable. In the case of the cation type, the carboxylic acid and the epoxy react with each other, so that a two-component mixed type is required.

  The carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) of the present invention and the reactive compound (C) other than (A) and (B), if necessary, are mixed to obtain the present invention. An active energy ray-curable resin composition can be obtained. At this time, you may add another component suitably according to a use.

  The active energy ray-curable resin composition of the present invention has a carboxylate compound (A) and / or a reactive polycarboxylic acid compound (B) of 97 to 5% by weight, preferably 87 to 10% by weight in the composition. A reactive compound (C) other than A) and (B) is contained in an amount of 3 to 95% by weight, more preferably 3 to 90% by weight. If necessary, other components may be contained up to about 70% by weight.

  The carboxylate compound (A) or the reactive polycarboxylic acid compound (B) in the active energy ray-curable resin composition of the present invention can be appropriately used depending on the application. For example, in the case of a so-called solvent development type in which a pattern is formed by a printing method or an unreacted site is washed away by a solvent or the like without developing even in the same solder resist application, a carboxylate compound (A) is used and alkaline water is used. In the case of developing by using a reactive polycarboxylic acid compound (B). In general, the reactive polycarboxylic acid compound (B) is often used for this application from the viewpoint that the alkaline water development type can easily form a fine pattern. Of course, there is no problem even if (A) and (B) are used in combination.

  The active energy ray-curable resin composition of the present invention is easily cured 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. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  The color pigment that can be used in the present invention is used to make the active energy ray resin composition of the present invention a coloring material. Since the balance between the carboxylate compound (A) used in the present invention and the hydroxyl group of the reactive polycarboxylic acid compound (B) is in a specific range, particularly excellent affinity to the pigment, that is, dispersibility is exhibited. It is guessed.

  Although this mechanism is not clear, since the dispersion proceeds well, the pigment concentration can be increased as a result, and in a composition that requires development, the dispersion is in a more favorable state. Good patterning characteristics are exhibited, and there are few development residues in the development and dissolution area, which is preferable.

  Examples of the color pigment include organic pigments such as phthalocyanine, azo, and quinacridone, carbon black, and inorganic pigments such as titanium oxide. Of these, carbon black is most preferred because of its high dispersibility.

  In the present invention, the molding material refers to a material in which an uncured composition is put into a mold or an object is molded by pressing the mold and then a curing reaction is caused by active energy rays, or a laser is applied to the uncured composition. It refers to a material that is used for applications in which it is irradiated with a focused light such as to cause a curing reaction to be molded.

  Specific applications include a sheet formed into a flat shape, a sealing material for protecting the element, a so-called nanoimprint material that performs fine molding by pressing a "mold" that has been micro-processed into an uncured composition, Furthermore, particularly suitable applications include peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have particularly severe thermal requirements.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. This corresponds to adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, after the film forming material is temporarily applied to the peelable substrate and formed into a film, it is bonded to the original target substrate to form a film, so-called dry film also corresponds to the film forming material. .

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

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

  In the present invention, the resist material composition is formed by forming a film layer of the composition on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, and the physical difference between irradiated and unirradiated parts. This refers to an active energy ray-sensitive composition that is intended to be drawn using. Specifically, the composition is used for the purpose of removing the irradiated part or the unirradiated part by dissolving the irradiated part or the non-irradiated part with, for example, a solvent or an alkaline solution.

  The active energy ray-curable resin composition for resists of the present invention can be applied to various materials that can be patterned, and is particularly useful for solder resist materials, interlayer insulating materials for build-up methods, and optical waveguides. It is also used for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates.

  As a particularly suitable application, taking advantage of the property that a tough cured product can be obtained, making use of a permanent resist application such as a solder resist, and the property of good pigment dispersibility, printing inks, color filters, etc. The use of a color resist, particularly a black matrix resist is preferred.

  In addition, it is particularly suitably used as a dry film application that requires mechanical strength before the curing reaction with active energy rays. That is, since the balance of the hydroxyl group and epoxy group of the epoxy resin (a) used in the present invention is in a specific range, the reactive carboxylate compound of the present invention has a relatively high molecular weight. Excellent developability can be exhibited.

  There are no particular restrictions on the method of forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater 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 and curing the active energy ray-curable resin composition of the present invention with active energy rays.

  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 resin composition up to 70% by weight. Examples of other components include a photopolymerization initiator, other additives, a coloring material, and a volatile solvent added for viscosity adjustment for the purpose of imparting coating suitability. Examples of other components that can be used are shown below.

  Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; ant such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Quinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide A general radical type photoinitiator is mentioned.

  As cationic photopolymerization initiators, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine initiator, borate initiator, And other photoacid generators.

  Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc., manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of the sulfonium salt of Lewis acid include triphenylsulfonium hexafluorophosphonate (such as Cyracure UVI-6990 manufactured by Union Carbide). And triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide). As the phosphonium salt of a Lewis acid, triphenyl phosphonium hexafluoroantimonate, and the like.

  Other halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (such as TrigonalPI manufactured by AKZO), 2.2-dichloro-1--4- (phenoxyphenyl) Examples include ethanone (such as Sandray 1000 manufactured by Sandoz), α, α, α-tribromomethylphenylsulfone (such as BMPS manufactured by Iron Chemical). Examples of the triazine-based initiator include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine (such as Triazine A manufactured by Panchi), 2,4 -Trichloromethyl- (4'-methoxystyryl) -6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl- (pipronyl) -6-triazine (such as TriazinePP manufactured by Panchim), 2,4-trichloro Methyl- (4′-methoxynaphthyl) -6-triazine (such as Triazine B manufactured by Panchim), 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s-triazine ( Sanwa Chemical Co., Ltd.), 2 (2'-furyl) Chiriden) -4,6-bis (manufactured by trichloromethyl) -s-triazine (Sanwa Chemical Co., Ltd.).

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

  In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. Further, both radical and cationic initiators may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

  Other additives include, for example, thermosetting catalysts such as melamine, thixotropy imparting 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 An inhibitor or the like can be used.

  Further, as other pigment materials, for example, those not intended for coloring, so-called extender pigments can be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.

  Other resins that are not reactive with active energy rays (so-called inert polymers), such as 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% by weight.

  In particular, when the reactive polycarboxylic acid compound (B) is to be used for solder resist applications, it is preferable to use a known general epoxy resin as a resin that does not show reactivity to active energy rays. This is because the carboxyl group derived from (B) remains even after being reacted and cured 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 group is further carboxylated to form a stronger cross-linked structure.

  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 50% by weight, more preferably up to 35% by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, a part shows a weight part.

The softening point and epoxy equivalent were measured under the following conditions.
1) Epoxy equivalent: Measured by a method according to JIS K 7236: 2001.
2) Softening point: measured by a method according to JIS K 7234: 1986 3) Acid value: measured by a method according to JIS K 0070: 1992 4) GPC measurement conditions are as follows.
Model: TOSOH HLC-8220GPC
Column: TSKGEL Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml per minute. 40 ° C
Detector: Differential refractometer Molecular weight standard: Polystyrene

Example 1: Preparation of carboxylate compound (A) NC-3000H (manufactured by Nippon Kayaku, softening point 70 ° C., epoxy equivalent 288 g / eq) 288 g, with one or more polymerizable ethylenically unsaturated groups in the molecule As compound (b) having one or more carboxyl groups, acrylic acid (abbreviation AA, Mw = 72) is listed in Table 1, 3 g of triphenylphosphine as catalyst, and 80% solid content of propylene glycol monomethyl ether monoacetate as solvent. And reacted at 100 ° C. for 24 hours to obtain a carboxylate compound solution.
The reaction end point was determined by the solid content acid value (AV), and the measured value was described in the table. The acid value was measured with a reaction solution and converted into an acid value as a solid content.

Comparative Example 1: Preparation of carboxylate compounds for comparison
  200 g of cresol novolac type epoxy resin EOCN-103S (Nippon Kayaku, softening point 80 ° C., epoxy equivalent 200 g / eq), having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule Acrylic acid (abbreviation AA, Mw = 72) as the compound (b) is described in the table, and dimethanolpropionic acid (abbreviation DMPA, Mw) as the compound (c) having one or more hydroxyl groups and one or more carboxyl groups in the molecule. = 134) was added in the amount shown in Table 1.
  3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so as to have a solid content of 80% and reacted at 100 ° C. for 24 hours to obtain a carboxylate compound solution.
  The reaction end point was determined by the solid content acid value (AV), and the measured value was described in the table. The acid value was measured with a reaction solution and converted into an acid value as a solid content.

Table 1: Example 1 and Comparative Example 1: Preparation of epoxycarboxylate compound (A)
Example AA amount (molar ratio) DMPA amount (molar ratio) AV (mgKOH / g)
Example 1 72 (1.0) 0 (0.0) 2.5
Comparative Example 1 36 (0.5) 67 (0.5) 2.5

Example 2: Preparation of reactive polycarboxylic acid compound (B)
  As the polybasic acid anhydride (d), tetrahydrophthalic anhydride (abbreviated as THPA) in Table 2 was added to 299 g of the carboxylate compound solution obtained in Example 1 and Comparative Example 1, and the solid content was 65% by weight as the solvent. Then, propylene glycol monomethyl ether monoacetate was added and heated to 100 ° C. to carry out an acid addition reaction to obtain a reactive polycarboxylic acid compound solution.

Table 2: Example 2 and Comparative Example 2:
Preparation of reactive polycarboxylic acid compound (B)
Example Compound (A) THPA amount Solid content acid value
Example 2-1 Example 1 88 g 101 mg KOH / g
Example 2-2 Example 1 37 g 52 mg KOH / g
Comparative Example 2 Comparative Example 1 88g 102mgKOH / g

Test Example 1: Storage stability of epoxycarboxylate compound
The epoxy carboxylate compound solutions obtained in Example 1 and Comparative Example 1 were stored in a freezing room at 5 ° C. below freezing, and the time taken to produce crystals was compared.

Table 3 Test Example 1: Storage stability of epoxycarboxylate compound
Test Example No. Compound (A) AA amount (molar ratio) DMPA amount (molar ratio) Time
Test Example 1 Example 1 72 (1.0) 0 (0.0) 3 weeks

Example 3 and Comparative Example 3: Preparation of hard coat composition
  20 g of the reactive carboxylate compound (A) synthesized in Example 1 and Comparative Example 1, 4 g of dipentaerythritol hexaacrylate, which is a radical curable monomer (C), and Irgacure 184 as an ultraviolet reactive initiator. 5 g was dissolved by heating.
  Further, this was coated on a polycarbonate plate by a hand applicator so as to have a film thickness of 20 microns at the time of drying, and solvent drying was carried out in an electric oven at 80 ° C. for 30 minutes. After drying, a multilayer material was obtained by irradiating and curing ultraviolet rays with an irradiation dose of 1000 mJ using an ultraviolet vertical exposure apparatus (Oak Seisakusho) equipped with a high-pressure mercury lamp.

Table 4 Example 3 and Comparative Example 3: Evaluation of hard coat composition
Example No. Compound (A) (b) / (c) Pencil hardness
Example 3 Example 1 1.0 / 0.0 3H
Comparative Example 3 Comparative Example 1 0.5 / 0.5 H

Example 4: Preparation of dry film resist composition
  54.44 g of the reactive polycarboxylic acid compound (B) obtained in Example 2 and HX-220 (trade name: Nippon Kayaku Co., Ltd. diacrylate monomer) as the other reactive compound (C) 3 .54g, Irgacure 907 (manufactured by Ciba Specialty Chemicals) as the photopolymerization initiator, 4.72g and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.47g as the curing component, GTR-1800 (Nipponization) 14.83 g (manufactured by Yakuhin), 1.05 g of melamine as a thermosetting catalyst and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent were kneaded with a bead mill and uniformly dispersed to obtain a resist resin composition.
  The obtained composition was uniformly applied to a polyethylene terephthalate film serving as a support film using a wire bar coater # 20, passed through a hot air drying furnace at a temperature of 70 ° C., and a resin layer having a thickness of 20 μm was formed. A polyethylene film serving as a protective film was pasted on the resin layer to obtain a dry film. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C., and a resin layer was attached to the entire surface of the substrate while peeling off the protective film.

  Next, in order to estimate the sensitivity of the mask on which the circuit pattern was drawn and the sensitivity using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW), 500 mJ / cm through Kodak Step Tablet No. 2 ² The ultraviolet rays were irradiated. Then, the film on a dry film was peeled and the peeling state was confirmed. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin on the non-irradiated part of the ultraviolet rays. After washing with water and drying, the printed circuit board was heat-cured for 60 minutes with a hot air dryer at 150 ° C. to obtain a cured film.

Sensitivity evaluation
  Sensitivity was determined by how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher sensitivity is determined in the dark part of the tablet (unit: step).
Developability evaluation
  The developability was evaluated based on the time until the pattern shape portion was completely developed, that is, the so-called break time when developing the exposed portion that passed through the pattern mask (unit: second).
  Curability evaluation
  The evaluation of curability was shown by the pencil hardness of the cured film after heating at 150 ° C.
  The evaluation method was based on JIS K5600-5-4: 1999.

Table 5 Example 4 and Comparative Example 4: Evaluation of dry film resist
Example Compound (B) (b) / (c) Sensitivity Developability Curability
Example 4-1 Example 2-1 1.0 / 0.0 9 50 4H
Example 4-2 Example 2-2 1.0 / 0.0 Development impossible 3H
Comparative Example 4 Comparative Example 2 0.5 / 0.5 9 45 3H

  As is clear from the above results, the resist composition in the present invention has a relatively high hardness.

Example 5: Evaluation of flame retardancy
  9.5 g of the resist composition prepared in Example 4 and 0.5 g of a phosphate ester flame retardant (SP-703H Shikoku Kasei) were mixed and stirred to obtain a curable resin composition. The composition was applied to a polyimide film having a film thickness of 25 microns with a wire bar coater # 20, and passed through a hot air drying furnace at a temperature of 70 ° C. to form a resin layer having a thickness of approximately 15 μm. 500 mJ / cm using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW) ² The ultraviolet rays were irradiated. After irradiation, the printed circuit board was subjected to a heat curing reaction for 60 minutes in a hot air dryer at 150 ° C. to obtain a cured film.
  The obtained cured film was cut out together with the polyimide base film in a strip shape having a length of 20 cm and a width of 2 cm. The cut out film was suspended vertically and lit by a lighter from the lower end to evaluate flame retardancy. (Table 6)
○: Ignite but extinguish before burning. X: It burns out completely.

Table 6 Example 5 and Comparative Example 5: Evaluation of flame retardancy
Example Compound (B) (b) / (c) Flame retardancy
Example 5 Example 4 1.0 / 0.0 ○
Comparative Example 5 Comparative Example 4 0.5 / 0.5 ×

  From the above results, it was clarified that the carboxylate compound of the present invention is excellent in flame retardancy.

Example 6: Evaluation of pigment dispersibility
  20 g of the reactive polycarboxylic acid compound (B) obtained in Example 2 and 5.0 g of DPHA (trade name: Nippon Kayaku Co., Ltd. acrylate monomer) as the other reactive compound (C), organic solvent 10 g of propylene glycol monomethyl ether acetate and 10 g of Mitsubishi Carbon Black MA-100 as a coloring pigment were mixed and stirred. 35 g of glass beads were put therein and dispersed for 1 hour with a paint shaker.
  The dispersion after the dispersion was coated on a polyethylene terephthalate film with a wire bar coater # 2, and dried for 10 minutes with a hot air dryer at 80 ° C.
  The gloss of the coating film surface after drying was measured using a 60 ° reflection gloss meter (Horiba IG-331 gloss meter) to evaluate the dispersibility of carbon black. At this time, a higher gloss indicates better pigment dispersibility. (Table 7)

  Table 7 Example 6 and Comparative Example 6: Evaluation of pigment dispersibility
Example Compound (B) (b) / (c) Gloss
Example 6-1 Example 2-1 1.0 / 0.0 35
Example 6-2 Example 2-2 1.0 / 0.0 31
Comparative Example 6 Comparative Example 2 0.5 / 0.5 23

  As apparent from the above results, the epoxy resin (a), which is the basic skeleton of the reactive polycarboxylic acid (B) in the present invention, has one or more polymerizable ethylenically unsaturated groups and one or more carboxyls in the molecule. It was revealed that the dispersibility of the pigment is improved by introducing the compound (b) having both groups.

  As an active energy ray curable resin of the present invention, as a material having both curability, flexibility, toughness, and flame retardancy, a hard coat material, a resist material that requires alkali developability, good pigment dispersion For example, active energy ray-curable printing inks, color resists, especially color resists for LCDs, especially black matrix, etc. as materials having both resist dispersibility and developability, etc. It can be used particularly preferably.

Claims (10)

A color pigment obtained by reacting the epoxy resin (a) represented by the general formula (1) with a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule. Reactive epoxycarboxylate compound (A) which is a dispersant of

Wherein R ₁ is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, m is an integer of 1 to 4, and n is a positive number of 1 to 10 on average. Respectively.) A reactive polycarboxylic acid compound (B), which is a color pigment dispersant, obtained by reacting the carboxylate compound (A) according to claim 1 with a polybasic acid anhydride (d). An active energy ray-curable resin composition comprising the carboxylate compound (A) according to claim 1 and / or the reactive polycarboxylic acid compound (B) according to claim 2. 4. The active energy ray-curable resin composition according to claim 3, further comprising a reactive compound (C) other than (A) and (B). Furthermore, a coloring pigment is contained, The active energy ray hardening-type resin composition of Claim 3 or 4 characterized by the above-mentioned. The active energy ray-curable resin composition according to claim 3, which is a molding material. The active energy ray-curable resin composition according to claim 3, which is a film forming material. It is a resist material composition, The active energy ray hardening-type resin composition as described in any one of Claims 3-5. Hardened | cured material of the active energy ray hardening-type resin composition as described in any one of Claims 3-5. An article overcoated with the active energy ray-curable resin composition according to any one of claims 3 to 5.