JP7378550B2 - Reactive polycarboxylic acid compound, active energy ray-curable resin composition using the same, cured product thereof, and uses thereof - Google Patents

Description

The present invention relates to a novel reactive polycarboxylic acid compound (A), an active energy ray-curable resin composition containing the same, and a cured product thereof. In particular, a novel reactive polycarboxylic acid compound suitable as a resist material that can also be used 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 higher precision and higher density in order to make mobile devices smaller and lighter and to improve communication speed.As a result, the requirements for the solder resist that covers the circuits themselves have become more and more sophisticated. There is a need for a film-forming material with even stronger hardening properties, as it is required to have performance that can withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability. ing.

Among these materials, carboxylate compounds obtained by reacting general epoxy resin with acrylic acid and compounds having carboxylic acid and hydroxyl groups are known as materials that have excellent developability despite 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 whose basic skeleton is a phenol aralkyl epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku Co., Ltd.) is generally known as a material that exhibits high toughness after curing. Studies are also being conducted on its use as a device (Patent Document 2).

In addition, an attempt has been made to disperse carbon black or the like in an acid-modified epoxy acrylate having a basic skeleton of a phenol aralkyl type epoxy resin and apply it to a black matrix resist used in liquid crystal display panels and the like (Patent Document 3). Furthermore, efforts have been made to apply other phenol-dicyclopentadiene skeletons to black resists, and it has been found that they have good affinity with color pigments, and the resulting compositions can be used even at high pigment concentrations. It has been found that this can be used as a resist material etc. with good developability (Patent Document 4).

Japanese Patent Application Publication No. 06-324490 Japanese Patent Application Publication No. 09-211860 Japanese Patent Application Publication No. 2004-295094 Japanese Patent Application Publication No. 2009-102501

However, acid-modified epoxy acrylate whose basic skeleton is an epoxy resin having a phenol-dicyclopentadiene skeleton has a good affinity with the resin and disperses coloring pigments such as carbon black, but has poor developability and requires a high pigment content. It is necessary to have developability at a certain density.
SUMMARY OF THE INVENTION The present invention aims to improve the problems of the prior art described above, and provides an acid-modified epoxy acrylate compound that has excellent dispersibility of color pigments and has good development characteristics even at high pigment concentrations, and an active energy containing the acid-modified epoxy acrylate compound. The purpose of the present invention is to provide a line-curable resin composition.

In order to solve the above problem, the present inventors conducted intensive studies and found that an epoxy resin having a phenol-dicyclopentadiene structure and a carboxylic acid containing an unsaturated group, and a hydroxyl group and a carboxyl group in one molecule as necessary. The inventors have discovered that a resin composition using a reactant with a specific polybasic acid anhydride as a reactant with a compound can solve the above-mentioned problems, and have arrived at the present invention.

That is, the present invention
[1] Add a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule to the epoxy resin (a) represented by the following formula (1), if necessary, in one molecule. A reactive epoxy carboxylate compound (d) obtained by reacting a compound (c) having both a hydroxyl group and a carboxyl 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, R may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and each a represents 1 to 3. n is an average value of 1 to 20. (Indicates an integer.)

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

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention not only provides a tough cured product, but also has excellent resin physical properties even in a state where the solvent is simply dried. ing. In addition, the cured product obtained by curing the active energy ray-curable resin composition of the present invention with active energy rays such as ultraviolet rays has excellent heat resistance and can be finely developed with alkali, so it can be used as a molding material or a coating. Suitable for forming materials and resist materials.
In addition, due to its high affinity with color pigments, the reactive polycarboxylic acid-modified compound of the present invention and the active energy ray-curable resin composition containing the same exhibit good developability even at high pigment concentrations. Suitable for resists, resist materials for color filters, especially black matrix materials, etc.

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 is resistant to high temperature, high humidity, and cold shock. Due to its high reliability, it is suitable for applications that require particularly high reliability, such as solder resists for printed wiring boards, interlayer insulation materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides. is also used.

The present invention will be explained in detail below.
The reactive polycarboxylic acid compound (A) of the present invention has an epoxy resin (a) having a structure represented by the following formula (1), and a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule. A reactive epoxy carboxylate compound (d) is obtained by reacting the carboxylic acid compound (b) with a compound (c) having both a hydroxyl group and a carboxyl group in one molecule, if necessary. Then, it can be obtained by reacting a polybasic acid anhydride (e) represented by the following formula (2) or formula (3).

(In the formula, R may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and each a represents 1 to 3. n is an average value of 1 to 20. (Indicates an integer.)

(In formula (2), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m represents an integer of 1 to 3.)
The hydrocarbon group having 1 to 4 carbon atoms in the formula (1) refers to saturated and unsaturated hydrocarbon groups such as methyl group, ethyl group, ethylene group, propyl group, propylene group, butyl group, and butylene group. .

First, a carboxylation step for imparting reactivity to a carboxylate compound to obtain a reactive epoxycarboxylate compound (d) will be described.

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

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

Examples of the carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or saturated or unsaturated Examples include a reaction product of a saturated dibasic acid and an unsaturated group-containing monoglycidyl compound. In the above, (meth)acrylic acids include (meth)acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, and Half esters are equimolar reaction products with (meth)acrylate derivatives having one hydroxyl group in the molecule, and equimolar reaction products of saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives. Monocarboxylic acid compounds containing one carboxy 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. Examples include polycarboxylic acid compounds having a plurality of carboxyl groups in one molecule, such as half esters which are equimolar reaction products of a dibasic acid and a glycidyl (meth)acrylate derivative having a plurality of epoxy groups.

Among these, in consideration of the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), the carboxylic acid compound (b) is preferably a monocarboxylic acid; Even when used in combination, it is preferable that the value expressed by the molar amount of monocarboxylic acid/molar amount of polycarboxylic acid is 15 or more.
Most preferred are (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid in terms of sensitivity when used as an active energy ray-curable resin composition.
As a compound having both one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, it is preferable that the compound does not have a hydroxyl group.

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 with the purpose of introducing a hydroxyl group into a carboxylate compound. It is something. These include compounds that have both one hydroxyl group and one carboxyl group in one molecule, compounds that have two or more hydroxyl groups and one carboxyl group in one molecule, and compounds that have one or more hydroxyl groups and two carboxy groups in one molecule. There are compounds that have both of the above carboxy groups.

Examples of compounds having one hydroxyl group and one carboxyl group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, and hydroxystearic acid. Compounds having two or more hydroxyl groups and one carboxyl group in one molecule include dimethylol acetic acid, dimethylol propionic acid, dimethylol butanoic 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.
Among these, those containing two or more hydroxyl groups in one molecule are preferred in view of the effects of the present invention. Furthermore, in consideration of the stability of the carboxylation reaction, it is preferable that one carboxy group is present in each molecule. Most preferably, one having two hydroxyl groups and one carboxyl group in one molecule is preferable. Considering the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable.
As a compound having both one or more hydroxyl group and one or more carboxyl group in one molecule, it is preferable that the compound does not have a polymerizable ethylenically unsaturated group.

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

On the other hand, by reducing the amounts of carboxylic acid compound (b) and compound (c) and leaving unreacted residual epoxy groups, the reactivity due to the introduced unsaturated bonds and the reaction due to the remaining epoxy groups, such as photocations, can be reduced. It is also possible to use a combination of catalytic polymerization reactions and thermal polymerization reactions. However, in this case, care should be taken in the storage of the reactive epoxycarboxylate compound (d) and in considering the manufacturing conditions.

When producing a reactive epoxy carboxylate compound (d) in which no epoxy group remains, the total amount of the carboxylic acid compound (b) and compound (c) is 90 to 120 equivalent % based on 1 equivalent of the epoxy resin (a). It is preferable. Within this range, production can be performed under relatively stable conditions. If the amount of carboxylic acid compound charged is larger than this, it is not preferable because excess carboxylic acid compound (b) and compound (c) will remain.

In addition, when the epoxy group is left to remain, it is preferable that the total amount of the carboxylic acid compound (b) and the compound (c) is 20 to 90 equivalent % based on 1 equivalent of the epoxy resin (a). If it deviates from this range, the effect of composite curing will be diminished. Of course, in this case, sufficient attention must be paid to gelation during the reaction and stability over time of the reactive epoxycarboxylate compound (d).

The carboxylation reaction can be carried out without a solvent or after diluting 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 adjusted appropriately depending on the viscosity of the resulting resin and the intended use, but it is preferably used so that the solid content is 90 to 30% by mass, more preferably 80 to 50% by mass. 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 petroleum ether and white mixtures thereof. Examples include gasoline, solvent naphtha, ester solvents, ether solvents, ketone solvents, and the like.

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, 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 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. Examples include ethers and cyclic ethers such as tetrahydrofuran.

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

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

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 catalyst used, that is, the epoxy resin (a), the carboxylic acid compound (b), the compound (c), and optionally the solvent. The amount is 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of reactants including other substances. The reaction temperature at that time is 60 to 150°C, and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, and octane. Examples include commonly known basic catalysts such as acid zirconium.

Moreover, a thermal polymerization inhibitor can also be used. As the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene, etc. are preferably used.

The carboxylation reaction is carried out with appropriate sampling, and the end point is when the acid value of the sample becomes 5 mgKOH/g or less, preferably 3 mgKOH/g or less.

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

If the molecular weight is smaller than the above, the cured product will not exhibit sufficient toughness, and if the molecular weight is too large, the viscosity will become high, making coating difficult.

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

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

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

The reaction of adding the polybasic acid anhydride (e) can be carried out by adding the polybasic acid anhydride (e) to the carboxylation reaction solution. The amount added should be changed as appropriate depending on the application.

For example, when the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkaline aqueous solution developable resist material, the amount of the polybasic acid anhydride (e) to be added is, for example, ) The solid content acid value (according to JIS K5601-2-1:1999) of the reactive polycarboxylic acid compound (A) finally obtained is preferably 20 to 120 mg·KOH/g, more preferably 30 to It is preferable to prepare a calculated value of 110 mg·KOH/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 developability in aqueous alkali solution. That is, 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 determined based on the amount of reaction obtained from the reactants, that is, the epoxy compound (a), the carboxylic acid compound (b), and the compound (c). The amount is 0.1 to 10 parts by mass based on the total amount of the reactants including the polybasic epoxy carboxylate compound (d), the polybasic acid anhydride (e), 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 catalysts that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, and octane. Examples include acid zirconium.

This acid addition reaction can be carried out without a solvent or after being 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, if the product is produced using a solvent in the carboxylation reaction, which is the previous step, it may be directly subjected to the acid addition reaction, which is the next step, without removing the solvent, provided that it is inert in both reactions. can. The solvents that can be used may be the same as those that can be used in the carboxylation reaction.

The preferred amount of the solvent to be used should be adjusted appropriately depending on the viscosity of the resulting resin and the intended use, but it is preferably used so that the solid content is 90 to 30% by mass, more preferably 80 to 50% by mass. It will be done.

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

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

This acid addition reaction is terminated when the acid value of the reactant reaches a range of plus or minus 10% of the set acid value, with appropriate sampling.

The preferable molecular weight range of the reactive polycarboxylic acid compound (A) obtained in this way is that the weight average molecular weight in terms of polystyrene measured by GPC is in the range of 500 to 50,000, more preferably 1,000 to 30,000. , particularly preferably from 1,000 to 10,000.

If the molecular weight is smaller than the above, the cured product will not exhibit sufficient toughness, and if the molecular weight is too large, the viscosity will become high, making coating difficult.

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

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

Polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, and ethylene 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, Hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of ε-caprolactone adduct of hydroxybivalic acid neopene glycol, poly of the reaction product of dipentaerythritol and ε-caprolactone (meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate, and its ethylene oxide adduct, pentaerythritol tri(meth)acrylate, and its ethylene Examples include oxide adducts, pentaerythritol tetra(meth)acrylate, and its ethylene oxide adducts, dipentaerythritol hexa(meth)acrylate, and its ethylene oxide adducts.

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, ethylene glycol divinyl ether, and the like. Styrenes include styrene, methylstyrene, ethylstyrene, and the like. Other vinyl compounds include triallylisocyanurate, trimetaallylisocyanurate, and the like.

Furthermore, so-called reactive oligomers include urethane acrylate, which has a functional group sensitive to active energy rays and a urethane bond in the same molecule; Examples include polyester acrylate, which is derived from other epoxy resins and has functional groups sensitive to active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination.

Further, the cation-reactive monomer is not particularly limited as long as it is a compound that generally has 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 (Union Carbide's "Silacure") UVR-6110, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (Union Carbide Co., Ltd.'s "ELR-4206", etc.), limonene dioxide (Daicel Chemical Industries, Ltd.) "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 (such as Union Carbide's "Cyracure UVR-6128"), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4- Examples include epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl)ether, and bis(3,4-epoxycyclohexyl)diethylsiloxane.

Among these, as the reactive compound (B), radical curable acrylates are most preferable. In the case of a cationic type, since the carboxylic acid and epoxy group react, it is necessary to use a two-liquid mixed type.

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

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 a reactive polycarboxylic acid compound (A) and 3 to 3 parts by mass of other reactive compounds (B). It contains 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 70 parts by weight. Other components include a photopolymerization initiator, other additives, coloring materials, curing accelerators, and volatile solvents added to adjust viscosity for the purpose of imparting coating suitability. Examples of other components that can be used are listed below.

The active energy ray-curable resin composition of the present invention can further contain a photopolymerization initiator. As the photopolymerization initiator, radical type photopolymerization initiators and cationic photopolymerization initiators are preferable.
Examples of radical 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 Acetophenones such as -one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc. Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; 2,4,6-trimethyl Commonly known radical photopolymerization initiators include phosphine oxides such as benzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

In addition, 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 Examples include other photoacid generators.

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

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

Examples of borate photopolymerization initiators include NK-3876 and NK-3881 manufactured by Nippon Kanko Shiki Co., Ltd.; other photoacid generators include 9-phenylacridine, 2,2'-bis(o-chlorophenyl )-4,4',5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Kurogane Kasei Co., Ltd., etc.), 2,2-azobis(2-amino-propane) dihydrochloride (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 (Irgacure 261 manufactured by CibaGeigy, etc.), bis(y5-cyclopentadienyl)bis[2,6 -difluoro-3-(1H-pyry-1-yl)phenyl]titanium (CGI-784 manufactured by CibaGeigy, etc.) and the like.

In addition, an azo initiator such as azobisisobutyronitrile, a heat-sensitive peroxide radical initiator such as benzoyl peroxide, etc. may also be used. Furthermore, both radical and cationic photopolymerization initiators may be used in combination. One type of photopolymerization initiator can be used alone, or two or more types can be used in combination.

Among these, radical type photoinitiators are particularly preferable in consideration of the characteristics 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 colored 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, clay, and the like.

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

In addition, examples of resins that do not show reactivity to active energy rays (so-called inert polymers) include 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. It is preferable to use up to 40 parts by mass of these in the resin composition.

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

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

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

In the present invention, a molding material refers to a material that is molded by putting an uncured composition into a mold or pressing a mold to mold an object, and then causing a curing reaction with active energy rays, or molding the uncured composition into a mold. Refers to a material used for irradiating focused light such as a laser to cause a curing reaction and molding.

Specific applications include flat sheets, encapsulants to protect elements, so-called nanoimprint materials that press microfabricated "molds" onto uncured compositions to form microscopic shapes, Furthermore, suitable applications include peripheral sealing materials 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 surface of a base material. Specific applications include ink materials such as gravure ink, flexographic ink, silk screen ink, and offset ink, coating materials such as hard coat, top coat, overprint varnish, and clear coat, and various adhesives for laminating, optical disks, etc. This includes adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, so-called dry films, in which a film-forming material is temporarily applied to a releasable base material to form a film, and then laminated to the intended base material to form a film, also fall under film-forming materials. .

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

Among these, introduction of a carboxy group into the reactive polycarboxylic acid compound (A) increases adhesion to the substrate, so it is preferable to use it for coating a plastic substrate or a metal substrate.

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

In the present invention, the resist material composition refers to the formation of a film layer of the composition on a base material, which is then partially irradiated with active energy rays such as ultraviolet rays, and the difference in physical properties between the irradiated and non-irradiated areas. Refers to active energy ray-sensitive compositions that are intended to be used for drawing. Specifically, it is a composition used for the purpose of drawing by removing the irradiated area or the unirradiated area by some method, such as dissolving it with a solvent 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, and is particularly useful for solder resist materials and interlayer insulation materials for build-up methods, Furthermore, it is used as an optical waveguide in electrical, electronic, and optical substrates such as printed wiring boards, optoelectronic boards, and optical boards.

Particularly suitable applications are photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, and circuit boards (laminated board applications, multilayer printed wiring boards), taking advantage of their good heat resistance and developability. It can be used in a wide range of applications that require resin compositions, such as solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, and component embedding resins. In particular, since it can exhibit good developability even at high pigment concentrations, it can be suitably used for color resists, resist materials for color filters, and especially black matrix materials.

Furthermore, resin compositions for insulating layers of multilayer printed wiring boards (multilayer printed wiring boards with insulating layers made of cured products of photosensitive resin compositions), resin compositions for interlayer insulating layers (cured products of photosensitive resin compositions), It can also be suitably used for a multilayer printed wiring board (with an interlayer insulating layer), a resin composition for forming plating (a 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 active energy ray-curable resin composition of the present invention is applied onto a substrate with a film thickness of 0.1 to 200 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or a spin coating method. A coating film can be formed by applying and drying the coating film at a temperature of usually 50 to 110°C, preferably 60 to 100°C. Thereafter, the coating film is directly or indirectly irradiated with high-energy rays such as ultraviolet rays at an intensity of usually about 10 to 2000 mJ/cm ² through a photomask on which an exposure pattern has been formed, and then sprayed, for example, using a developer described later. The desired pattern can be obtained by vibrating dipping, paddling, brushing, etc.

Examples of the alkaline aqueous solution used in the above development include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, and potassium phosphate, and tetramethylammonium hydroxide. , tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, and other organic alkali aqueous solutions can be used. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

In addition, it is particularly suitable for use in dry film applications that require mechanical strength before curing reaction with active energy rays. That is, because the balance of hydroxyl groups and epoxy groups in the epoxy resin (a) used in the present invention is within a specific range, even though the reactive polycarboxylic acid compound (A) of the present invention has a relatively high molecular weight. First, good developability can be exhibited.

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

An article overcoated with the active energy ray-curable resin composition of the present invention refers to at least two or more layers obtained by forming and curing the active energy ray-curable resin composition of the present invention on a base material. Indicates a material consisting of layers.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these Examples. Further, in the examples, unless otherwise specified, % indicates mass %.

Softening point, epoxy equivalent, and acid value were measured under the following conditions.
1) Epoxy equivalent: Measured according to JIS K7236:2001.
2) Softening point: Measured according to JISK7234:1986.
3) Acid value: Measured according to JIS K0070:1992.
4) The GPC measurement conditions 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) Acrylic acid (AA) or methacrylic acid (MAA) was added in the amount shown in Table 1 as compound (b), and dimethylolpropionic acid (hereinafter abbreviated as "DMPA") was added in the amount shown in Table 1 as compound (c). 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added to give a solid content of 80%, 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) Add 200 g of the obtained reactive epoxycarboxylate compound (d) solution to the polybasic acid anhydride (e) listed in Table 2. Propylene glycol monomethyl ether monoacetate was added as a compound, amount (g), and solvent so that the solid content was 65%, heated to 100°C, and then subjected to an acid addition reaction to form a reactive polycarboxylic acid compound. (A) A solution was obtained. The solid content acid value (AV: mgKOH/g) of the obtained reactive polycarboxylic acid compound (A) is listed in Table 2. The solid content acid value (mg·KOH/g) was measured as a solution and converted into a value based on solid content.

HTMA: 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, Mitsubishi Gas Chemical Co., Ltd. NTA: Norbornanetricarboxylic anhydride, synthetic product referenced in patent 5532123 THPA: 1,2,3,6-tetrahydro Phthalic anhydride, manufactured by Shin Nippon Chemical Co., Ltd. SA: Rikacid SA Succinic anhydride, manufactured by Shin Nippon Chemical Co., Ltd.

(Example 2, 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) 3.54 g of HX-220 (trade name: diacrylate monomer manufactured by Nippon Kayaku Co., Ltd.), 4.72 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and Kayacure DETX-S (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator. Added 0.47 g of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) as a curing agent component, 1.05 g of melamine as a curing accelerator, and 20.95 g of methyl ethyl ketone as a concentration adjustment solvent. The mixture was 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 with a thickness of 30 μm. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution, and the developability was evaluated based on the time required for complete development, the so-called break time (unit: seconds). Table 3 shows the results.

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

(Example 3 and Comparative Example 3): Evaluation of heat decomposition resistance 8 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, and Irgacure 907 (Ciba Specialty) as a photopolymerization initiator. 0.24 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.01 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.403 g of NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) as a curing agent component, and triphenyl as a curing accelerator. Add 0.017 g of phosphine and 0.446 g of propylene glycol monomethyl ether monoacetate, apply it uniformly to a polyimide film, pass 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 expose to ultraviolet rays. Exposure was performed using a device (manufactured by Oak Seisakusho Co., Ltd., model HMW-680GW) to obtain a cured product. The produced cured product is cut out to a width of 5 mm. Thereafter, it was set in a viscoelasticity measuring device RSA-G2 manufactured by TA instruments, and heated at a frequency of 10 Hz and a heating rate of 2° C./min in an air atmosphere. tan δ was measured, and the temperature at the maximum value of tan δ was defined as Tg. Table 4 shows the results.

From the above results, it can be seen that the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention has excellent heat resistance compared to the comparative resin composition.

(Example 4 and Comparative Example 4): Evaluation regarding pigment dispersibility 20g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and Comparative Example 1, and DPHA (trade name) as other reactive compound (B) 5.0 g of acrylate monomer (manufactured by Nippon Kayaku Co., Ltd.), 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 for 1 hour using a paint shaker. After the dispersion was completed, the dispersion liquid was coated on a polyethylene terephthalate film using a wire bar coater #2, and dried for 10 minutes using a hot air dryer at 80°C. After drying, the gloss of the coating surface was measured using a 60° reflection gloss meter (Horiba IG-331 gloss meter), and the dispersibility of carbon black was evaluated. Table 5 shows the results. The higher the gloss value, the better the pigment dispersibility.

As is clear from the above results, the coating film obtained from the resin composition containing the reactive polycarboxylic acid compound (A) obtained in Example 1 has a higher gloss value and pigment dispersion than that of the comparative example. It can be confirmed that this product has excellent properties. Furthermore, in the resin composition containing the reactive polycarboxylic acid compound (A) of the present invention, there was no change in the gloss value even when the content of the colored pigment was large. On the other hand, it can be seen that in the reactive polycarboxylic acid compound of the comparative example, as the content of the colored pigment increases, the gloss decreases and the content dispersibility is low. Therefore, it can be confirmed that the pigment dispersibility of the reactive polycarboxylic acid compound (A) of the present invention is excellent regardless of the content of the colored pigment.

From the 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 alkali, so it can be used as a molding material or as a coating. 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, and especially black matrix materials.

Claims (9)

In the epoxy resin (a) represented by the following formula (1), only a carboxylic acid compound (b) having both a (meth)acrylic group and a carboxyl group in one molecule, or a (meth)acrylic group and a carboxylic acid compound in one molecule. An active energy ray- reactive epoxy carboxylate compound (d) obtained by reacting only a carboxylic acid compound (b) having both groups with a compound (c) having both a hydroxyl group and a carboxy group in one molecule as necessary, An active energy ray- reactive polycarboxylic acid compound (A) reacted with a polybasic acid anhydride (e) represented by formula (2).

(In the formula, R may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and each a represents 1 to 3. n is an average value of 1 to 20. (Indicates an integer.)

(In formula (2), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m represents an integer of 1 to 3.) An active energy ray -curable resin composition comprising the active energy ray-reactive polycarboxylic acid compound (A) according to claim 1. The active energy ray- curable resin composition according to claim 2, 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, containing 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. 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 the cured product according to claim 8.