JP2011099034A - Polycarboxylic acid resin and polycarboxylic acid resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarboxylic acid resin that forms a cured coating film having excellent adhesion to various kinds of materials and excellent heat resistance and exhibits excellent developability, sensitivity and solvent resistance when mixed with an organic colorant such as pigment or dye. <P>SOLUTION: The polycarboxylic acid resin is obtained by reacting a straight-chain addition polymer (A) obtained by reacting one or more epoxy resins (a) containing two glycidyl groups with one or more dibasic acids (b) represented by formula (1): HOOC-R'-COOH (wherein R' is 2-8C alkylene, hydroxyalkylene, alkenylene, cycloalkylene or cycloalkenylene) having carbon atoms of ≥4 and ≤10 and one or more ethylenically unsaturated monocarboxylic acids (c) with one or more polybasic acid anhydrides (d) and one or more ethylenic unsaturated double bond-containing isocyanates (e). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention provides a color filter for use in an organic EL display capable of color display using a black matrix, a color filter, a photo spacer, a transparent protective film and an organic EL element for manufacturing a liquid crystal display panel, and further, a color filter is produced by inkjet. The present invention relates to a polycarboxylic acid resin that can be used as a thermosetting and / or photosensitive resin material that can be applied.

In recent years, radiation curable resins that can be cured with ultraviolet rays or electron beams have been widely used in the fields of printing, paints, and adhesives from the viewpoint of resource saving and energy saving.
In the field of electronic devices such as printed wiring boards, solder resist is used for protecting circuit boards after mounting components for a long period of time. Acid pendant type novolak epoxy acrylate is generally used as a material for printed wiring boards by the photoresist method, but the adhesion to copper plating is not sufficient, and when used for multilayer printed wiring boards, it is a conductor. In addition to the problem that sufficient adhesion strength between the circuits cannot be obtained, there is also a problem that it is easy to break due to poor flexibility.
In order to solve these problems, a method of mixing an inorganic filler into a photosensitive resin composition using a (meth) acrylic copolymer has been proposed (for example, Patent Document 1), but an acid pendant type novolak epoxy is proposed. The subject that heat resistance was inferior to acrylate remained.

Color filters are used in color liquid crystal display devices and solid-state image sensors, and these are colored colors in which three colors of red (R), green (G), and blue (B) are formed in a predetermined pattern on a substrate. It consists of a coating film and a black black matrix between these three color filters of RGB. Usually, a black matrix is formed on a transparent substrate such as glass, and then R, G, and B patterns are sequentially formed.
In general, color filters include production methods such as a dyeing method, a printing method, a pigment dispersion method, and an electrodeposition method. Among these, in particular, a photocurable resin composition mainly composed of an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a pigment and a solvent is used, applied onto a transparent substrate, and exposed, developed, and postcured. The pigment dispersion method created by the repeated photolithographic method is currently mainstream because it has excellent durability such as light resistance and heat resistance and has few defects such as pinholes.

While the pigment dispersion method has the above-mentioned advantages, the pattern of black matrix, R, G, and B is repeatedly formed, so that high heat resistance is required for the alkali-soluble resin that becomes the binder of the coating film.
Conventionally, as a method for improving heat resistance, a resin composition (for example, Patent Document 2) containing a (meth) acrylic acid ester having a cyclic structure in the side chain as a copolymerization component, or a monomer containing maleimide is used. A resin composition (for example, Patent Document 3), which is a copolymerization component, has been proposed.
However, in the former resin composition with (meth) acrylic acid ester having a cyclic structure in the side chain as a copolymerization component, the side chain is thermally decomposed during post-curing and becomes a volatile component, which contaminates the production line. There was a problem to do. In addition, the resin composition having the latter maleimide-containing monomer as a copolymerization component has a yellow to yellow-brown color caused by nitrogen atoms contained in the molecule, and the transparency of the coating film is improved. make worse. Furthermore, there has been a problem that coloring proceeds during post-curing after heat treatment.

In addition, a polycarboxylic acid resin that can be easily dried at the time of preheating drying, shows an improvement in tack-free property, and is excellent in developability with an alkaline aqueous solution, a polycarboxylic acid resin composition containing the polycarboxylic acid resin, and a cured product thereof Is disclosed (for example, Patent Document 4).
However, even when this resin is used, the sensitivity may not be sufficient. With the recent advancement of technology, development of a photosensitive resin capable of forming a pattern with higher accuracy has been demanded.

JP 2006-190848 A JP 2004-240396 A JP 2003-29018 A JP 2004-67814 A

  The present invention has been made to solve the above-described problems, and forms a cured coating film excellent in adhesion to various materials and heat resistance, and is mixed with organic colorants such as pigments and dyes. It is an object of the present invention to provide a polycarboxylic acid resin having excellent developability, sensitivity, and solvent resistance.

  The present invention includes at least one epoxy resin (a) having two glycidyl groups and at least one dibasic acid (b) represented by the following general formula (1) having 4 to 10 carbon atoms. A linear addition polymer (A) obtained by reacting one or more ethylenically unsaturated monocarboxylic acids (c) with one or more polybasic acid anhydrides (d) and ethylenically unsaturated doubles. A polycarboxylic acid resin (hereinafter sometimes referred to as polycarboxylic acid resin (I)) obtained by further reacting with one or more isocyanate (e) having a bond.

  The polycarboxylic acid resin is preferably represented by the following general formula (2).

  The present invention also relates to a radically polymerizable compound (f) having one glycidyl group in the carboxylic acid group produced by the reaction between the linear addition polymer (A) and the polybasic acid anhydride (d). ) Is further obtained by further reaction (hereinafter, may be referred to as polycarboxylic acid resin (II)).

  The epoxy resin (a) having two glycidyl groups is preferably an epoxy resin represented by the following general formula (7).

  The ethylenically unsaturated monocarboxylic acid (c) is preferably acrylic acid, methacrylic acid or a mixture thereof.

  Moreover, this invention contains the said polycarboxylic acid resin and a photopolymerizable monomer (g), It is a polycarboxylic acid resin composition characterized by the above-mentioned.

  The polycarboxylic acid resin composition may further contain at least one of a solvent (h), a photopolymerization initiator (i), and a dye (j).

  According to the present invention, a cured coating film having excellent adhesion and heat resistance to various materials is formed, and when an organic colorant such as a pigment or a dye is mixed, the developing property, sensitivity, and solvent resistance are excellent. Carboxylic acid resins can be provided.

Hereinafter, the polycarboxylic acid resin of the present invention will be described in detail.
The polycarboxylic acid resin (I) of the present invention includes at least one epoxy resin (a) having two glycidyl groups and a dibasic represented by the following general formula (1) having 4 to 10 carbon atoms. A linear addition polymer (A) obtained by reacting at least one acid (b) with at least one ethylenically unsaturated monocarboxylic acid (c) is converted into one polybasic acid anhydride (d). These are obtained by further reacting with one or more isocyanate (e) having an ethylenically unsaturated double bond.

  The polycarboxylic acid resin (II) of the present invention is obtained by further reacting the carboxylic acid group of the polycarboxylic acid resin (I) with a radical polymerizable compound (f) having one glycidyl group. is there.

  The epoxy resin (a) having two glycidyl groups used in the present invention can be used without particular limitation as long as it has two glycidyl groups in one molecule. Specific examples of the epoxy resin (a) having two glycidyl groups include glycidyl ether type, bisphenol type epoxy resin such as bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, and bisphenol fluorene. What can be obtained by reacting bisphenols with epichlorohydrin and / or methyl epichlorohydrin, or those obtained by reacting glycidyl ether of bisphenol A with a condensate of the above phenols with epichlorohydrin and / or methyl epichlorohydrin, biphenol and epichlorohydrin And / or obtained by reacting with methyl epichlorohydrin (for example, Epicoat YX-4000 manufactured by Japan Epoxy Edin); dihydroxynaphth What is obtained by reacting Len with epichlorohydrin and / or methyl epichlorohydrin (for example, EPICLON HP-4032 manufactured by Dainippon Ink and Chemicals); What is obtained by reacting alkyldiphenol with epichlorohydrin and / or methyl epichlorohydrin ( For example, EPICLON EXA-7120 manufactured by Dainippon Ink & Chemicals, Inc., glycidyl ester dimer acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, glycidyl amine diglycidyl aniline, diglycidyl toluidine, etc. Cyclic type alicyclic diepoxy acetals, alicyclic diepoxy adipates, alicyclic diepoxycarboxylates, the above epoxy resins and diisocyanates are reacted Having an oxazolidone ring obtained Te (e.g., Asahi Kasei Epoxy Ltd. Araldite AER4152) and others as mentioned, is not limited thereto. Moreover, you may use these epoxy resins (a) which have these two glycidyl groups 1 type or in mixture of 2 or more types. Among them, particularly preferred as the epoxy resin (a) is one having a structure represented by the following general formula (7). This epoxy resin is excellent in heat resistance and chemical resistance, and has two glycidyl groups in the molecule, and therefore has a feature that the molecular weight increases linearly without gelation in the reaction.

  The dibasic acid (b) used by this invention should just be represented by the said General formula (1) whose carbon number is 4-10. By adopting such a carbon number and a saturated or unsaturated chain or cyclic structure, the glycidyl group of the epoxy resin (a) having two glycidyl groups and the carboxyl group of the dibasic acid (b) The proportion of the hydroxyl group produced by the reaction in the repeating unit of the linear addition polymer (A) having a high molecular weight is increased, and rapid alkali solubility can be exhibited.

  Therefore, when the number of carbon atoms of the dibasic acid (b) is 11 or more, a polycarboxylic acid resin that dissolves in a sufficient alkali targeted by the present invention cannot be obtained. On the other hand, when the number of carbon atoms is 10 or less, the proportion of the hydroxyl groups in the linear addition polymer (A) is preferably an amount sufficient to dissolve in an alkali, more preferably 8 or less, and most preferably. Is 6 or less. Examples of the dibasic acid (b) include succinic acid, fumaric acid, maleic acid, glutaric acid, itaconic acid, adipic acid, tetrahydrophthalic acid, hexahydrophthalic acid, ethylene glycol / 2-mole maleic anhydride adduct, etc. Can be mentioned. In particular, itaconic acid is preferably used because it has an ethylenically unsaturated bond in the structure, so that the curability of the polycarboxylic acid resin of the present invention is improved and a good cured product is obtained.

  In addition, the dibasic acid (b) to be reacted with the epoxy resin (a) having two glycidyl groups may be a carboxylic acid having a hydroxyl group, which is more directly than the reaction between the glycidyl group and the carboxyl group. This is useful for the purpose of increasing the hydroxyl groups of the chain addition polymer (A) and improving the developability and adhesion to the substrate of the polycarboxylic acid resin of the present invention. Examples of the carboxylic acid having a hydroxyl group include malic acid, tartaric acid, mucinic acid, and the like. The above-mentioned dibasic acid (b) may be used alone or in combination of two or more.

  The ethylenically unsaturated monocarboxylic acid (c) used in the present invention introduces an ethylenically unsaturated group as a photosensitive group into the terminal of the polycarboxylic acid resin of the present invention, and the linear addition polymer (A). It plays a role in controlling the molecular weight. Examples of the ethylenically unsaturated monocarboxylic acid (c) include (meth) acrylic acid, crotonic acid, cinnamic acid and the like. In addition, as the component (c), a polyfunctional (meth) acrylate having one hydroxyl group and one or more (meth) acryloyl groups (for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl ( (Meth) acrylate, trimethylolpropane di (meth) acrylate and the like) and a polybasic acid anhydride can also be used. The ethylenically unsaturated monocarboxylic acid (c) described above may be used alone or in combination of two or more. Among these, it is preferable to use (meth) acrylic acid from the viewpoint of reactivity and cost.

  The ratio of the dibasic acid (b) to the ethylenically unsaturated monocarboxylic acid (c) in the production of the linear addition polymer (A) is 1:20 to 5: 1 as the former: the latter in a molar ratio. The range is preferably 1, and more preferably in the range of 1: 5 to 1: 1. If the proportion of the ethylenically unsaturated monocarboxylic acid (c) is too small, the molecular weight will increase too much, and the polycarboxylic acid resin of the present invention may not be suitable as a photosensitive resin material. If the ratio of the acid (c) is too large, the effect of increasing the molecular weight may not be obtained.

  Furthermore, the ratio of the epoxy resin (a) having two glycidyl groups, the dibasic acid (b) and the ethylenically unsaturated monocarboxylic acid (c) in the case of producing the linear addition polymer (A) is The sum of the carboxyl group equivalents of the dibasic acid (b) and the ethylenically unsaturated monocarboxylic acid (c) is 0.9 with respect to 1 equivalent of the epoxy group of the epoxy resin (a) having two glycidyl groups. It is preferable that it is -1.1 equivalent, and it is still more preferable that it is 0.95-1.05 equivalent. If the carboxyl group equivalent is less than 0.9, gelation is likely to occur during the reaction with the polybasic acid anhydride (d), and if it exceeds 1.1, the amount of unreacted acid will increase and the stability after compounding the resist will be reduced. It tends to be.

  Examples of the polybasic acid anhydride (d) used in the present invention include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. , Endomethylenetetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and the like. These may be used alone or in combination of two or more. May be used. The addition amount of the polybasic acid anhydride (d) is preferably 5 to 80 mol% when the sum of the dibasic acid (b) and the ethylenically unsaturated monocarboxylic acid (c) is 100 mol%, More preferably, it is 10-60 mol%, Most preferably, it is 15-40 mol%. If the addition amount of the polybasic acid anhydride (d) is less than 5 mol%, the addition amount of the radical polymerizable compound (f) having one glycidyl group is unfavorable. Moreover, when the addition amount of polybasic acid anhydride (d) exceeds 80 mol%, the addition amount of isocyanate (e) having an ethylenically unsaturated double bond decreases, and the effect on the adhesion and sensitivity to the base material is reduced. Thinning is not preferable.

  The isocyanate (e) having an ethylenically unsaturated double bond used in the present invention is not particularly limited. For example, it has a structure represented by the following general formula (8), and specifically, And (meth) acryloyloxyalkyl isocyanate. As (meth) acryloyloxyalkyl isocyanate, a (meth) acryloyloxy group is bonded to an isocyanate group (—NCO) via an alkylene group having 1 to 6 carbon atoms, specifically, 2-acryloyloxyethyl. Examples include isocyanate and 2-methacryloyloxyethyl isocyanate.

  The addition amount of the isocyanate (e) having an ethylenically unsaturated double bond is preferably 5 to 5 when the sum of the dibasic acid (b) and the ethylenically unsaturated monocarboxylic acid (c) is 100 mol%. It is 80 mol%, More preferably, it is 10-60 mol%, Most preferably, it is 15-40 mol%. If the addition amount of isocyanate (e) is less than 5 mol%, the adhesion to the substrate is lowered, and the crosslinking density is lowered, so that the solvent resistance is lowered, which is not preferable. On the other hand, when the addition amount of isocyanate (e) exceeds 80 mol%, the amount of secondary hydroxyl group decreases, and the developability, particularly the development form tends to deteriorate, such being undesirable.

  Furthermore, the ratio of the total of the polybasic acid anhydride (d) and the isocyanate (e) having an ethylenically unsaturated double bond is the ratio between the dibasic acid (b) and the ethylenically unsaturated monocarboxylic acid (c). When the sum is 100 mol%, it is preferably 98 mol% or less. If it exceeds 98 mol%, the amount of unreacted monomer increases, which causes undesired outgassing during post-baking. In addition, as a method of adding the linear addition polymer (A), (d), and (e), the component (e) is added after the addition of (d), and the component (e) is added (d). The component (e) may be added, and the component (e) and the component (d) may be added simultaneously. However, since the component (e) reacts with a hydroxyl group and a carboxylic acid, the component (e) is added after the component (e) is added. It is easier to adjust the acid value when adding.

  The radically polymerizable compound (f) having one glycidyl group used in the present invention is not particularly limited. For example, 3,4-epoxycyclohexylmethyl (meta) having glycidyl (meth) acrylate and alicyclic epoxy is used. ) Acrylates and lactone adducts thereof [eg, Cyclomer A200, M100 manufactured by Daicel Chemical Industries, Ltd.], mono (meth) acrylic acid ester of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate , Epoxidized product of dicyclopentenyl (meth) acrylate, epoxidized product of dicyclopentenyloxyethyl (meth) acrylate, etc., but glycidyl (meth) acrylate and 3,4-epoxycyclohexyl are available because of easy availability of raw materials. Methyl (meth) acryl Over doors are preferably used. These radically polymerizable compounds (f) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The addition amount of the radically polymerizable compound (f) having one glycidyl group is preferably in the range where the acid value of the polycarboxylic acid resin (II) is 5 to 120 KOHmg / g.

  The acid value of the polycarboxylic acid resins (I) and (II) is preferably in the range of 5 to 120 KOHmg / g, more preferably in the range of 15 to 70 KOHmg / g. If the acid value is less than 5 KOH mg / g, the alkali development rate is slow, and if it exceeds 120 KOH mg / g, pattern shape after alkali development tends to occur, which is not preferable.

The molecular weight of the polycarboxylic acid resins (I) and (II) is in the range of 1,000 to 40,000, preferably in the range of 3,000 to 20,000, in terms of polystyrene weight average molecular weight. If the weight average molecular weight is less than 1,000, pattern-shaped chipping after alkali development tends to occur, and if the molecular weight exceeds 40,000, the alkali development time becomes long.
In addition, the value of the weight average molecular weight (Mw) of polycarboxylic acid resin (I) and (II) in this invention is measured on the following conditions using gel permeation chromatography (GPC), and is converted into polystyrene. Is calculated.
Column: Shodex KF-802 + KF-802
Column temperature: 40 ° C
Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Shodex RI-101)
Flow rate: 1 mL / min

  The polycarboxylic acid resin (I) and / or the polycarboxylic acid resin (II) obtained as described above are added to the photopolymerizable monomer (g), and if necessary, the solvent (h), a photopolymerization initiator (i ), Dye (j), and the like are added to obtain a polycarboxylic acid resin composition.

The photopolymerizable monomer (g) that can be used is not particularly limited as long as it can react with the polycarboxylic acid resin (I) and / or the polycarboxylic acid resin (II). Specific examples of the photopolymerizable monomer (g) include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, diallylbenzenephosphonate; Polycarboxylic acid monomers such as vinyl and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meta ) Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane di ( (Meth) acrylic such as tri (meth) acrylate of tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate Monomer; triallyl cyanurate and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
The addition amount of the photopolymerizable monomer (g) is usually 10 to 200 parts by mass, preferably 20 to 150 parts per 100 parts by mass of the polycarboxylic acid resin (I) and / or the polycarboxylic acid resin (II). Part by mass. By setting it as the said range, photocurability can be maintained in an appropriate range, and also a viscosity can be adjusted. Moreover, depending on the kind of photopolymerizable monomer (g) to be used, a solvent (h) may be further added in order to adjust the viscosity of the photosensitive resin composition.

The solvent (h) that can be used is not limited as long as it is an inert solvent that does not react with the polycarboxylic acid resin (I) and / or the polycarboxylic acid resin (II) and the photopolymerizable monomer (g). it can.
Specific examples of the solvent (h) include, for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Examples include tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, it is preferable to use propylene glycol monomethyl ether acetate preferably used in the radical polymerization reaction.
The amount of the solvent (h) added is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass with respect to 100 parts by mass of the polycarboxylic acid resin (I) and / or the polycarboxylic acid resin (II). is there. By setting it as the said range, a viscosity can be kept moderate.

  When the polycarboxylic acid resin composition of the present invention is photocured using active light such as ultraviolet rays as active energy rays, a photopolymerization initiator (i) can be added. Usable photopolymerization initiators include, for example, benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4 Acetophenones such as-(1-t-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; 2,4-dimethyl Thioxanthones such as thioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, 4- (1-t Benzophenones such as butyldioxy-1-methylethyl) benzophenone and 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; acylphosphine oxides and xanthones. These may be used individually by 1 type and may be used in combination of 2 or more type. The addition amount of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 100 parts by mass of the solid content in the polycarboxylic acid resin composition of the present invention. Is 1 to 10 parts by mass. By setting the addition amount of the photopolymerization initiator to 0.1 to 30 parts by mass, the photocurability can be maintained in an appropriate range.

Although it does not specifically limit as dye (j), The acidic dye which has acidic groups, such as carboxylic acid, from the solubility with an organic solvent or an alkali developing solution, interaction with the other component in a curable composition, heat resistance, etc. Further, salts of acidic dyes with nitrogen compounds, sulfonamides of acidic dyes, and the like are used.
Specific examples of the dye that can be used include, for example, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 13 , 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17 19; acid yellow 1,3,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116; food yellow3 And derivatives thereof.
Among them, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These organic dyes are used alone or in combination of two or more according to the color of the target pixel.

  A known colorant such as a pigment, a dispersant, an antifoaming agent, a coupling agent, a leveling agent, and the like can be added to the polycarboxylic acid resin composition of the present invention as necessary.

  Specific examples of pigments that can be used include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as CI Pigment Green 7 and 36; I. C.I. Brown pigments such as CI Pigment Brown 23 and 25; I. And black pigments such as CI pigment blacks 1 and 7, carbon black, titanium black, and iron oxide. These pigment machine pigments are used singly or in combination of two or more according to the color of the target pixel.

  In order to improve the dispersibility of the pigment, a known dispersant may be added. As the dispersant, a polymer dispersant is preferably used because of excellent dispersion stability with time. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified ester. And the like, and the like. Specific examples of such a dispersant are trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), and SOLPERSE (manufactured by GENECA). Etc.

  The polycarboxylic acid resin composition of the present invention is applied, for example, on a printed wiring board by a screen printing method, a roll coater method, a curtain coater method, a spray coater method, a spin coat method, and the like, after photocuring a necessary portion. The development is performed by washing away the uncured (unexposed) portion with an alkaline aqueous solution.

  As an aqueous alkali solution used for development, an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or the like, or an amine type, an aminophenol type compound is also useful, but a p-phenylenediamine type compound is preferably used. Representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N- Examples include ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and aqueous solutions of these sulfates, hydrochlorides or p-toluenesulfonates. It is done.

  Furthermore, thermosetting is possible by adding a known epoxy resin and a curing accelerator to the polycarboxylic acid resin composition of the present invention, and it can also be applied to thermosetting ink jet methods.

  As a light source used for curing the coated surface by light irradiation, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metahalide lamp, or the like is used.

  The polycarboxylic acid resin of the present invention and the composition containing the same are, for example, a solder resist for manufacturing a printed wiring board, an electroless plating resist, an insulating layer of a build-up printed wiring board or a wide range of printing plates, for liquid crystal display materials It can be used as a photosensitive material for plasma displays and organic EL displays, has high exposure sensitivity, and good developability with an alkaline aqueous solution. The cured product after development is a photosensitive material capable of forming a cured coating film excellent in electrical characteristics, mechanical characteristics, heat resistance, chemical resistance, and the like.

(Synthesis Example 1)
In a reactor equipped with a stirrer, thermometer, air-sealed tube and reflux condenser in a four-necked flask, bisphenol A type epoxy resin [Araldite AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., epoxy equivalent 189] 189 parts by mass, adipine While charging 40.2 parts by mass of acid, 31.0 parts by mass of acrylic acid, 206.5 parts by mass of propylene glycol monomethyl ether acetate, 0.8 parts by mass of triphenylphosphine and 0.2 parts by mass of methyl hydroquinone, The mixture was heated to 120 ° C. and reacted for about 20 hours to obtain a reaction product having an acid value of 0.5 KOH mg / g.
Next, 93.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI, manufactured by Showa Denko KK) was charged into the flask and reacted at 80 ° C. for 3 hours until the absorption peak of isocyanate disappeared by infrared absorption analysis. Next, 30.4 parts by mass of tetrahydrophthalic anhydride was added, and the mixture was further reacted at 100 ° C. for 6 hours until the absorption peak of acid anhydride disappeared by infrared absorption analysis, and 368.7 parts by mass of propylene glycol monomethyl ether acetate was added. A polycarboxylic acid resin having a weight-average molecular weight of 8,000 in terms of polystyrene having a solid content acid value of 31.0 KOH mg / g and a solid content concentration of 40% was obtained.

(Synthesis Example 2)
In a reactor having the same configuration as in Synthesis Example 1, 189 parts by mass of bisphenol A type epoxy resin [Araldite AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., epoxy equivalent 189], 7.3 parts by mass of adipic acid, and 63.4 parts by mass of acrylic acid , 206.3 parts by weight of propylene glycol monomethyl ether acetate, 0.8 part by weight of triphenylphosphine and 0.2 part by weight of methylhydroquinone were charged, heated to 120 ° C. while blowing air, and reacted for about 20 hours. A reaction product of 0.5 KOH mg / g was obtained.
Next, 93.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI, manufactured by Showa Denko KK) was charged into the flask and reacted at 80 ° C. for 3 hours until the absorption peak of isocyanate disappeared by infrared absorption analysis. Next, 30.4 parts by mass of tetrahydrophthalic anhydride was charged, and further reacted at 100 ° C. for 6 hours until the absorption peak of acid anhydride disappeared by infrared absorption analysis, and 368.3 parts by mass of propylene glycol monomethyl ether acetate was charged. A polycarboxylic acid resin having a weight-average molecular weight of 3,000 in terms of polystyrene having a solid content acid value of 31.1 KOH mg / g and a solid content concentration of 40% was obtained.

(Synthesis Example 3)
In the reactor having the same configuration as in Synthesis Example 1, 189 parts by mass of bisphenol A type epoxy resin [Araldite AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., epoxy equivalent 189], 51.1 parts by mass of adipic acid, and 20.2 parts by mass of acrylic acid , 181.2 parts by mass of propylene glycol monomethyl ether acetate, 0.8 part by mass of triphenylphosphine and 0.2 part by mass of methyl hydroquinone were charged, heated to 120 ° C. while blowing air, and reacted for about 20 hours. A reaction product of 0.5 KOH mg / g was obtained.
Next, 15.5 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI, manufactured by Showa Denko KK) was charged into the flask, and reacted at 80 ° C. for 3 hours until there was no isocyanate absorption peak by infrared absorption analysis. Next, 60.8 parts by mass of tetrahydrophthalic anhydride was charged, and further reacted at 100 ° C. for 6 hours until the absorption peak of acid anhydride disappeared by infrared absorption analysis, and 323.5 parts by mass of propylene glycol monomethyl ether acetate was charged, A polycarboxylic acid resin having a weight-average molecular weight of 15,000 in terms of polystyrene having a solid content acid value of 69.1 KOH mg / g and a solid content concentration of 40% was obtained.

(Synthesis Example 4)
In a reactor having the same configuration as in Synthesis Example 1, 189 parts by mass of bisphenol A type epoxy resin [Araldite AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., epoxy equivalent 189], 40.2 parts by mass of adipic acid, and 31.0 parts by mass of acrylic acid , 194.4 parts by mass of propylene glycol monomethyl ether acetate, 0.8 part by mass of triphenylphosphine and 0.2 part by mass of methylhydroquinone were charged, heated to 120 ° C. while blowing air, and allowed to react for about 20 hours. A reaction product of 0.5 KOH mg / g was obtained.
Next, 70.5 parts by mass of 2-acryloyloxyethyl isocyanate (AOI, manufactured by Showa Denko KK) was charged into the flask and reacted at 80 ° C. for 3 hours until the absorption peak of isocyanate disappeared by infrared absorption analysis. Next, 60.8 parts by mass of tetrahydrophthalic anhydride was added, and further reacted at 100 ° C. for 6 hours until the absorption peak of acid anhydride disappeared by infrared absorption analysis, and 347.2 parts by mass of propylene glycol monomethyl ether acetate was prepared. A polycarboxylic acid resin having a solid content acid value of 33.0 KOH mg / g and a solid content concentration of 40% in terms of polystyrene and having a weight average molecular weight of 7,000 was obtained.

(Synthesis Example 5)
In a reactor having the same configuration as in Synthesis Example 1, 189 parts by mass of bisphenol A type epoxy resin [Araldite AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., epoxy equivalent 189], 40.2 parts by mass of adipic acid, and 31.0 parts by mass of acrylic acid , 197.8 parts by mass of propylene glycol monomethyl ether acetate, 0.8 part by mass of triphenylphosphine and 0.2 part by mass of methylhydroquinone were charged, heated to 120 ° C. while blowing air, and reacted for about 20 hours. A reaction product of 0.5 KOH mg / g was obtained.
Next, 46.5 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI, manufactured by Showa Denko KK) was charged into the flask, and reacted at 80 ° C. for 3 hours until the absorption peak of isocyanate disappeared by infrared absorption analysis. Next, 60.8 parts by mass of tetrahydrophthalic anhydride was charged, and the mixture was further reacted at 100 ° C. for 6 hours until the absorption peak of acid anhydride disappeared by infrared absorption analysis. Next, 28.4 parts by mass of glycidyl methacrylate was charged, reacted at 120 ° C. for 10 hours, charged with 395.9 parts by mass of propylene glycol monomethyl ether acetate, converted to polystyrene with a solid content acid value of 31.5 KOHmg / g and a solid content concentration of 40%. A polycarboxylic acid resin having a weight average molecular weight of 9,000 was obtained.

(Synthesis Example 6)
In a reactor having the same configuration as in Synthesis Example 1, 170 parts by mass of bisphenol F type epoxy resin [Epototo YD-128, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 170], 35.8 parts by mass of itaconic acid, 31.0 parts of acrylic acid Parts by weight, propylene glycol monomethyl ether acetate 168.4 parts by weight, triphenylphosphine 0.8 parts by weight and methylhydroquinone 0.2 parts by weight, heated to 120 ° C. while blowing air, and allowed to react for about 20 hours, A reaction product having an acid value of 0.5 KOH mg / g was obtained.
Next, 15.5 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI, manufactured by Showa Denko KK) was charged into the flask, and reacted at 80 ° C. for 3 hours until there was no isocyanate absorption peak by infrared absorption analysis. Next, 50.0 parts by mass of succinic anhydride was added, and the mixture was further reacted at 100 ° C. for 6 hours until the absorption peak of acid anhydride disappeared by infrared absorption analysis. Next, 42.6 parts by mass of glycidyl methacrylate was charged, reacted at 120 ° C. for 10 hours, 354.6 parts by mass of propylene glycol monomethyl ether acetate was added, and the polystyrene conversion with a solid content acid value of 37.0 KOHmg / g and a solid content concentration of 40% A polycarboxylic acid resin having a weight average molecular weight of 10,000 was obtained.

(Synthesis Example 7)
In a reactor having the same configuration as in Synthesis Example 1, bisphenol F type epoxy resin [Epototo YD-128, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 170] 170 parts by mass, itaconic acid 45.5 parts by mass, acrylic acid 20.2 Parts by weight, 166.8 parts by weight of propylene glycol monomethyl ether acetate, 0.8 parts by weight of triphenylphosphine and 0.2 parts by weight of methylhydroquinone, heated to 120 ° C. while blowing air, and allowed to react for about 20 hours, A reaction product having an acid value of 0.5 KOH mg / g was obtained.
Next, 14.1 parts by mass of 2-acryloyloxyethyl isocyanate (AOI, Showa Denko KK) was charged into the flask and reacted at 80 ° C. for 3 hours until the absorption peak of isocyanate disappeared by infrared absorption analysis. Next, 60.0 parts by mass of succinic anhydride was charged, and the mixture was further reacted at 100 ° C. for 6 hours until the absorption peak of acid anhydride disappeared by infrared absorption analysis. Next, 8.5 parts by weight of glycidyl methacrylate was charged and reacted at 120 ° C. for 10 hours, 310.2 parts by weight of propylene glycol monomethyl ether acetate was added, and converted to polystyrene with a solid content acid value of 98.5 KOHmg / g and a solid content concentration of 40%. A polycarboxylic acid resin having a weight average molecular weight of 16,000 was obtained.

(Comparative Synthesis Example 1)
Bisphenol A type epoxy resin (Araldite AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., epoxy equivalent 189), 189 parts by mass, acrylic acid 70.6 parts by mass, propylene glycol monomethyl ether acetate 164. 3 parts by mass, 0.8 parts by mass of triphenylphosphine and 0.2 parts by mass of methylhydroquinone were charged, heated to 120 ° C. while blowing air, reacted for about 20 hours, and a reaction product having an acid value of 0.5 KOHmg / g Got.
Next, 45.6 parts by mass of tetrahydrophthalic anhydride was placed in the flask and reacted at 100 ° C. for another 6 hours until the absorption peak of acid anhydride disappeared by infrared absorption analysis, and 293.4 mass of propylene glycol monomethyl ether acetate. The resin with a weight-average molecular weight of 1,000 in terms of polystyrene having a solid content acid value of 55.2 KOH mg / g and a solid content concentration of 40% was obtained.

(Comparative Synthesis Example 2)
In a reactor having the same configuration as in Synthesis Example 1, o-cresol type epoxy resin [Epototo YDCN-704L, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 214] 214 parts by mass, acrylic acid 70.6 parts by mass, propylene glycol monomethyl ether 194.2 parts by mass of acetate, 0.8 part by mass of triphenylphosphine and 0.2 part by mass of methylhydroquinone were charged, heated to 120 ° C. while blowing air, reacted for about 20 hours, and an acid value of 0.5 KOH mg / g. The reaction product was obtained.
Next, 76.0 parts by mass of tetrahydrophthalic anhydride was placed in the flask and reacted at 100 ° C. for another 6 hours until the absorption peak of the acid anhydride disappeared by infrared absorption analysis, and 346.6 parts by mass of propylene glycol monomethyl ether acetate. A resin with a weight-average molecular weight of 8,000 in terms of polystyrene having a solid content acid value of 77.8 KOH mg / g and a solid content concentration of 40% was obtained.

(Comparative Synthesis Example 3)
In the reaction apparatus having the same configuration as in Synthesis Example 1, 189 parts by mass of bisphenol A type epoxy resin [Araldite AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., epoxy equivalent 189], 32.5 parts by mass of itaconic acid, 34.6 parts by mass of acrylic acid , 162.4 parts by mass of propylene glycol monomethyl ether acetate, 0.8 part by mass of triphenylphosphine and 0.2 part by mass of methylhydroquinone were charged, heated to 120 ° C. while blowing air, and allowed to react for about 20 hours. A reaction product of 0.5 KOH mg / g was obtained.
Next, 45.6 parts by mass of tetrahydrophthalic anhydride was placed in the flask and reacted at 100 ° C. for another 6 hours until the absorption peak of acid anhydride disappeared by infrared absorption analysis. 290.1 mass of propylene glycol monomethyl ether acetate The resin with a weight average molecular weight of 4,000 in terms of polystyrene having a solid content acid value of 55.8 KOH mg / g and a solid content concentration of 40% was obtained.

(Comparative Synthesis Example 4)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 229.2 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 120 ° C. Next, 10 parts by mass of t-butylperoxy-2-ethylhexanoate was added to 100 parts by mass of the monomer mixture to a monomer mixture consisting of 147.8 parts by mass of benzyl methacrylate and 56.8 parts by mass of methacrylic acid. This was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 120 ° C. for 2 hours to obtain a copolymer. Next, the inside of the flask was replaced with air substitution, and 21.3 parts by mass of glycidyl methacrylate, 0.54 parts by mass of triphenylphosphine, 0.11 parts by mass of methylhydroquinone and 25.5 parts by mass of propylene glycol monomethyl ether acetate were combined. The mixture was put into a combined solution and the reaction was continued at 120 ° C. to obtain a resin having a solid content acid value of 93.5 KOH mg / g and a solid content concentration of 40% in terms of polystyrene and a weight average molecular weight of 10,000.

[Examples 1-14 and Comparative Examples 1-8]
Each component shown below was mix | blended using resin obtained from the synthesis examples 1-7 and the comparative synthesis examples 1-4, and each photocurable resin composition was obtained. As examples using pigments, compositions using Synthesis Examples 1, 2, 3, 4, 5, 6, 7 and Comparative Synthesis Examples 1, 2, 3, 4 were used in Examples 1, 2, 3 respectively. 4, 5, 6, 7 and Comparative Examples 1, 2, 3, and 4. Further, as examples using dyes, compositions using Synthesis Examples 1, 2, 3, 4, 5, 6, 7 and Comparative Synthesis Examples 1, 2, 3, 4 and Examples 8, 9, 10 respectively. 11, 12, 13, 14 and Comparative Examples 5, 6, 7, and 8.

<Preparation of transparent resist resin cured coating>
A resin composition prepared by adding 30 parts by mass of pentaerythritol tetraacrylate and 4 parts by mass of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator to 100 parts by mass of the solid content of each resin solution was obtained with an applicator. It is applied to a glass substrate with a thickness of 10 μm when wet, and low-boiling substances are volatilized in a hot air dryer at 100 ° C. Then, using an ultra-high pressure mercury lamp manufactured by Oak Manufacturing Co., Ltd., 50 mJ through a mask as necessary. After being exposed at / cm ² to obtain a cured coating film having a thickness of 2 μm, alkali development was performed.

(1) Evaluation of heat resistance Each cured coating film was cut out and subjected to thermogravimetric analysis (TGA). The cut sample was heated to 220 ° C., and the weight change rate when held for 2 hours was measured.
○: Less than −2.0% ×: −2.0% or more

(2) Evaluation of heat-resistant discoloration The coating film formed on the glass substrate was left in a dryer at 230 ° C. for 1 hour, and the coloring of the coating film before and after the heat treatment was compared with a color difference meter.
○: ΔE * ab is less than 0.3 ×: ΔE * ab is 0.3 or more

(3) Evaluation of transparency The coating film formed on the glass substrate is left in a dryer at 230 ° C. for 1 hour, and the light transmittance at 400 nm of the coating film before and after the heat treatment is measured with a spectrophotometer. did.
○: Change rate of transmittance is less than 1% ×: Change rate of transmittance is 1% or more

(4) Evaluation of adhesion The cross-cut test was performed on the cured coating film according to JIS K5400, and the peeled state of 100 cross-cuts was visually observed and evaluated according to the following criteria.
○: No separation was observed.
Δ: Peeling is observed in less than 10% of the whole.
X: Exfoliation is recognized in 10% or more of the whole.

<Preparation of color resist (pigment type)>
(Preparation of green pigment dispersion)
In a SUS container filled with 180 parts by mass of zirconia beads having a diameter of 0.5 mm, C.I. 10.00 parts by mass of I Pigment Green 36, 33.75 parts by mass of solvent (PGMAc), and 6.25 parts by mass of a dispersant (Bicchemy Japan Co., Ltd. Disperbyk-161) are added and dispersed for 3 hours with a paint shaker. Thus, a green pigment dispersion was obtained.

Using the green pigment dispersion obtained above, a color resist (pigment type) was prepared at a blending ratio shown in Table 1 below.

<Preparation of color resist (dye type)>
A color resist (dye type) was prepared using the dye “Acid Green 3” at a blending ratio shown in Table 2 below.

<Preparation of color resist cured coating>
A color resist was spin-coated on a 5 cm square glass substrate (non-alkali glass) so as to have a film thickness of 2.2 μm when dried, prebaked at 80 ° C. for 3 minutes, and a photomask was placed at a distance of 100 μm from the coating film. The exposure was performed at 150 mJ / cm ² . Next, spray development was performed with a 0.1 wt% aqueous sodium carbonate solution at a water pressure of 0.3 MPa, and then post-baking was performed at 230 ° C. for 30 minutes to obtain a cured color resist coating film.

(5) Evaluation of alkali developability The cured coating film exposed through a mask was spray-developed at 23 ° C. with a 0.1% aqueous sodium carbonate solution, and the time when the pattern was completely visible and the presence or absence of a residue after development. Was visually evaluated.
○: No visual residue ×: Visual residue

(6) Development mode In the development process of the negative resist, the unexposed portion of the resist layer that has not been cured is dissolved by the alkaline developer and is released from the substrate. There are a peeling type in which the part is peeled off mainly as a large lump, and a dissolving type in which the dye is gradually dissolved and diffused so as to dissolve in water. The former peeling type is a development mode that is not preferred because the solid-liquid mass remains in the system as a foreign substance and easily contaminates the pixels of other colors, and the latter dissolution type is a development type that the latter is desired. .
×: Peeling type ○: Dissolving type

(7) Evaluation of sensitivity The cured coating film exposed through the mask was subjected to spray development for 30 seconds using a 0.1% aqueous sodium carbonate solution at 23 ° C., and the amount of film loss before and after alkali development was measured. The smaller the film loss, the better the sensitivity.
○: Less than 0.20 μm ×: 0.20 μm or more

(8) Evaluation of solvent resistance A cured coating film was prepared in the same manner as the evaluation of (7) sensitivity, except that in the preparation of a color resist cured coating film, front exposure was performed without using a photomask. Next, 200 ml of n-methyl 2-pyrrolidone was placed in a 500 ml glass bottle capable of being covered, and the cured coating film was immersed therein, and the color change after 23 ° C.-60 minutes was compared with a color difference meter.
○: ΔE * ab is less than 0.3 ×: ΔE * ab is 0.3 or more In addition, transparent resists (1) to (4), color resists using pigments (5) to (8), dyes The used color resist was evaluated for items (2) to (8).

Claims (7)

At least one epoxy resin (a) having two glycidyl groups, at least one dibasic acid (b) represented by the following general formula (1) having 4 to 10 carbon atoms, A linear addition polymer (A) obtained by reacting one or more saturated monocarboxylic acids (c) with one or more polybasic acid anhydrides (d) and an isocyanate having an ethylenically unsaturated double bond (E) A polycarboxylic acid resin obtained by further reacting with one or more kinds.

The polycarboxylic acid resin according to claim 1, wherein the polycarboxylic acid resin is represented by the following general formula (2).

  The carboxylic acid group produced by the reaction of the linear addition polymer (A) and the polybasic acid anhydride (d) is further reacted with a radical polymerizable compound (f) having one glycidyl group. The polycarboxylic acid resin according to claim 1, wherein the polycarboxylic acid resin is obtained. The polycarboxylic acid according to any one of claims 1 to 3, wherein the epoxy resin (a) having two glycidyl groups is an epoxy resin represented by the following general formula (7). resin.

  The polycarboxylic acid resin according to any one of claims 1 to 4, wherein the ethylenically unsaturated monocarboxylic acid (c) is acrylic acid, methacrylic acid or a mixture thereof.   A polycarboxylic acid resin composition comprising the polycarboxylic acid resin according to any one of claims 1 to 5 and a photopolymerizable monomer (g).   The polycarboxylic acid resin composition according to claim 6, further comprising at least one of a solvent (h), a photopolymerization initiator (i), and a dye (j).