TWI554827B - Coloring the fake composition - Google Patents

Description

Coloring photosensitive composition

The present invention relates to a coloring photosensitive composition suitable for forming a color image of a color filter used in a liquid crystal display element or a solid-state image sensor.

The color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel is manufactured using a coloring photosensitive composition. It is known that such a coloring photosensitive composition contains a coloring agent, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the coloring agent is a composition of CI Pigment Green 36 and CI Pigment Yellow 150 (Patent Document 1) .

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2005-157311

The green filter formed by using the coloring photosensitive composition described above does not necessarily sufficiently satisfy the color separation ability with the red color filter.

The present invention provides the following [1] to [8].

[1] A coloring photosensitive composition containing a coloring agent, a polymerizable compound, a polymerization initiator, and a solvent, and the coloring agent contains a copper halide titanium phthalocyanine pigment, a zinc halide phthalocyanine pigment, and a quinacone pigment coloring agent .

[2] The coloring photosensitive composition of the above [1], which is 20 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass of the content of the zinc halide titanium phthalocyanine pigment.

[3] The coloring photosensitive composition of the above [1], which is 50 parts by mass or more and 200 parts by mass or less, based on 100 parts by mass of the content of the quinone quinone pigment.

[4] The content of the copper oxytetraphthalocyanine pigment is 20 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the zinc halide titanium phthalocyanine pigment, and the content of the quinacridone pigment is relative to the zinc halide titanium phthalocyanine pigment. The coloring photosensitive composition of the above [1] is 50 parts by mass or more and 200 parts by mass or less.

[5] The color-sensitive photosensitive composition according to any one of the above [1] to [4], wherein the copper oxytetraphthalocyanine pigment is a C.I.

[6] The quinone ketone pigment is a colored photosensitive resin composition according to any one of the above [1] to [3].

[7] The colored photosensitive composition according to any one of the above [1] to [6], which contains a coloring agent, a polymerizable compound, a polymerization initiator, a solvent, and a resin.

[8] A color filter light sheet formed by the colored photosensitive composition according to any one of the above [1] to [7].

According to the colored photosensitive composition of the present invention, a green filter excellent in color separation ability with a red filter can be obtained.

[Best Mode for Carrying Out the Invention]

The coloring photosensitive composition of the present invention contains a coloring agent (A), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), and the coloring agent contains a copper oxyhalide pigment and a zinc halide A pigmented photosensitive composition of a phthalocyanine pigment and a quinacridone pigment. The colored photosensitive composition of the present invention is preferably a resin (B).

Further, the compounds exemplified as the respective components in the present specification may be used singly or in combination, without particular limitation.

The coloring agent (A) used in the coloring photosensitive composition of the present invention contains a copper halide titanium phthalocyanine pigment, a zinc halide titanium phthalocyanine pigment, and a quinophthalone pigment.

As the copper oxyhalide pigment, the copper chloride phthalocyanine pigment is preferred, and the C.I. pigment green 7 is more preferred. When the copper halide phthalocyanine pigment is the above pigment, the transmittance in the vicinity of 600 nm can be lowered, and the color separation ability with the red filter is excellent.

As the zinc halide titanium cyanine pigment, C.I. Pigment Green 58 is preferred.

The content of the copper oxyhalide pigment is preferably 20 parts by mass or more and 150 parts by mass or less, more preferably 80 parts by mass or more and 120 parts by mass or less, per 100 parts by mass of the content of the zinc halide titanium cyanine pigment. When the content of the copper oxyhalide pigment is in the above range, the high transmittance at 520 nm can be maintained, the transmittance in the vicinity of 600 nm can be lowered, the color separation ability with the red filter can be excellent, and the high-resolution green filter can be obtained. sheet. When such a green filter is used as a filter for a green pixel provided in a display device such as a liquid crystal display device, the color reproducibility of the display device can be improved.

The colorant (A) further contains a quinophthalone pigment. The content of the quinacridone pigment is preferably 50 parts by mass or more and 200 parts by mass or less, more preferably 120 parts by mass or more and 200 parts by mass or less, per 100 parts by mass of the content of the zinc halide titanium cyanine pigment. The quinacridone pigment is preferably C.I. Pigment Yellow 138. By containing the above-described quinophthalone pigment, the color separation ability with the blue filter tends to be excellent.

The pigment may be subjected to a rosin treatment, a surface treatment such as a pigment derivative or a pigment dispersant introduced with an acidic group or a basic group, a graft treatment of a pigment surface with a polymer compound or the like, a sulfuric acid micronization method, or the like. The micronization treatment, the removal treatment of an organic solvent or water to remove impurities, the removal treatment of an ionic impurity by an ion exchange method, or the like. Further, the pigment is preferably uniform in particle diameter. By dispersing the pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

As the pigment dispersant, a commercially available surfactant can be used. Examples of the surfactant include an anthrone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, propylene-based, and urethane-based interface. Active agent. In addition to the above-mentioned surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amines Examples of the polyurethanes, polyethyleneimines, and the like include, for example, the trade name KP (Shin-Etsu Chemical Co., Ltd.), Fu Ruolin (manufactured by Kyoei Chemical Co., Ltd.), and SOLSPERS (Zeneca). )), EFKA (manufactured by CIBA Co., Ltd.), AJISPER (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (manufactured by BYK Japan Co., Ltd.), and the like. These may be used alone or in combination of two or more.

When a pigment dispersant is used, the amount thereof to be used is preferably 100% by mass or less, and more preferably 5 to 50% by mass based on the total mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 5 to 45% by mass, based on the solid content of the coloring photosensitive composition. In the foregoing range, the desired spectral or color density can be obtained. Here, the solid fraction refers to the total amount of solvent removed by the colored photosensitive composition.

The colored photosensitive composition of the present invention is preferably a resin (B).

The resin (B) used in the coloring photosensitive composition of the present invention is preferably a resin having alkali solubility. Here, the alkali solubility means the property of the developing solution dissolved in the aqueous solution of the alkali compound.

The resin having an alkali solubility is, for example, a resin (B-1): at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (a) (hereinafter also referred to as "(a)" a copolymer (B-2) polymerized with a compound (b) having a carbon number of 2 to 4 (hereinafter referred to as "(b)"): (a) and (b) Copolymerized monomer (c) (however, a cyclic ether having no carbon number of 2 to 4) (hereinafter also referred to as "(c)"), a copolymer obtained by polymerizing (a) and (b), or a resin (B-3): a copolymer obtained by polymerizing (a) and (c), a resin (B-4): a copolymer obtained by polymerizing (a) and (c), and a resin resin obtained by reacting (b) (B-5): a copolymer obtained by polymerizing (b) and (c) and a resin obtained by the reaction of (a).

(a) specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid; maleic acid, rich Horse acid, citraconic acid, methyl fumarate, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1, An unsaturated dicarboxylic acid such as 2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1, 4-cyclohexene dicarboxylic acid; methyl-5-norbornene- 2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene a carboxyl group-containing bicyclic unsaturated compound of 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid Formic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrogen Phthalic anhydride, 5,6-dicarboxyl Ring [2.2.1] an unsaturated dicarboxylic anhydride such as hept-2-ene anhydrate (nadic anhydride); succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid Unsaturated mono[(meth)acryloxyalkyl]ester of a polyvalent carboxylic acid of 2 or more units such as mono[2-(methyl)acryloxyethyl)]; α-(hydroxymethyl) An acrylic acrylate-like unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used from the viewpoint of copolymerization reactivity or alkali solubility.

Here, in the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The descriptions of "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

(b) polymerization of a cyclic ether having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (dioxolane ring)) Sex compounds. (b) a monomer having a cyclic ether having 2 to 4 carbon atoms and an ethylenically unsaturated bond, preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group Better.

(b), for example, a monomer having an epoxy group (b1) (hereinafter also referred to as "(b1)") or a monomer having an oxetanyl group (b2) (hereinafter also referred to as "(b2)" "), and a monomer having a tetrahydrofuranyl group (b3) (hereinafter also referred to as "(b3)").

The monomer having an epoxyethyl group (b1) means a polymerizable compound having an epoxy group. (b1), for example, a monomer (b1-1) (hereinafter also referred to as "(b1-1)") having a structure in which a chain olefin is epoxidized and an ethylenically unsaturated bond, and a cycloolefin An epoxidized structure and an ethylenically unsaturated bonded monomer (b1-2) (hereinafter also referred to as "(b1-2)").

(b1) It is preferred to have a monomer having an epoxy group and an ethylenically unsaturated bond, and a monomer having an epoxy group and a (meth)acryloxy group, preferably having a (meth) propylene group. The oxy group (b1-2) is even better.

(b1-1) specifically, for example, epoxypropyl (meth) acrylate, β-methyl propyl propyl (meth) acrylate, β-ethyl propyl propyl (meth) acrylate , propylene propyl vinyl ether, o-vinyl benzyl epoxy propyl ether, m-vinyl benzyl epoxy propyl ether, p-vinyl benzyl epoxy propyl ether, α-methyl- O-vinylbenzyl epoxypropyl ether, α-methyl-m-vinylbenzyl epoxypropyl ether, α-methyl-p-vinylbenzyl epoxypropyl ether, 2,3- Bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6 -bis(glycidoxymethyl)styrene, 2,3,4-cis (glycidoxymethyl)styrene, 2,3,5-glycol (glycidoxymethyl)benzene Ethylene, 2,3,6-glycol (glycidoxymethyl)styrene, 3,4,5-glycol (glycidoxymethyl)styrene, 2,4,6-parade (epoxy A compound described in the publication of Japanese Patent Publication No. Hei 7-248625.

(b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4- Epoxycyclohexyl methacrylate (for example, CYCLMERA 400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, CYCLMERM100; manufactured by Daicel Chemical Industry Co., Ltd.), I) the compound represented by the formula, the compound represented by the formula (II), and the like.

【化1】

In the formulae (I) and (II), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ¹ and X ² are each independently a single ^{bond, -R 3 -, * - R} 3 -O -, * - R 3 -S -, * - R 3 -NH-.

R ³ is an alkanediyl group having 1 to 6 carbon atoms.

* is the key with O. ]

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

The hydroxyalkyl group may, for example, be a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group or a 1-hydroxy-1-methyl group. Base, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ¹ and R ^{2 are} preferably, for example, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

The alkanediyl group may, for example, be a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group or a pentane-1,5. - Diyl, hexane-1,6-diyl and the like.

X ¹ and X ^{2 are} preferably, for example, a single bond, a methylene group, an ethylene group, a *-CH ₂ -O- (* is a bond bond with O) group, and a *-CH ₂ CH ₂ -O- group. More preferably, it is a single bond, *-CH ₂ CH ₂ -O- group.

The compound represented by the formula (I) may, for example, be a compound represented by the formula (I-1) to the formula (I-15). Preferably, for example, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), the formula (I-11) to the formula (I) -15). More preferably, it is a formula (I-1), Formula (I-7), Formula (I-9), Formula (I-15).

[Chemical 2]

The compound represented by the formula (II) may, for example, be a compound represented by the formula (II-1) to the formula (II-15). Preferably, for example, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), the formula (II-11) to the formula (II) -15).

More preferably, it is a formula (II-1), Formula (II-7), Formula (II-9), Formula (II-15).

[化3]

The compound represented by the formula (I) and the compound represented by the formula (II) can be used singly. Also, they can be mixed at any ratio. In the case of mixing, the mixing ratio is in molar ratio, preferably Formula (I): Formula (II) is 5:95 to 95:5, more preferably 10:90 to 90:10, and particularly preferably 20: 80 to 80:20.

The oxetanyl group-containing monomer (b2) means a polymerizable compound having an oxetanyl group. (b2) It is preferred to have a monomer having an oxetanyl group and an ethylenically unsaturated bond, and more preferably a monomer having an oxetanyl group and a (meth)acryloxy group. In the aspect of (b2), for example, 3-methyl-3-(methyl)propenyloxymethyloxetane, 3-ethyl-3-(methyl)propenyloxymethyloxalate Cyclobutane, 3-methyl-3-(methyl)propenyloxyethyloxetane, and 3-ethyl-3-(methyl)propenyloxyethyloxetane .

The monomer (b3) having a tetrahydrofuran group means a polymerizable compound having a tetrahydrofuran group. (b3) A monomer having a tetrahydrofuranyl group and an ethylenically unsaturated double bond is preferred, and a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferred.

(b3) Specific examples thereof include tetrahydrofurfuryl acrylate (for example, Bisko V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(C), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- Alkyl (meth)acrylates such as butyl (meth) acrylate; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] 癸-8-yl (meth) acrylate (a customary name in the technical field to which the invention pertains is dicyclopentanyl (meth) acrylate.), dicyclopentanoxyethyl (methyl) a (meth)acrylic acid cyclic alkyl ester such as acrylate or isobornyl (meth) acrylate; (meth) acrylate, benzyl (meth) acrylate, etc. Aryl or aralkyl acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate; 2-hydroxyethyl (meth) acrylate, Hydroxyalkyl esters such as 2-hydroxypropyl (meth) acrylate; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-B Bicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene , 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1 Hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6 - bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2- Alkene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxy Carbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1] a bicyclic unsaturated compound of hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-ring Hexylmalanimine, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide Butyl ester, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide Dicarbonyl quinone imine derivatives such as esters, N-(9-acridinyl) maleimine; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene , vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, Isoprene and 2,3-dimethyl-1,3-butadiene.

Among these, styrene, N-phenyl maleimine, N-cyclohexylmaleimide, N-benzyl maleimide, bicyclo [2.2.1] hept-2-ene, etc. From the viewpoint of copolymerization reactivity and alkali solubility, it is preferred.

In the resin (B-1), the ratio of the structural unit derived from each monomer to the total number of moles of the structural unit constituting the resin (B-1) is preferably in the following range.

Structural unit from (a); 5 to 60 mol% (preferably 10 to 50 mol%)

Construction unit from (b); 40 to 95 mol% (preferably 50 to 90 mol%)

When the ratio of the structural unit of the resin (B-1) is in the above range, the stability, developability, solvent resistance, heat resistance, and mechanical strength tend to be good.

The resin (B-1) is preferably a resin in which (b) is a resin of (b1) and (b) is a resin of (b1-2).

For the resin (B-1), for example, the method described in the document "Experimental method for polymer synthesis" (Otsuka Ryokan, Ltd., 1st edition, 1st edition, 1st issue, March 1, 1972) and the document Manufactured by reference to the literature.

Specifically, for example, a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are added to a reaction vessel, and oxygen is substituted by oxygen to deoxidize, and the mixture is stirred, heated, and kept warm. Further, the polymerization initiator, solvent and the like used herein are not particularly limited and can be generally used by users in the field. a polymerization initiator such as an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and an organic peroxide (benzene) In the case where the solvent is a solvent, the solvent can be used as the solvent for coloring the photosensitive composition, and a solvent or the like described later can be used.

Further, the obtained copolymer may be used as it is, or may be used as a solid (powder) by using a solution which is concentrated or diluted, or by reprecipitation or the like. In particular, as a solvent in the polymerization, a solution obtained by reacting with the same solvent as the solvent (E) described later can be used as it is, and the production steps can be simplified.

In the resin (B-2), the ratio of the structural unit derived from each monomer to the total number of moles of the total structural unit constituting the resin (B-2) is preferably in the following range.

Construction unit from (a); 2 to 40 mol% (preferably 5 to 35 mol%)

Structural unit from (b); 2 to 95 mol% (preferably 5 to 80 mol%)

Structural unit derived from (c); 1 to 65 mol% (preferably 1 to 60 mol%)

When the ratio of the structural unit of the resin (B-2) is in the above range, the stability, developability, solvent resistance, heat resistance, and mechanical strength tend to be good.

The resin (B-2) is preferably a resin in which (b) is a resin of (b1) and (b) is a resin of (b1-2).

The resin (B-2) can be produced by the same method as the resin (B-1).

In the resin (B-3), the ratio of the structural unit derived from each monomer to the total number of moles of the total structural unit constituting the resin (B-3) is preferably in the following range.

Construction unit from (a); 2 to 40 mol% (preferably 5 to 35 mol%)

Structural unit from (c); 60 to 98 mol% (preferably 65 to 95 mol%)

When the ratio of the structural unit of the resin (B-3) is in the above range, the stability, developability, and solvent resistance tend to be good.

The resin (B-3) can be produced by the same method as the resin (B-1).

The resin (B-4) and the resin (B-5) can be produced, for example, in a two-stage process. In this case, you can refer to the above-mentioned document "Experimental method for polymer synthesis" (the method described in the first issue of the first issue of the Otsuka Ryokan Institute of Chemicals, the first issue of the first brush, March 1, 1972), JP-A-2001-89533 It is produced by the method described in the bulletin.

Resin (B-4) First, in the first stage, a copolymer of (a) and (c) is obtained in the same manner as in the above-described method for producing the resin (B-1).

In this case, as described above, the copolymer obtained can be used as it is, and a concentrated or diluted solution can be used, or a solid (powder) can be taken out by a method such as reprecipitation.

The ratio of the structural units derived from (a) and (c) is preferably in the following range with respect to the total number of moles of the entire structural unit constituting the above-mentioned copolymer.

Construction unit from (a); 5 to 50 mol% (preferably 10 to 45 mol%)

Construction unit from (c); 50 to 95 mol% (preferably 55 to 90 mol%)

Next, in the second stage, a part of the carboxylic acid and the carboxylic anhydride of (a) from the obtained copolymer is reacted with the cyclic ether of (b). The cyclic ether is highly reactive, and the unreacted (b) is less likely to remain, and (b) is preferably (b1) and further preferably (b1-1).

Specifically, the environment inside the flask is replaced by nitrogen instead of air, and 5 to 80 mol% of (b), relative (a), (b) and (c) are relative to the number of moles of (a). A total of 0.001 to 5% by mass of a reaction catalyst of a carboxyl group and a cyclic ether (for example, dimethylaminomethyl phenol), and a total of (a), (b), and (c) A polymerization inhibitor (for example, hydroquinone) of 0.001 to 5% by mass is placed in a flask, and the reaction is carried out at 60 to 130 ° C for 1 to 10 hours to obtain a resin (A-4). Further, similarly to the polymerization conditions, the heat generation amount by the production equipment or the polymerization can be considered, and the feeding method or the reaction temperature can be appropriately adjusted.

Further, the number of moles of (b) at this time is preferably from 10 to 75 mol%, more preferably from 15 to 70 mol%, with respect to the number of moles of (a). The molar ratio of (b) tends to be good in the balance of storage stability, solvent resistance, and heat resistance in this range.

Specific resin (B-4), for example, a copolymer of (meth)acrylic acid/dicyclopentanyl (meth) acrylate and a reaction of a glycidyl (meth) acrylate, (meth)acrylic acid/ Copolymer of benzyl (meth) acrylate copolymer with epoxy propyl (meth) acrylate, copolymer of (meth) acrylate / cyclohexyl (meth) acrylate and epoxy propyl (A Acrylate-reactive resin, copolymer of (meth)acrylic acid/styrene and epoxypropyl (meth)acrylate-reacted resin, (meth)acrylic acid/(meth)acrylic acid methyl group Resin reactive with epoxypropyl (meth) acrylate, copolymer of (meth)acrylic acid/N-cyclohexylmaleimide and epoxypropyl (meth) acrylate reactive resin, (A Copolymer of acrylic acid/dicyclopentanyl (meth) acrylate/benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth)acrylic acid / bicyclo a copolymer of a pentyl (meth) acrylate/cyclohexyl (meth) acrylate copolymer with a glycidyl (meth) acrylate, (meth)acrylic acid / dicyclopentanyl ( Copolymer of acrylate/styrene copolymer with epoxypropyl (meth) acrylate, (meth)acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate a copolymer of a copolymer with a glycidyl (meth) acrylate, a copolymer of (meth)acrylic acid/dicyclopentanyl (meth) acrylate/N-cyclohexylmaleimide and a ring An oxypropyl (meth) acrylate-reacted resin, a copolymer of crotonic acid/dicyclopentanyl (meth) acrylate and a epoxypropyl (meth) acrylate-reacted resin; crotonic acid/benzyl group Copolymer of (meth) acrylate copolymer with epoxypropyl (meth) acrylate, copolymer of crotonic acid / cyclohexyl (meth) acrylate and epoxy propyl (meth) acrylate Resin, crotonic acid/styrene copolymer and epoxypropyl (meth) acrylate reactive resin, crotonic acid / crotonic acid methyl copolymer and epoxy propyl (meth) acrylate reactive resin a resin for reacting a copolymer of crotonic acid/N-cyclohexylmaleimide with a glycidyl (meth) acrylate, crotonic acid/dicyclopentanyl (A) a resin in which an acrylate/benzyl (meth) acrylate copolymer is reacted with a glycidyl (meth) acrylate, crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (methyl Copolymer of acrylate copolymer with epoxypropyl (meth) acrylate, copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene and epoxy propyl (methyl) Acrylate-reacted resin, resin of crotonic acid/dicyclopentanyl (meth) acrylate/crotonate methyl group reacted with epoxypropyl (meth) acrylate, crotonic acid/dicyclopentane Resin copolymerized with a copolymer of a base (meth)acrylate/N-cyclohexylmaleimine and a glycidyl (meth)acrylate; maleic acid/dicyclopentanyl (meth)acrylate Resin copolymerized with epoxy propyl (meth) acrylate, copolymer of maleic acid / benzyl (meth) acrylate and epoxy propyl (meth) acrylate resin, Malay Copolymer of acid/cyclohexyl (meth) acrylate copolymer with epoxy propyl (meth) acrylate, copolymer of maleic acid / styrene and epoxy propyl (methyl) Copolymer of enoate-reactive resin, maleic acid/maleic acid methyl copolymer and epoxypropyl (meth) acrylate-reacted resin, maleic acid/N-cyclohexylmaleimide Resin reactive with glycidyl (meth) acrylate, copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate and epoxy propyl (methyl Acrylate-reactive resin, maleic acid/dicyclopentanyl (meth) acrylate/cyclohexyl (meth) acrylate copolymer and epoxy propyl (meth) acrylate resin, horse Copolymer of acid/dicyclopentanyl (meth) acrylate/styrene copolymer with epoxy propyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate Resin of maleic acid methyl copolymer and epoxypropyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide Resin copolymerized with epoxypropyl (meth) acrylate; copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth) acrylate with epoxypropyl (methyl) Acrylate reaction Resin, (meth)acrylic acid/maleic anhydride/benzyl (meth) acrylate copolymer and epoxypropyl (meth) acrylate reactive resin, (meth)acrylic acid / maleic anhydride / cyclohexyl Copolymer of (meth) acrylate copolymer with epoxy propyl (meth) acrylate, copolymer of (meth) acrylate / maleic anhydride / styrene and epoxy propyl (meth) acrylate Reactive resin, resin of (meth)acrylic acid/maleic anhydride/(meth)acrylic acid methyl group and epoxypropyl (meth)acrylate reactive resin, (meth)acrylic acid/maleic anhydride/N a resin in which a copolymer of cyclohexylmaleimide is reacted with a glycidyl (meth) acrylate, (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth) acrylate/benzyl group (Meth) acrylate copolymer and epoxy propyl (meth) acrylate resin, (meth) acrylate / maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (A (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth) acrylate/styrene copolymerized with acrylate copolymer and epoxypropyl (meth) acrylate a copolymer of a copolymer with a glycidyl (meth) acrylate, a copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth)acrylate/(meth)acrylic acid methyl group and Copolymer of epoxypropyl (meth) acrylate-reacted resin, copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth) acrylate/N-cyclohexylmaleimide and ring An oxypropyl (meth) acrylate-reacted resin; a copolymer of (meth)acrylic acid/dicyclopentanyl (meth) acrylate reacted with 3,4-epoxycyclohexylmethyl methacrylate Resin, copolymer of (meth)acrylic acid/benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, (meth)acrylic acid/cyclohexyl (methyl) Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of (meth)acrylic acid/styrene and 3,4-epoxycyclohexylmethyl methacrylate Reaction resin, resin of (meth)acrylic acid/(meth)acrylic acid methyl group and 3,4-epoxycyclohexylmethyl methacrylate resin, (meth)acrylic acid/N-cyclohexyl Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, (meth)acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (methyl) Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, (meth)acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of (meth)acrylic acid / dicyclopentanyl (meth) acrylate / styrene and 3,4- Epoxycyclohexylmethyl methacrylate-reacted resin, (meth)acrylic acid/dicyclopentanyl (meth) acrylate/(meth)acrylic acid methyl copolymer and 3,4-epoxy ring Hexylmethyl methacrylate-reacted resin, copolymer of (meth)acrylic acid/dicyclopentanyl (meth) acrylate/N-cyclohexylmaleimide and 3,4-epoxycyclohexyl Methyl methacrylate-reacted resin; resin of crotonic acid/dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid/benzyl Base (methyl) propyl Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of crotonic acid/cyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl a methacrylate-reacted resin, a copolymer of crotonic acid/styrene and a resin reacted with 3,4-epoxycyclohexylmethyl methacrylate, a copolymer of crotonic acid/crotonate methyl and 3,4- Epoxycyclohexylmethyl methacrylate-reacted resin, copolymer of crotonic acid/N-cyclohexylmaleimide and 3,4-epoxycyclohexylmethyl methacrylate-reacted resin, crotonic acid a resin in which a copolymer of dicyclopentanyl (meth) acrylate/benzyl (meth) acrylate is reacted with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid/dicyclopentane Resin for copolymerization of a base (meth) acrylate/cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid / dicyclopentanyl (methyl) Resin copolymerized with acrylate/styrene and 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid/dicyclopentanyl (meth) acrylate/crotonate methyl Copolymer of copolymer with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexyl maleimide and 3 , 4-epoxycyclohexylmethyl methacrylate-reacted resin; copolymer of maleic acid/dicyclopentanyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate Reaction resin, copolymer of maleic acid/benzyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate resin, maleic acid/cyclohexyl (meth) acrylate a copolymer of a copolymer of 3,4-epoxycyclohexylmethyl methacrylate, a copolymer of maleic acid/styrene and a resin reacted with 3,4-epoxycyclohexylmethyl methacrylate, a copolymer of a maleic acid/maleic acid methyl group copolymer with 3,4-epoxycyclohexylmethyl methacrylate, a copolymer of maleic acid/N-cyclohexylmaleimide and 3, 4-epoxycyclohexylmethyl methacrylate-reacted resin, copolymer of maleic acid/dicyclopentanyl (meth) acrylate/benzyl (meth) acrylate and 3,4-epoxy Cyclohexylmethylmethyl propyl Resin-reactive resin, copolymer of maleic acid/dicyclopentanyl (meth) acrylate/cyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate Resin, maleic acid / dicyclopentanyl (meth) acrylate / styrene copolymer and 3,4-epoxycyclohexyl methyl methacrylate resin, maleic acid / dicyclopentane Resin copolymerized with 3,4-epoxycyclohexylmethyl methacrylate copolymer of alkyl (meth) acrylate / maleic acid methyl, maleic acid / dicyclopentanyl (meth) acrylate a resin in which a copolymer of ester/N-cyclohexylmaleimide is reacted with 3,4-epoxycyclohexylmethyl methacrylate; (meth)acrylic acid/maleic anhydride/dicyclopentanyl group (A) a copolymer of a acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, a copolymer of (meth)acrylic acid/maleic anhydride/benzyl (meth) acrylate, and 3, 4-epoxycyclohexylmethyl methacrylate-reacted resin, (meth)acrylic acid/maleic anhydride/cyclohexyl (meth) acrylate copolymer and 3,4-epoxycyclohexylmethylmethyl Acrylate reaction tree , (meth)acrylic acid/maleic anhydride/styrene copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, (meth)acrylic acid/maleic anhydride/(meth)acrylic acid Copolymer of methyl copolymer with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of (meth)acrylic acid/maleic anhydride/N-cyclohexylmaleimide and 3,4 - epoxycyclohexylmethyl methacrylate-reacted resin, (meth)acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer and 3 , 4-epoxycyclohexylmethyl methacrylate-reacted resin, copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth) acrylate/cyclohexyl (meth) acrylate Resin reactive with 3,4-epoxycyclohexylmethyl methacrylate, copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth)acrylate/styrene and 3,4 - an epoxycyclohexylmethyl methacrylate-reacted resin, a copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth)acrylate/(meth)acrylic acid methyl group, and 3, 4-epoxy ring Methyl methacrylate-reacted resin, copolymer of (meth)acrylic acid/maleic anhydride/dicyclopentanyl (meth) acrylate/N-cyclohexylmaleimide and 3,4-ring Oxycyclohexylmethyl methacrylate-reacted resin, and the like.

In the first stage of the resin (B-5), a copolymer of (b) and (c) is obtained in the same manner as in the above-described method for producing the resin (B-1).

In this case, as described above, the copolymer obtained can be used as it is, and a concentrated or diluted solution can be used, or a solid (powder) can be taken out by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of the entire structural unit constituting the above-mentioned copolymer.

Structural unit derived from (b); 5 to 95 mol% (preferably 10 to 90 mol%)

Structural unit derived from (c); 5 to 95 mol% (preferably 10 to 90 mol%)

Further, similarly to the method for producing the resin (B-4), the cyclic ether derived from (b) in the copolymer of (b) and (c) may be reacted with the carboxylic acid or carboxylic anhydride having (a) And got it. The hydroxyl group produced by the reaction of the cyclic ether with a carboxylic acid or a carboxylic anhydride can be further reacted with a carboxylic anhydride.

The amount of (a) to be reacted in the above copolymer is preferably from 5 to 80 mol% based on the number of moles of (b). The cyclic ether is highly reactive, and the unreacted (b) is less likely to remain, and (b) is preferably (b1) and further preferably (b1-1).

Specific examples of the resin (B-5) include a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate/epoxypropyl (meth) acrylate with (meth)acrylic acid, and a benzyl group. Copolymer of (meth) acrylate/epoxypropyl (meth) acrylate with (meth)acrylic acid, cyclohexyl (meth) acrylate / epoxy propyl (meth) acrylate Resin copolymerized with (meth)acrylic acid, copolymer of styrene/epoxypropyl (meth)acrylate and (meth)acrylic resin, methyl (meth)acrylate/epoxypropyl Copolymer of (meth) acrylate copolymer with (meth)acrylic acid, copolymer of N-cyclohexylmaleimide/epoxypropyl (meth) acrylate and (meth)acrylic acid Copolymer, copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / epoxy propyl (meth) acrylate with (meth) acrylic acid, dicyclopentane Copolymer of a (meth) acrylate/cyclohexyl (meth) acrylate/epoxypropyl (meth) acrylate copolymer with (meth)acrylic acid, dicyclopentanyl (methyl) Copolymer of acrylate/styrene/epoxypropyl (meth) acrylate copolymer with (meth)acrylic acid, (dicyclopentyl (meth) acrylate / methyl (meth) acrylate / Copolymer of a copolymer of glycidyl (meth) acrylate with (meth)acrylic acid, dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / epoxy propyl ( a resin in which a copolymer of a methyl acrylate is reacted with (meth)acrylic acid; a copolymer in which a copolymer of dicyclopentanyl (meth) acrylate/epoxypropyl (meth) acrylate is reacted with crotonic acid, Copolymerization of a benzyl (meth) acrylate/epoxypropyl (meth) acrylate copolymer with crotonic acid, cyclohexyl (meth) acrylate / epoxy propyl (meth) acrylate a resin which reacts with crotonic acid, a copolymer of styrene/epoxypropyl (meth) acrylate, a resin which reacts with crotonic acid, a copolymer of methyl crotonate/epoxypropyl (meth) acrylate and a resin of a crotonic acid reaction, a copolymer of N-cyclohexylmaleimide/epoxypropyl (meth) acrylate, and a resin reacted with crotonic acid, dicyclopentanyl ( Copolymer of acrylate/benzyl (meth) acrylate/epoxypropyl (meth) acrylate copolymer with crotonic acid, dicyclopentanyl (meth) acrylate / cyclohexyl (A Copolymer of acrylate/epoxypropyl (meth) acrylate copolymer with crotonic acid, dicyclopentanyl (meth) acrylate / styrene / epoxy propyl (meth) acrylate Resin copolymerized with crotonic acid, copolymer of dicyclopentanyl (meth) acrylate/methyl crotonate/epoxypropyl (meth) acrylate, resin reacted with crotonic acid, dicyclopentane a resin in which a copolymer of an alkyl (meth) acrylate/N-cyclohexylmaleimide/epoxypropyl (meth) acrylate is reacted with crotonic acid; dicyclopentanyl (meth) acrylate Copolymer of /epoxypropyl (meth) acrylate copolymer with maleic acid, copolymer of benzyl (meth) acrylate / epoxy propyl (meth) acrylate reacted with maleic acid Resin, cyclohexyl (meth) acrylate / epoxy propyl (meth) acrylate copolymer with maleic acid resin, styrene / epoxy propyl (meth) acrylate Resin copolymerized with maleic acid, copolymer of methyl maleate/epoxypropyl (meth) acrylate, resin reacted with maleic acid, N-cyclohexylmaleimide/epoxy Copolymer of propyl (meth) acrylate copolymer with maleic acid, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / epoxy propyl (meth) acrylate Resin copolymerized with maleic acid, copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / epoxy propyl (meth) acrylate reacted with maleic acid a resin, a copolymer of dicyclopentanyl (meth) acrylate/styrene/epoxypropyl (meth) acrylate, a resin reacted with maleic acid, dicyclopentanyl (meth) acrylate /Methyl maleate/epoxypropyl (meth) acrylate copolymer with maleic acid, dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / a copolymer of a copolymer of glycidyl (meth) acrylate and maleic acid; a copolymer of dicyclopentanyl (meth) acrylate/epoxypropyl (meth) acrylate and (methyl) )Acrylic and horse Anhydride-reactive resin, a copolymer of benzyl (meth) acrylate/epoxypropyl (meth) acrylate, a resin reactive with (meth)acrylic acid and maleic anhydride, cyclohexyl (meth) acrylate / a copolymer of a copolymer of epoxy propyl (meth) acrylate with a (meth)acrylic acid and maleic anhydride, a copolymer of styrene/epoxypropyl (meth) acrylate, and (meth)acrylic acid and Maleic anhydride-reactive resin, copolymer of (meth)acrylic acid/epoxypropyl (meth)acrylate, and (meth)acrylic acid and maleic anhydride-reactive resin, (N-cyclohexylmalanium) Copolymer of imine/epoxypropyl (meth) acrylate copolymer with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate Copolymer of /epoxypropyl (meth) acrylate with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / ring Copolymer of oxypropyl (meth) acrylate with (meth)acrylic acid and maleic anhydride, dicyclopentyl (meth) acrylate / styrene / Copolymer of oxypropyl (meth) acrylate with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / epoxy propyl Copolymer of (meth) acrylate copolymer with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / epoxy propyl ( Copolymer of methyl acrylate copolymer with (meth)acrylic acid and maleic anhydride; copolymerization of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate a resin which reacts with (meth)acrylic acid, a copolymer of benzyl (meth) acrylate/3,4-epoxycyclohexylmethyl methacrylate, a resin which reacts with (meth)acrylic acid, a cyclohexyl group ( Copolymer of methyl acrylate/3,4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid, styrene/3,4-epoxycyclohexylmethyl methacrylate Resin copolymerized with (meth)acrylic acid, copolymer of methyl (meth)acrylate/3,4-epoxycyclohexylmethyl methacrylate and (meth)acrylic acid a copolymer of N-cyclohexylmaleimide/3,4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid, dicyclopentanyl (meth) acrylate/ Copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid, dicyclopentanyl (meth) acrylate / cyclohexyl Copolymer of (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid, dicyclopentanyl (meth) acrylate / styrene / 3 , a copolymer of 4-epoxycyclohexylmethyl methacrylate and (meth)acrylic acid, dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3, 4- Copolymer of epoxycyclohexylmethyl methacrylate reacted with (meth)acrylic acid, dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-ring Copolymer of a copolymer of oxycyclohexylmethyl methacrylate and (meth)acrylic acid; copolymerization of dicyclopentanyl (meth) acrylate/3,4-epoxycyclohexylmethyl methacrylate Reacts with crotonic acid Resin, benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with crotonic acid resin, cyclohexyl (meth) acrylate / 3, 4- epoxy a copolymer of a cyclohexylmethyl methacrylate copolymer reacted with crotonic acid, a copolymer of styrene/3,4-epoxycyclohexylmethyl methacrylate and a resin reacted with crotonic acid, methyl crotonate/ Copolymerization of a copolymer of 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, copolymerization of N-cyclohexylmaleimide/3,4-epoxycyclohexylmethyl methacrylate Copolymer with crotonic acid, copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate reacted with crotonic acid Resin, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer and croton acid resin, two rings Copolymer of pentyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer with crotonic acid, dicyclopentanyl (methyl) propyl Copolymer of enoate/methyl crotonate/3,4-epoxycyclohexylmethyl methacrylate and crotonic acid, dicyclopentanyl (meth) acrylate/N-cyclohexyl a resin which reacts a copolymer of quinone imine/3,4-epoxycyclohexylmethyl methacrylate with crotonic acid; dicyclopentanyl (meth) acrylate/3,4-epoxycyclohexyl a copolymer of a methacrylic acid ester copolymer with maleic acid, a copolymer of benzyl (meth) acrylate/3,4-epoxycyclohexylmethyl methacrylate, and a resin reacted with maleic acid, Copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymerized with maleic acid, styrene / 3,4-epoxycyclohexylmethyl methacrylate a copolymer of an ester copolymer with maleic acid, a copolymer of methyl maleate/3,4-epoxycyclohexylmethyl methacrylate, a resin reacted with maleic acid, N-cyclohexylmalanium Copolymer of imine/3,4-epoxycyclohexylmethyl methacrylate copolymerized with maleic acid, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3 4-epoxycyclohexyl Resin copolymerized with maleic acid, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Copolymer of an ester copolymer with maleic acid, a copolymer of dicyclopentyl (meth) acrylate/styrene/3,4-epoxycyclohexylmethyl methacrylate reacted with maleic acid Copolymer, dicyclopentanyl (meth) acrylate / methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid, dicyclopentanyl (meth)acrylate/N-cyclohexylmaleimide/3,4-epoxycyclohexylmethyl methacrylate copolymer with maleic acid; dicyclopentanyl (methyl) Copolymer of acrylate/3,4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid and maleic anhydride, benzyl (meth) acrylate / 3,4-epoxy Copolymerization of a copolymer of cyclohexylmethyl methacrylate with a resin reactive with (meth)acrylic acid and maleic anhydride, cyclohexyl (meth) acrylate/3,4-epoxycyclohexylmethyl methacrylate Object and Acrylic acid and maleic anhydride-reactive resin, copolymer of styrene/3,4-epoxycyclohexylmethyl methacrylate, (meth)acrylic acid and maleic anhydride-reacted resin, (meth)acrylic acid Copolymer of methyl ester/3,4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid and maleic anhydride, N-cyclohexylmaleimide/3,4-epoxy Copolymer of cyclohexylmethyl methacrylate with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4- a copolymer of epoxycyclohexylmethyl methacrylate with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3, Copolymer of 4-epoxycyclohexylmethyl methacrylate with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / styrene / 3, 4-epoxy Copolymer of cyclohexylmethyl methacrylate with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3, 4-ring Copolymer of cyclohexylmethyl methacrylate with (meth)acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3, 4 a resin obtained by reacting a copolymer of epoxycyclohexylmethyl methacrylate with (meth)acrylic acid and maleic anhydride.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000. When the weight average molecular weight of the resin (B) is in the above range, the coating property tends to be good, and film formation is less likely to occur during development, and the non-exposed portion removal property tends to be good at the time of development.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is in the above range, the developability tends to be excellent.

The acid value of the resin (B) is preferably from 20 to 150 mg/g-KOH, more preferably from 50 to 135 mg/g-KOH, still more preferably from 70 to 135 mg/g-KOH. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution.

When the colored photosensitive composition of the present invention contains the resin (B), the content of the resin (B) is usually from 5 to 95% by mass, preferably from 20 to 95% by mass based on the total amount of the resin (B) and the polymerizable compound (C). 80% by mass, more preferably 40 to 60% by mass. When the content of the resin (B) is in the above range, the developability, the adhesion, the solvent resistance of the cured pattern, and the mechanical properties tend to be good.

The colored photosensitive composition of the present invention contains a polymerizable compound (C).

The polymerizable compound (C) may be a compound which is polymerized by an active radical, an acid or the like generated by the polymerization initiator (D), and may, for example, be a compound having a polymerizable ethylenically unsaturated bond, preferably (A) Base) acrylate compound.

The polymerizable compound (C) having one polymerizable ethylenically unsaturated bond may, for example, be the same as the compound as described in the above (a), (b) and (c), wherein (meth) acrylate The class is better.

The polymerizable compound (C) having two polymerizable ethylenically unsaturated bonds may, for example, be 1,3-butanediol di(meth)acrylate or 1,3-butanediol (meth)acrylate. 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate , triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether, ethoxy Bisphenol bis(meth) acrylate, propoxylated neopentyl glycol di(meth) acrylate, ethoxylated neopentyl glycol di(meth) acrylate, 3-methyl pentyl Alkylene glycol di(meth)acrylate or the like.

The polymerizable compound (C) having three polymerizable ethylenically unsaturated bonds may, for example, be trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate or ginseng (2-hydroxy group B). Isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol Tetrakis (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol a reaction of hexa(meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate with an acid anhydride, dipentaerythritol penta (meth) acrylate a reaction product of an ester and an acid anhydride, a tripentaerythritol hepta (meth) acrylate and an acid anhydride caprolactone-modified trimethylolpropane tri(meth) acrylate, a caprolactone-modified pentaerythritol tri(meth) acrylate, Caprolactone modified ginseng (2-hydroxyethyl) isocyanurate tris(methyl) ) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Ester-modified tripentaerythritol tetra(meth)acrylate, caprolactone modified tripellitate penta (meth) acrylate, caprolactone modified tripellitate hexa(meth) acrylate, caprolactone modified tripentaerythritol Hexa (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate and anhydride reaction, caprolactone modified dipentaerythritol A reaction product of a (meth) acrylate and an acid anhydride, a caprolactone-modified tripentaerythritol hepta (meth) acrylate, an acid anhydride, or the like.

Among them, a trifunctional or higher monomer is preferred, and dipentaerythritol hexa(meth)acrylate is more preferred.

The content of the polymerizable compound (C) is preferably from 5 to 95% by mass, more preferably from 20 to 80% by mass, based on the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerizable compound (C) is in the above range, the smoothness, letterability, and mechanical strength of the sensitivity or the obtained pattern tend to be good.

The colored photosensitive composition of the present invention contains a polymerization initiator (D).

The polymerization initiator (D) is a compound which can initiate polymerization by generating active radicals, an acid or the like by light action, and is not particularly limited, and a conventional polymerization initiator can be used.

The polymerization initiator (D) is preferably a biimidazole compound, an alkylphenone compound, a triazine compound, a mercaptophosphine oxide compound or an anthracene compound. Further, a photocationic polymerization initiator (for example, a ruthenium cation and an anion derived from Lewis acid) described in JP-A-2008-181087 can also be used.

The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, JP-A-6-75372 and JP-A-6-75373), 2, 2'-double (2) -Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis ( 2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, Japanese Patent Publication No. Sho 48-38403 and JP-A-62-174204). An imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with a carbonyl alkoxy group (for example, JP-A-7-10913). Preferred are, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl). -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole .

The above alkylphenone compound may, for example, be diethoxyacetophenone or 2-methyl-2-morpholino-1-(4-methylsulfonylphenyl)propan-1-one, 2 -Dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2 -(4-methylphenylmethyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2- Methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropene An oligomer or the like of phenyl)propan-1-one, preferably 2-methyl-2-morpholino-1-(4-methylsulfonylphenyl)propan-1-one, 2- Dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one and the like. Commercial products such as IRGACURE 369 and 907 (above, manufactured by BASF Japan) can also be used.

The aforementioned triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloromethane). 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxythionyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2- (5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

The above-mentioned mercaptophosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. Commercial products such as IRGACURE 819 (manufactured by BASF Japan Co., Ltd.) can also be used.

The above hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylsulfonylphenyl)butan-1-one-2-imine or N-benzylideneoxy-1-( 4-phenylsulfonylphenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)- 9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl -2,4-dioxolylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine and the like. Commercial products such as IRGACUREOXE-01, OXE-02 (above, manufactured by BASF Japan), and N-1919 (made by ADEKA) can also be used.

Further, the polymerization initiator (D) may, for example, be a benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether; benzophenone or o-benzylidene group Methyl benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (tert-butyl peroxidation) a benzophenone compound such as carbonyl)benzophenone or 2,4,6-trimethylbenzophenone; a quinone compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone or the like; -butyl-2-chloroacridone, benzyl ester, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine compound described later) which will be described later.

The colored photosensitive composition of the present invention may contain a polymerization initiation aid (D1). The polymerization initiation aid (D1) can be used in combination with the polymerization initiator (D), and is a compound or a sensitizer used to promote polymerization of a polymerizable compound which starts polymerization by a polymerization initiator.

The polymerization initiation aid (D1) may, for example, be an amine compound, a thiazoline compound, an alkoxyfluorene compound, a thioxanthone compound, a carboxylic acid compound or the like.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethylamine. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzol Ketones and the like, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The thiazoline compound may, for example, be a compound represented by the formula (III-1) to the formula (III-3).

【化4】

The alkoxy ruthenium compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl-9. , 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

The thioxanthone compound may, for example, be 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone or 1-chloro -4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfonyl acetic acid, methylphenylsulfonyl acetic acid, ethylphenylsulfonyl acetic acid, methylethylphenylsulfonyl acetic acid, and dimethylphenylsulfonate. Acetic acid, methoxyphenylsulfonyl acetic acid, dimethoxyphenylsulfonyl acetic acid, chlorophenylsulfonyl acetic acid, dichlorophenylsulfonyl acetic acid, N-phenylglycine, benzene Oxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

The content of the polymerization initiator (D) is preferably from 0.1 to 40% by mass, more preferably from 1 to 30% by mass, based on the total amount of the resin (B) and the polymerizable compound (C).

When the total amount of the polymerization initiator (D) is within this range, the coloring photosensitive composition becomes highly sensitive, and the chemical resistance, mechanical strength, and surface smoothness of the obtained pattern tend to be good.

When the polymerization initiator (D1) is used, the amount thereof is preferably 0.01 to 50% by mass, and more preferably 0.1 to 40% by mass based on the total amount of the resin (B) and the polymerizable compound (C). Further, 1 mole of the polymerization initiator (D) is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles.

When the amount of the polymerization starting aid (D1) is in this range, the sensitivity of the obtained colored photosensitive composition becomes higher, and the productivity of the obtained pattern tends to be improved.

Further, the colored photosensitive composition of the present invention may further contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) is a compound having two or more sulfonyl groups in the molecule. In particular, when a compound having two or more sulfonyl groups adjacent to an aliphatic hydrocarbon group is used, the sensitivity of the colored photosensitive composition of the present invention is high, which is preferable.

The polyfunctional thiol compound (T) may, for example, be hexanedithiol, decanedithiol, 1,4-bis(methylsulfonyl)benzene or butanediol bis(3-sulfonylpropionic acid). Ester), butanediol bis(3-sulfonyl acetate), ethylene glycol bis(3-sulfonyl acetate), trimethylolpropane ginseng (3-sulfonyl acetate), Butanediol bis(3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonyl acetate), pentaerythritol Indole (3-sulfonylpropionate), pentaerythritol oxime (3-sulfonylacetate), hydroxyethyl ginseng (3-sulfonylpropionate), pentaerythritol bismuth (3-sulfonyl butylate) Ester), 1,4-bis(3-sulfonylbutoxy)butane, and the like.

The content of the polyfunctional thiol compound (T) is preferably from 0.5 to 20% by mass, more preferably from 1 to 15% by mass, based on the polymerization initiator (D). When the content of the polyfunctional thiol compound (T) is in this range, the sensitivity tends to be high and the developability tends to be good.

The colored photosensitive composition of the present invention contains a solvent (E). The solvent (E) is not particularly limited, and a solvent which is usually used in the field can be used. For example, it can be used in an ester solvent (a solvent containing -COO-, a solvent containing no -O-), an ether solvent other than an ester solvent (a solvent containing -O-, a solvent containing no -COO-), an ether ester solvent (molecule) a solvent containing a solvent other than -COO- and -O-, a solvent other than an ester solvent (a solvent containing -CO-, a solvent containing no -COO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, and Choose from methyl hydrazine.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and isoamyl acetate. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexanol Acetate, γ-butyrolactone, and the like.

The ether solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether or diethylene glycol. Alcohol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methyl anisole, and the like.

The ether ester solvent may, for example, be methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate or methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate and the like.

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone, isophorone and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, toluene, and trimethylbenzene.

Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used singly or in combination of two or more kinds.

Among the above solvents, an organic solvent having a boiling point of 1 atm of from 120 ° C to 180 ° C is preferred from the viewpoint of coatability and drying property. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, etc. good.

The content of the solvent (E) in the coloring photosensitive composition is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass based on the coloring photosensitive composition. In other words, the solid content of the colored photosensitive composition is preferably from 5 to 40% by mass, more preferably from 10 to 30% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating tends to be good.

The colored photosensitive composition of the present invention preferably contains a surfactant (F). Examples of the surfactant include an anthrone-based surfactant, a fluorine-based surfactant, and an anthrone-based surfactant having a fluorine atom. By including a surfactant, the flatness at the time of coating tends to be good.

The anthrone-based surfactant may, for example, be a surfactant having a siloxane coupling.

Specifically, for example, toray silicone DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, a polyether modified fluorenone oil SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials ‧ Japan contract company )Wait.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain.

Specifically, for example, Fluorinert (registered trademark) FC430, FC431 (Sumitomo 3M (share) system), MEGAFACE (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same R30 (DIC) (share) system, EFTOP (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, same S382, same SC101, same as SC105 (Asahi Glass ( ())), E5844 ((share) Daikin Institute of Precision Chemistry).

The anthrone-based surfactant having a fluorine atom may, for example, be a surfactant having a siloxane chain and a fluorocarbon chain. Specifically, for example, MEGAFACE (registered trademark) R08, the same BL20, the same F475, the same F477, the same F443 (DIC system), and the like can be given. It is preferably MEGAFACE (registered trademark) F475.

The surfactant (F) is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less based on the coloring photosensitive composition. When the surfactant is contained in this range, the flatness of the coating film can be improved.

The colored photosensitive composition of the present invention may contain various additives such as a filler, other polymer compound, adhesion promoter, antioxidant, ultraviolet absorber, light stabilizer, and chain transfer agent as necessary.

The colored photosensitive composition of the present invention can be prepared as follows.

First, the pigment of the coloring agent (A) is mixed with the solvent (E) so that the average particle diameter of the pigment is about 0.2 μm or less, and dispersion is carried out using a bead mill or the like. At this time, some or all of the pigment dispersant and the resin (B) may be used as needed. In the obtained pigment dispersion liquid, a polymerizable compound (C), a polymerization initiator (D), a residual resin (B) contained as needed, and other components, and optionally a solvent (E) are added thereto. At a specific concentration, a desired color-sensitive photosensitive composition can be obtained.

The colored photosensitive composition of the present invention is processed by a filter, for example, by the steps shown in the following (1) to (4).

(1) A step of obtaining a coating film by applying the colored photosensitive composition of the present invention to a substrate

(2) Step of coating the film after exposure of the coating film through the mask to obtain an exposure film

(3) Step of developing a post-exposure coating film by an alkali developing solution to obtain a pattern

(4) Steps of baking the pattern to obtain a hardened pattern

Examples of the method for obtaining the pattern include a photolithography method, an inkjet method, a printing method, and the like. Among them, the light lithography method is preferred.

The photolithography method is a method in which the coloring photosensitive composition is applied onto a substrate, dried, exposed to a photomask, and developed to obtain a pattern.

Examples of the substrate include glass, metal, and plastic, and may be in the form of a plate or a film.

Examples of the plastic material include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, and poly(methyl). Acrylates, cellulose esters, polycarbonates, polybenzazoles, polyether oximes, polyether ketones, polyphenylene sulfides, and polyphenylene ethers. Here, (meth)acrylic acid means at least one selected from the group consisting of acrylic acid and methacrylic acid.

A structure such as a color filter, various insulating or conductive films, and a driving circuit can be formed on the substrate.

According to the colored photosensitive composition of the present invention, a hardened pattern can be formed at a lower temperature, especially when used for forming a pattern on a plastic substrate.

Examples of the method of applying the substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Further, a dip coater, a roll coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (also referred to as a die coater, a curtain coater, or the like) can be used. A coating device such as a non-rotating coater or an inkjet is applied. Among them, it is preferred to apply it by using a slit coater, a spin coater, a roll coater or the like.

The method of drying the substrate coating film may, for example, be a method such as heat drying, natural drying, air drying, or reduced pressure drying. Complex methods can also be combined.

The drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C. The heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

Drying under reduced pressure is preferably carried out at a temperature of from 50 to 150 Pa and at a temperature of from 20 to 25 °C.

The film thickness of the coating film after drying is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, etc., and is usually 0.1 to 20 μm, preferably 1 to 6 μm.

The dried coating film is exposed through a photomask for forming a desired pattern.

The shape of the pattern on the photomask at this time is not particularly limited, and a pattern shape for the intended purpose can be used.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, it is possible to perform selective masking by using a filter that shields light of less than 350 nm and filters in the wavelength range, and a band pass filter that takes out light in the vicinity of 436 nm, near 408 nm, and around 365 nm, and the like. Specifically, for example, a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, or the like can be given.

It is preferable to uniformly illuminate the entire surface of the exposed surface to align the position of the mask and the substrate, and to use a mask to align the exposure machine, the stepper, or the like.

After the exposure, the contact developing solution is allowed to dissolve and develop a specific portion, for example, an unexposed portion, to obtain a pattern. The developer may be an organic solvent. However, since the exposed portion of the coating film is less likely to be dissolved or swollen by the developer, a good shape pattern can be obtained, and an aqueous solution of a basic compound is preferred.

The developing method may be any one of a stirring paddle method, a dipping method, a spray method, and the like. Further, the substrate can be tilted at an arbitrary angle during development.

It is preferred to carry out water washing after development.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, and carbonic acid. Inorganic basic compound of sodium, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonium, etc.; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethyl An organic basic compound such as a base amine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine or ethanolamine. Among them, potassium hydroxide, sodium hydrogencarbonate and tetramethylammonium hydroxide are preferred.

The concentration in the aqueous solution of the inorganic and organic basic compound is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass.

The aqueous solution of the aforementioned basic compound may contain a surfactant.

Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, ethylene oxide/propylene oxide block copolymers, and the like. A sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a glycerin fatty acid ester, a polyoxyethylene fatty acid ester, a polyoxyethylene alkylamine, etc. Ionic surfactant; anionic interfacial activity of sodium lauryl sulfate, sodium oleyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate, etc. A cationic surfactant such as stearylamine hydrochloride or lauryl trimethylammonium chloride.

The concentration of the surfactant in the aqueous solution of the basic compound is preferably from 0.01 to 10% by mass, more preferably from 0.05 to 8% by mass, even more preferably from 0.1 to 5% by mass.

Further, post-baking can be performed as necessary. Post-baking is preferably carried out, for example, at a temperature of from 50 to 230 ° C for from 2 to 240 minutes.

The colored photosensitive composition of the present invention can obtain a pattern having good color density, brightness, contrast, sensitivity, resolution, heat resistance, and the like, and a color filter. Moreover, these color filters or patterns can be used in a conventional manner as a display device of a part of the component, such as a conventional liquid crystal display device, an organic EL device, a solid-state imaging device, or an electronic paper. Wait for the color image related machine.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples. In the example, "%" and "part" are not specifically described, and are % by mass and part by mass.

Synthesis Example 1

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 182 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was changed from nitrogen to nitrogen, and then the temperature was raised to 100 ° C. Benzyl methacrylate 70.5 g (0.40 mol), methacrylic acid 43.0 g (0.5 mol), tricyclodecane skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22.0 g ( A solution of 3.6 g of azobisisobutyronitrile added to a mixture of 136 g of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate was dropped from the dropping funnel to the flask for 2 hours, and further stirred at 100 ° C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and epoxy propyl methacrylate was 35.5 g [0.25 mol, (50 mol% based on the carboxyl group of methacrylic acid used in the reaction)] 0.9 g of lysylmethylphenol and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C for 6 hours to obtain a resin solution B1 having a solid content of 79 mg KOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 13,000 and the molecular weight distribution (Mw/Mn) was 2.1.

Synthesis Example 2

Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a gas introduction tube, 250 parts of propylene glycol monomethyl ether acetate was introduced. Thereafter, the nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere inside the flask was replaced with a nitrogen gas. Thereafter, the solution in the flask was heated to 100 ° C, and then 152.6 parts of benzyl methacrylate, 41.7 parts of methacrylic acid, 1.5 parts of azobisisobutyronitrile, and 150 parts of propylene glycol monomethyl ether acetate were prepared. The mixture was dropped into the flask using a dropping funnel for 2 hours, and after the completion of the dropwise addition, the mixture was further stirred at 100 ° C for 2.5 hours to obtain a weight average molecular weight Mw of 2.3 × 10 ⁴ , a solid content of 34% by mass, and a solution acid value of 47 mg - KOH / g. Resin solution B2.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained by the synthesis example were measured by the following conditions using the GPC method.

Device; K2479 (made by Shimadzu Corporation)

Pipe string; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

Detector; RI

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution.

Example 1 [Modulation of coloring photosensitive composition]

Make

Pigment: C.I. Pigment Green 58 51 parts

Propylene pigment dispersant 10 parts

Resin solution B2 (solid content conversion) 20 parts

Propylene glycol monomethyl ether acetate 267 parts

a pigment dispersion A in which the pigment is sufficiently dispersed by using a bead mill,

Pigment: C.I. Pigment Yellow 138 81 parts

Propylene pigment dispersant 12 parts

Resin solution B2 (solid content conversion) 28 parts

Propylene glycol monomethyl ether acetate 402 parts

a pigment dispersion liquid B which is mixed and used to sufficiently disperse the pigment using a bead mill,

Pigment: C.I. Pigment Green 7 29 parts

Propylene pigment dispersant 5.7 parts

Resin solution B2 (solid content conversion) 11 parts

Propylene glycol monomethyl ether acetate 173 parts

a pigment dispersion liquid C which is mixed and used to sufficiently disperse the pigment using a bead mill,

versus

Resin: Resin solution B1 (solid content conversion) 66 parts,

Polymeric compound: dipentaerythritol hexaacrylate

(Nippon Chemical Co., Ltd.) 57 copies,

Polymerization initiator: 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one (IRGACURE 369; manufactured by BASF Japan) 15 parts,

Polymerization initiation aid: 4,4'-bis(diethylamino)benzophenone (EAB-F; manufactured by Hodogaya Chemical Industry Co., Ltd.) 4.9 parts,

Solvent: propylene glycol monomethyl ether acetate 450 parts, and

Additive: Sumi-Epoxy ESCN-195XL (Sumitomo Chemical Co., Ltd.) 6.1 parts

The coloring photosensitive composition was obtained by mixing.

Comparative example [Modulation of coloring photosensitive composition]

will

Pigment: C.I. Pigment Green 36 5.5 parts

Pigment: C.I. Pigment Yellow 150 2.4 parts

Polyester pigment dispersant 1.2 parts

Propylene glycol monomethyl ether acetate 38 parts

Mixing and using a bead mill to fully disperse the pigment dispersion, mixing

Resin: Resin solution B1 (solid content conversion) 6.6 parts

Polymeric compound: dipentaerythritol hexaacrylate

(Nippon Chemical Co., Ltd.) 5.7 copies

Polymerization initiator: 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one (IRGACURE 369; manufactured by BASF Japan) 1.5 parts

Polymerization starter: 4,4'-bis(diethylamino)benzophenone (EAB-F Baotu Valley Chemical Industry Co., Ltd.) 0.49 parts

Additive: Sumi-Epoxy ESCN-195XL (manufactured by Sumitomo Chemical Co., Ltd.) 0.61

Solvent: propylene glycol monomethyl ether acetate 38 parts

A colored photosensitive composition was obtained.

<Model work>

A PET film (Toray Road Milla 75-T60) was bonded to a 2-inch square glass plate to prepare a substrate. The colored photosensitive composition was applied on the PET film side of the substrate by a spin coating method, and prebaked on a hot plate at 80 ° C for 2 minutes. After cooling, the distance between the substrate on which the colored photosensitive composition was applied and the mask made of quartz glass was 10 μm, and an exposure machine (TME-150RSK; TOPCON) was used, and in an atmosphere of 200 mJ/cm. The exposure amount of ² (365 nm reference) was irradiated with light. Further, at this time, the irradiation of the colored photosensitive composition is performed by passing the emitted light from the ultrahigh pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Separation Co., Ltd.). The mask is formed using a line and interval pattern of 10 to 100 μm. After light irradiation, it was immersed in a tetramethylammonium 0.1% aqueous solution at 23 ° C for 80 seconds to carry out development, and washed with pure water to form a pattern. The film thickness of the obtained pattern was measured to be 2 μm using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

The pattern formed in the same manner as above was further heated (post-baking) at 50 ° C for 5 minutes to obtain a hardened pattern. Further, the pattern formed in the same manner as described above was further heated (post-baking) at 100 ° C for 5 minutes to obtain a cured pattern. The film thickness of the obtained hardened pattern was measured in the same manner as described above, and both were 2 μm.

<Color Performance Evaluation>

The spectral spectrum of the obtained pattern was measured for a transmittance (T1) at 600 nm and a transmittance (T2) at 520 nm by a microscopic spectrometer (OSP-SP200 OLYMPUS). The smaller the T1 ratio (T1/T2) of T2, the better the color separation ability with the red filter. The results are shown in Table 1.

<Solvent resistance evaluation>

1 ml of propylene glycol monomethyl ether acetate was dropped on the pattern formed on the substrate, and after 30 seconds of standstill, it was rotated by a spin coater at 1000 rpm for 10 seconds to remove propylene glycol on the pattern. Monomethyl ether acetate.

The film thickness value measured by the following formula was calculated from the film thickness value measured before and after contact with propylene glycol monomethyl ether acetate. The higher the film thickness retention rate, the better the curing property, and when the coloring photosensitive composition other than green is repeatedly applied, the dissolution of the solvent contained in the coloring photosensitive composition is suppressed, and mixing can be prevented when the color filter is produced. ). The results are shown in Table 2.

(film thickness retention ratio) (%) = (film thickness after contact) / (film thickness before contact)

<Resolution Evaluation>

The obtained pattern was observed with a laser microscope (manufactured by Axio Imager MAT Carl Zeiss Co., Ltd.) to make the resolution minimum size as the resolution. The higher the resolution, the higher the fine color filter can be produced. The results are shown in Table 2.

[Industrial use]

According to the colored photosensitive composition of the present invention, a green filter excellent in color separation ability with a red filter can be obtained.

Claims (5)

A colored photosensitive composition containing a coloring agent, a polymerizable compound, a polymerization initiator, and a solvent, and the coloring agent contains a copper oxyhalide pigment, a zinc halide pigment, and a quinophthalone pigment. The content of the colorant, the copper oxyhalide pigment, is 20 parts by mass or more and 150 parts by mass or less, and the content of the quinacridone pigment is relative to the zinc halide titanium phthalocyanine pigment, based on 100 parts by mass of the content of the zinc halide titanium cyanine pigment. The content is 50 parts by mass or more and 200 parts by mass or less in terms of 100 parts by mass. The colored photosensitive composition according to claim 1, wherein the copper oxytitanium halide pigment is C.I. Pigment Green 7. The colored photosensitive composition according to claim 1, wherein the quinacridone pigment is C.I. Pigment Yellow 138. The colored photosensitive composition according to claim 1, which contains a coloring agent, a polymerizable compound, a polymerization initiator, a solvent, and a resin. A color filter formed by the colored photosensitive composition described in claim 1.