JP2012185430A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition capable of forming a pattern having excellent solvent resistance.SOLUTION: A colored curable resin composition includes (A), (B), (C), (D), (E) and (F): (A) colorant; (B) binder resin; (C) compound having at least one kind of group selected from the group consisting of acryloyl group and methacryloyl group (where the compound has no vinyloxy group); (D) compound having vinyloxy group; (E) radical polymerization initiator; and (F) acid generator.

Description

  The present invention relates to a colored curable resin composition.

  The color filter is used in a display device such as a liquid crystal display panel, an electroluminescence panel, a plasma display panel, or electronic paper, and is manufactured from a colored curable resin composition. As such a colored curable resin composition, a colored curable resin composition containing dipentaerythritol hexaacrylate as a polymerizable compound is known (Patent Document 1).

JP 2007-41343 A

  A pattern obtained from the above-mentioned conventionally known colored curable resin composition has not been sufficiently satisfactory with respect to solvent resistance.

The present invention provides the following [1] to [6].
[1] A colored curable resin composition comprising (A), (B), (C), (D), (E) and (F).
(A) Colorant (B) Binder resin (C) Compound having at least one group selected from the group consisting of acryloyl group and methacryloyl group (however, it does not have vinyloxy group)
(D) Compound having vinyloxy group (E) Radical polymerization initiator (F) Acid generator [2] Colored curable resin composition according to [1], wherein (D) is a compound having three or more vinyloxy groups object.
[3] The colored curable resin composition according to [1] or [2], wherein (C) is a compound having three or more of at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.
[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].

  According to the colored curable resin composition of the present invention, a pattern having excellent solvent resistance can be obtained.

The colored curable resin composition of the present invention is a colored curable resin composition containing (A), (B), (C), (D), (E) and (F).
(A) Colorant (hereinafter sometimes referred to as “colorant (A)”)
(B) Binder resin (hereinafter sometimes referred to as “binder resin (B)”)
(C) a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (hereinafter sometimes referred to as “(meth) acryloyl group”) (hereinafter referred to as “(meth) acryloyl compound (C)”). (However, it does not have a vinyloxy group.)
(D) Compound having a vinyloxy group (hereinafter sometimes referred to as “vinyl ether compound (D)”)
(E) Radical polymerization initiator (hereinafter sometimes referred to as “polymerization initiator (E)”)
(F) Acid generator (hereinafter sometimes referred to as “acid generator (F)”)
In the present specification, notations such as “(meth) acrylic acid” and “(meth) acrylate” also have the same meaning as “(meth) acryloyl”.

  The colored curable resin composition of the present invention contains a colorant (A). Examples of the colorant (A) include pigments and dyes. Especially, it is preferable that a pigment is included at the point of heat resistance and light resistance.

Examples of pigments include compounds classified as pigments by the Color Index (published by The Society of Dyers and Colorists).
Examples of the pigment 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;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. 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;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 242, 254, C.I. I. Pigment violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Green 7, 36, and 58 are preferable. By including the pigment, the transmission spectrum can be easily optimized. These pigments may be used alone or in combination of two or more.

If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), and Ajispur (Ajinomoto Fine). (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment (A2). When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

  Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to solid content in a colored curable resin composition, More preferably, it is 5-45 mass%. When the content of the colorant (A) is in the above range, a desired spectrum and color density can be obtained. Here, solid content in this specification means the total amount of the component remove | excluding the solvent from the colored photosensitive resin composition.

  The colored curable resin composition of the present invention contains a binder resin (B). Although it does not specifically limit as binder resin (B), It is preferable that it is alkali-soluble resin. Here, the alkali solubility means a property of being dissolved in a developer which is an aqueous solution of an alkali compound. Examples of the binder resin (B) include the following resins [K1] to [K6].

[K1] at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”).
[K2] (a), (b), and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) [K3] Copolymer of (a) and (c) [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c).
[K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).
[K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 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 Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

  (B) has, for example, a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. It refers to a polymerizable compound. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.

  Examples of (b) include a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  (B1) is, for example, a monomer (b1-1) having a structure obtained by epoxidizing an alkene (hereinafter sometimes referred to as “(b1-1)”), or a monomer having a structure obtained by epoxidizing a cycloalkene (B1-2) (hereinafter may be referred to as “(b1-2)”).

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

[In Formula (I) and Formula (II), R ^a and R ^b 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 is a hydroxy group May be substituted.
X ^a and ^{X b} are each independently a single ^{bond, -R c -, * - R} c -O -, * - R c -S -, * - represents the R c -NH-.
R ³ represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

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.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ¹ and R ² are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O), or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) Is mentioned. More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, it is called dicyclopentanyl (meth) acrylate as a common name), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (Meta Acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) (meth) acrylic acid esters such as acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

  Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [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-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [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-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

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, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 40 mol%)
Structural unit derived from (b); 50 to 98 mol% (more preferably 60 to 90 mol%)
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and stirred, heated, and kept warm in a deoxygenated atmosphere. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer, and a solvent (H) described later can be used as a solvent for the colored curable resin composition.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using a solvent (H) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%)
Structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%)
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, heat resistance, and mechanical strength tend to be excellent.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].
Specifically, a predetermined amount of (a), (b) and (c), a polymerization initiator, and a solvent are charged into a reaction vessel, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
(A) 2 to 50 mol%, more preferably 5 to 40 mol%
(C) 50 to 98 mol%, more preferably 60 to 95 mol%
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (c) has a cyclic ether having 2 to 4 carbon atoms, and / or is added to a carboxylic acid anhydride. Can be manufactured.
First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
(B) 5 to 50 mol%, more preferably 10 to 45 mol%
(C) 50 to 95 mol%, more preferably 55 to 90 mol%

Next, the carboxy group and / or part of the carboxylic acid anhydride contained in the structural unit derived from (c) in the copolymer is reacted with a C2-C4 cyclic ether of (b). .
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and 5 to 80 mol% of (b), carboxylic acid or 0.001 to 5% by mass of a polymerization catalyst of carboxylic acid anhydride and cyclic ether (for example, tris (dimethylaminomethyl) phenol) with respect to the total amount of (a), (b) and (c), and polymerization An inhibitor (for example, hydroquinone etc.) etc. is put into a flask 0.001-5 mass% with respect to the total amount of (a), (b), and (c), for example, at 60-130 degreeC, 1- Resin [K4] can be obtained by reacting for 10 hours. The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
In this case, the amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable.
Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
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 all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product. A carboxylic acid anhydride may be further reacted with a hydroxy group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride) and the like. It is done.

Specific examples of the binder resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.02 ^{. 6} ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / ( (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- Resin such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylic Relate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer resin [K3]; glycidyl (meth) acrylate added to benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) Resin such as resin obtained by adding glycidyl (meth) acrylate to acrylic acid copolymer [K4]; (meth) acrylic acid is reacted with dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin, dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin such as a resin obtained by reacting (meth) acrylic acid with a copolymer of a rate [K5]; (meth) acrylic acid reacted with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate And resin [K6] such as a resin obtained by further reacting tetrahydrophthalic anhydride with the resin.

  Among these, as the binder resin (B), resin [K3], resin [K4] and resin [K6] are preferable, resin [K3] is more preferable, and benzyl (meth) acrylate / (meth) acrylic acid copolymer is preferable. Further preferred.

The weight average molecular weight in terms of polystyrene of the binder resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the molecular weight is in the above range, the coating property tends to be excellent, the solubility of the unexposed portion in the developer tends to be high, and the remaining film ratio of the resulting pattern tends to be high.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4. When the molecular weight distribution is in the above range, the developability tends to be excellent.

  The acid value of binder resin (B) becomes like this. Preferably it is 20-150 mg-KOH / g, More preferably, it is 50-135 mg-KOH / g, More preferably, it is 70-135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

  The content of the binder resin (B) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, particularly preferably 30 to 60% by mass, based on the solid content of the colored curable resin composition. It is. When the content of the binder resin (B) is in the above range, the solubility of the unexposed area in the developer tends to be high.

  The colored curable resin composition of the present invention contains a (meth) acryloyl compound (C). The (meth) acryloyl compound (C) is a compound having a (meth) acryloyl group, and is preferably a compound having three or more (meth) acryloyl groups.

  Examples of the compound having three or more (meth) acryloyl groups include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripentaerythritol octa (meth) acrylate. , Tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, and the like.

  The acid value of the (meth) acryloyl compound (C) is preferably less than 20 mg-KOH / g. As the (meth) acryloyl compound (C), dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable, and dipentaerythritol hexamethacrylate is more preferable. Said (meth) acryloyl compound may be used individually or in combination of 2 or more types.

  1-50 mass% is preferable with respect to solid content of a colored curable resin composition, and, as for content of a (meth) acryloyl compound (C), 5-45 mass% is more preferable. When the content of the (meth) acryloyl compound (C) is in the above range, the resulting pattern tends to be excellent in strength, solvent resistance, and mechanical properties.

  The colored curable resin composition of the present invention contains a vinyl ether compound (D). The vinyl ether compound (D) is a compound having a vinyloxy group, and is preferably a compound having three or more vinyloxy groups.

  Examples of the compound having three or more vinyloxy groups include trimethylolpropane trivinyl ether, trimethylolpropane ethyloxytrivinyl ether, pentaerythritol tetravinyl ether, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol pentavinyl ether, Examples include pentaerythritol tetravinyl ether and dipentaerythritol trivinyl ether.

  0.1-50 mass% is preferable with respect to solid content of a colored curable resin composition, and, as for content of a vinyl ether compound (D), 1-30 mass% is more preferable. When the content of the vinyl ether compound (D) is in the above range, the resulting pattern tends to be excellent in strength, solvent resistance, and mechanical properties.

The colored curable resin composition of the present invention contains a polymerization initiator (E). The polymerization initiator (E) is particularly limited as long as it generates an active radical by the action of light or heat and can initiate polymerization of the (meth) acryloyl compound (C) and / or the vinyl ether compound (D). A known radical polymerization initiator can be used without any problem.
The polymerization initiator (E) is preferably a compound that generates an active radical by the action of light, more preferably an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, an oxime compound and a biimidazole compound, an acyl phosphine oxide compound and an alkyl. More preferred are phenone compounds.

  Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl. Butan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- And oligomers of [4- (1-methylvinyl) phenyl] propan-1-one, etc. Examples thereof include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. It is done. Commercial products such as Irgacure 369, 907 (above, manufactured by BASF) may be used.

  As triazine compounds, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine. Although a triazine compound can be used also as an acid generator, when the coloring curable resin composition of this invention contains a triazine compound, the content is counted as content of a polymerization initiator (E).

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by Ciba Japan) may be used.

  Examples of oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2. -Imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6 {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxypheny ) Biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), an imidazole in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group And compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

Furthermore, as the polymerization initiator (E), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (G) (particularly amines) described later.
The above polymerization initiators may be used alone or in combination of two or more.

  The content of the polymerization initiator (E) is preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the binder resin (B), (meth) acryloyl compound (C) and vinyl ether compound (D). More preferably, it is 1-30 mass parts. When the content of the polymerization initiator (E) is in the above range, a pattern can be formed with high sensitivity, and the resulting pattern tends to be excellent in solvent resistance, mechanical strength, and surface smoothness.

  The colored curable resin composition of the present invention contains an acid generator (F). The acid generator (F) is not particularly limited as long as it is a compound that generates an acid by the action of light or heat, and a known acid generator can be used. The acid generator includes a nonionic compound and an ionic compound. As the acid generator (F), alone or in combination with the polymerization initiation assistant (G), an acid generator that generates an acid by the action of light having a wavelength of 250 to 450 nm (preferably 300 to 400 nm), or An acid generator having a thermal decomposition temperature of 100 ° C. or higher and 180 ° C. or lower (preferably 120 ° C. or higher and 150 ° C. or lower) is preferable. The thermal decomposition temperature can be measured by differential scanning calorimetry (DSC).

  Examples of nonionic compounds include diazoketone compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, sulfonyloxyimide compounds, and sulfonyloxybenzotriazole compounds.

  Examples of the diazo ketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Preferred diazo ketone compounds include ester compounds of 1,2-naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid and 2,3,4,4′-tetrahydroxybenzophenone, 1,2 -Ester compound of naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid and 1,1,1-tris (4-hydroxyphenyl) ethane, 1,2-naphthoquinonediazide-5-sulfone Esters of acid or 1,2-naphthoquinonediazide-4-sulfonic acid with 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] diphenol Is mentioned.

  Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylylsulfonyl) diazomethane. Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane Etc.

  Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryl disulfone compounds, and the like. Preferred examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-chlorophenyl-4-methylphenyldisulfone compound, and the like.

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, and imino sulfonate. Preferred examples include benzoin tosylate, pyrogallol trimesylate, trobenzyl-9,10-diethoxyanthracene-2-sulfonate, 2,6-dinitrobenzylbenzenesulfonate, and the like. As iminosulfonate, for example, PAI-101 (manufactured by Midori Chemical Co., Ltd.), PAI-106 (manufactured by Midori Chemical Co., Ltd.), CGI-1311 (manufactured by Ciba Japan Co., Ltd.) can be used.

  Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

  Examples of the sulfonyloxyimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenyl). Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) di Phenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) ) Diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (tri Fluoromethylsulfonyloxy) -7-oxa Cyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarbo Silimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2 2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyl Imido, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [ 2.2.1] Heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicycle [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- ( Pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide, N- (d Rusulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyl) Examples include oxy) naphthyl dicarboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, and the like.

  Examples of the sulfonyloxybenzotriazole compound include 1-trifluoromethanesulfonyloxybenzotriazole, 1-nonafluorobutylsulfonyloxybenzotriazole, 1- (4-methylphenylsulfonyloxy) -benzotriazole, and the like.

As an ionic compound, what is comprised from the onium cation and the anion derived from a Lewis acid or a proton acid can be used.
Examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (p -Octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p-tolyl) Sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butylphenyl) sulfonium, tris (p-cyano) Eniru) sulfonium, tris (p- chlorophenyl) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium and the like. Among them, preferable onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium or tris (p-tert-). Butylphenyl) sulfonium and the like.

Examples of the anion derived from a Lewis acid include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate.
Examples of the anion derived from a protonic acid include methanesulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, camphorsulfonate, and the like.
As the anion, hexafluoroantimonate or tetrakis (pentafluorophenyl) borate is preferable. The onium cation and the anion derived from Lewis acid or proton acid can be arbitrarily combined.

  Examples of the ionic compound include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexafluorophosphate. Bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoro Phosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate DOO, methyl naphthyl hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate;

  Triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2,6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert- Butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexafluorophosphate, dimethyl (tris (trichloro Methyl) methyl) sulfonium hexafluorophosphate ;

  Diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl) iodonium hexafluoroarsenate, bis (p -Octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, methylnaphthyl iodonium Oxafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate, tris (p-isopropylphenyl) sulfonium hexafluoroarsenate, tris (2, 6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate , Dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroarsenate;

  Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p -Octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl naphthalate Tyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris ( 2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoro Antimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthyl Sulfo hexafluoroantimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroantimonate;

  Diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate, bis (P-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) iodoniu Tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyliodonium tetrakis ( Pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) Sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) Rufonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) Sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) borate;

  Diphenyliodonium trifluoromethanesulfonate, bis (p-tolyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, tris (p-tolyl) sulfonium trifluoromethanesulfonate, tris (p-isopropylphenyl) sulfonium trifluoromethanesulfonate, tris (2 , 6-Dimethylphenyl) sulfonium trifluoromethanesulfonate.

  Among them, preferably bis (p-tolyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, 4-methylphenyl [ 4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroantimony Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium Hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p -Isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, more preferably bis (P-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroa Timonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, 4-methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluoroantimonate, Tris (P-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (P-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) Examples thereof include borate and tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

The above acid generators may be used alone or in combination of two or more.
The content of the acid generator (F) is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and 1 to 12% by mass with respect to (solid content of the colored curable resin composition). Is more preferable. When the content of the acid generator (F) is in the above range, the resulting pattern tends to be excellent in strength, solvent resistance, and adhesion.

The colored curable resin composition of the present invention may contain a polymerization initiation assistant (G). When the polymerization initiation assistant (G) is contained, it is usually used in combination with at least one selected from the group consisting of a polymerization initiator (E) and an acid generator (F). The polymerization initiation assistant (G) is a compound used for accelerating the polymerization of the polymerizable compound initiated by the polymerization initiator (E), or from the polymerization initiator (E) and the acid generator (F). A sensitizer acting on at least one selected from the group consisting of 250 to 450 nm (preferably 300 to 400 nm) at least one selected from the group consisting of a polymerization initiator (E) and an acid generator (F). It is preferable that the compound is sensitized with light having a wavelength of.
Examples of the polymerization initiation aid (G) include thioxanthone compounds, amine compounds, alkoxyanthracene compounds, thiazoline compounds, carboxylic acid compounds, and the like, and thioxanthone compounds are preferred.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

Examples of the thiazoline compound include compounds represented by formula (V-1) to formula (V-3).

Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
The above polymerization initiation assistants may be used alone or in combination of two or more.

  Further, when the polymerization initiation assistant (G) is used, the content thereof is preferably based on 100 parts by mass of the total amount of the binder resin (B), the (meth) acryloyl compound (C) and the vinyl ether compound (D). It is 0.01-50 mass parts, More preferably, it is 0.1-40 mass parts. Moreover, it is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol per mol of the polymerization initiator (E). Since the pattern can be formed with high sensitivity when the content of the polymerization initiation assistant (G) is in the above range, the productivity of the pattern tends to be improved.

  The colored curable resin composition of the present invention may contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) is a compound having two or more sulfanyl groups. Among these, a compound having two or more sulfanyl groups bonded to a carbon atom derived from an aliphatic hydrocarbon group is preferable because a pattern can be formed with high sensitivity.

As the polyfunctional thiol compound (T), hexanedithiol, decanedithiol, 1,
4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate) ), Butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), Pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyltris (3-sulfanylpropionate), pentaerythritol tetrakis (3-s Phenylsulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) butane and the like. These polyfunctional thiol compounds may be used alone or in combination of two or more.

  The content of the polyfunctional thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polymerization initiator (E). 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 excellent.

The colored curable resin composition of the present invention preferably contains a solvent (H).
A solvent (H) is not specifically limited, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), ketones other than ester solvents A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, or the like can be selected and used.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol 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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like diethylene glycol monobutyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

  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, xylene, mesitylene and the like.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Among these, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, propylene glycol monomethyl ether, and ethyl 3-ethoxypropionate are preferable, and propylene glycol monomethyl ether acetate, cyclohexanone, and propylene glycol monomethyl ether are more preferable.

  The content of the solvent (H) in the colored curable resin composition is preferably 60 to 95% by mass and more preferably 70 to 90% by mass with respect to the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. When the content of the solvent (H) is in the above range, the flatness at the time of coating is excellent, and when the color filter is formed, the color density does not become insufficient, and thus the display characteristics tend to be excellent.

The colored curable resin composition of the present invention preferably further contains a surfactant (J). Examples of the surfactant (J) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan GK) Manufactured) and the like.

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck (trade name) F142D, F171, F172, F173, F177, F183, F183, R30, RS-718-K (manufactured by DIC Corporation), EFtop (trade name) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (tradename) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.

  The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.1% by mass with respect to the colored curable resin composition. Below, more preferably 0.01 mass% or more and 0.05 mass% or less. When the content of the surfactant (F) is in the above range, a coating film with high flatness can be obtained.

  The colored curable resin composition of the present invention includes various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, and the like as necessary. May be included.

  The colored curable resin composition of the present invention can be prepared, for example, as follows. First, the pigment of the colorant (A) is preliminarily mixed with the solvent (H) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and binder resin (B) as needed. In the obtained pigment dispersion, the remainder of the binder resin (B), the (meth) acryloyl compound (C), the vinyl ether compound (D), the polymerization initiator (E) and the acid generator (F) are used as necessary. Other components to be added, and if necessary, an additional solvent may be added so as to have a predetermined concentration to obtain a desired colored curable resin composition.

Examples of a method for forming a color filter pattern using the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. In the photolithographic method, the colored curable resin composition is applied to a substrate, a volatile component such as a solvent is removed (dried) to form a colored layer, and the colored layer is exposed and developed through a photomask. Is the method. In the photolithographic method, a coating film may be formed by not using a photomask and / or not developing during exposure.
The film thickness of the pattern to be produced is not particularly limited and can be appropriately adjusted depending on the material used, the use, and the like. For example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm. It is.

Examples of the substrate include glass, metal, plastic and the like, and may be plate-like or film-like.
Examples of the plastic include polyolefins such as polyethylene, polypropylene, norbornene-based polymers, polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, poly (meth) acrylate, cellulose ester, polycarbonate, polysulfone, polyethersulfone, polyetherketone, Examples include polyphenylene sulfide and polyphenylene oxide. Here, (meth) acrylic acid means at least one selected from the group consisting of acrylic acid and methacrylic acid. Structures such as a color filter, various insulating or conductive films, and a drive circuit may be formed on these substrates.

  Coating methods include extrusion coating, direct gravure coating, reverse gravure coating, CAP coating, die coating, dip coating, roll coating, bar coating, spin coating, slit and spin coating, and slit coating. And the like (including the die coating method, the curtain flow coating method, and the spinless coating method) and the inkjet coating method. Of these, the slit coat method, the spin coat method, and the roll coat method are preferable.

  As a method of forming each color pixel by the photolithography method, a known or commonly used method can be used. For example, it can be formed as follows.

A colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed (dried) to obtain a smooth coating film. Examples of the drying method include methods such as heat drying, natural drying, ventilation drying, and vacuum drying. A plurality of methods may be combined.
10-120 degreeC is preferable and, when performing heat drying, natural drying, and ventilation drying, 25-100 degreeC is more preferable. Moreover, it is preferable that it is below the thermal decomposition temperature of the acid generator (F) contained in a colored curable resin composition. The drying time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coating film after drying is not specifically limited, It can adjust suitably with the material to be used, a use, etc., for example, is 0.1-20 micrometers, Preferably it is 0.5-6 micrometers.

After drying, the coating film is exposed through a photomask for forming a target pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended application is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an apparatus such as a mask aligner or a stepper because the entire exposed surface can be irradiated with parallel rays uniformly and accurate alignment between the mask and the substrate can be performed.

After exposure, a pattern can be obtained by contacting a developing solution to dissolve a predetermined portion, for example, an unexposed portion, and developing. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, tetramethylammonium hydroxide and the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.
Furthermore, you may post-bake as needed. The post-baking temperature is preferably 25 ° C. or higher and 230 ° C. or lower, more preferably 25 ° C. or higher and 200 ° C. or lower, further preferably 25 ° C. or higher and 160 ° C. or lower, and particularly preferably 25 ° C. or higher and 120 ° C. or lower. The post-bake time is 1 to 300 minutes, preferably 1 to 180 minutes, and more preferably 1 to 60 minutes.

  According to the colored curable resin composition of the present invention, a color filter particularly excellent in contrast can be produced. The color filter is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, etc.), electronic paper, a solid-state image sensor, and the like.

  Next, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Examples 1 and 2 and Comparative Example 1
Each component was mixed so that it might become a composition shown in Table 1, and the colored curable resin composition was obtained.

In Table 1, each component represents the following. Moreover, binder resin (B) showed the mass part of solid content conversion.
Colorant (A): (A-1): C.I. I. Pigment Blue 15: 6
Binder resin (B): (B-1): Copolymer of benzyl methacrylate and methacrylic acid (mass composition ratio of benzyl methacrylate unit and methacrylic acid unit: 80/20, weight average molecular weight in terms of polystyrene: 28,000, Acid value: 91 mg-KOH / g)
(Meth) acryloyl compound (C): (C-1): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Vinyl ether compound (D): (F-1): Compound represented by the following formula (TMPEOTVE-60; manufactured by Nippon Carbide Industries Co., Ltd.)

Polymerization initiator (E): (E-1): Bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (Irgacure 819; manufactured by BASF)
Polymerization initiator (E): (E-2): 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF)
Acid generator (F): (F-1): 4-methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate (Rhodosyl 2074; manufactured by Rhodia)
Polymerization initiation assistant (G): (G-1): 2,4-diethylthioxanthone (KAYACURE DETX; manufactured by Nippon Kayaku Co., Ltd.)
Solvent (H): (H-1): Propylene glycol monomethyl ether acetate Solvent (H): (H-2): Cyclohexanone Surfactant (J): (J-1): Polyether-modified silicone oil (Tore Silicone SH8400 ; Toray Dow Corning Co., Ltd.)

<Pattern preparation>
A PET film (Lumirror 75-T60; manufactured by Toray Industries, Inc.) was bonded onto a 2-inch square glass plate to prepare a substrate. The colored curable resin composition was applied to the PET film side of the substrate by spin coating, and prebaked at 80 ° C. for 2 minutes on a hot plate. After standing to cool, the distance between the substrate coated with the colored curable resin composition and the quartz glass photomask is set to 150 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) is used in an air atmosphere at 150 mJ. Light was irradiated at an exposure amount of / cm ² (based on 365 nm). As the photomask, one having a 3 to 100 μm line and space pattern was used. After light irradiation, the film was developed by immersing in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 50 seconds, and washed with pure water. Then, the pattern was formed by post-baking at 60 degreeC for 5 minute (s). The film thickness of the obtained pattern was 2 μm when measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Resolution evaluation>
The obtained pattern was observed with a laser microscope (Axio Imager MAT; manufactured by Carl Zeiss), and the minimum dimension in which the pattern was resolved was defined as the resolution. The higher the resolution, the higher definition color filter can be produced. The results are shown in Table 2.

<Solvent resistance evaluation>
1 ml of propylene glycol monomethyl ether acetate was dropped onto the obtained pattern, and after standing for 30 seconds, the spin coater was used for rotation for 10 seconds at a rotation speed of 1000 rpm, and the propylene glycol monomethyl ether acetate on the pattern was shaken off.
The film thickness was measured before and after contact with propylene glycol monomethyl ether acetate, and the film thickness retention was calculated from the measured value according to the following formula.
(Film thickness retention) (%) = (film thickness after contact) / (film thickness before contact) × 100
Further, xy chromaticity coordinates (x, y) and brightness Y were measured before and after contact with propylene glycol monomethyl ether acetate, and the color difference was calculated from the measured values by the method described in JIS Z 8730. The xy chromaticity coordinates (x, y) and lightness Y were measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the CIE was measured using the characteristic function of the C light source. The xy chromaticity coordinates (x, y) and brightness Y in the XYZ color system were obtained. The results are shown in Table 2.
The higher the film thickness retention rate and the smaller the color difference, the better the solvent resistance, and color mixing can be prevented when producing a color filter.

  From the above results, it was confirmed that the pattern formed by the colored curable resin composition of the present invention was excellent in solvent resistance despite being formed at a low post-bake temperature. Moreover, the pattern formed with the colored curable resin composition of this invention has high resolution. From this, it can be seen that according to the colored curable resin composition of the present invention, it is possible to produce a color filter having excellent durability and high definition.

  According to the colored curable resin composition of the present invention, a pattern having excellent solvent resistance can be formed.

Claims (5)

A colored curable resin composition comprising (A), (B), (C), (D), (E) and (F).
(A) Colorant (B) Binder resin (C) Compound having at least one group selected from the group consisting of acryloyl group and methacryloyl group (however, it does not have vinyloxy group)
(D) Compound having vinyloxy group (E) Radical polymerization initiator (F) Acid generator   The colored curable resin composition according to claim 1, wherein (D) is a compound having three or more vinyloxy groups.   The colored curable resin composition according to claim 1 or 2, wherein (C) is a compound having at least three groups selected from the group consisting of an acryloyl group and a methacryloyl group.   The color filter formed with the colored curable resin composition as described in any one of Claims 1-3.   A display device comprising the color filter according to claim 4.