JP6622616B2 - Colored curable resin composition, color filter, and display device including the same - Google Patents

Description

  The present invention relates to a colored curable resin composition, a color filter, and a display device including the same.

  In recent years, liquid crystal display devices have been developed to widen the displayable color reproduction range, and as part of this, a darker color filter is required. As a method for darkening the color filter, there is a method of increasing the colorant concentration in the color filter. However, when the colorant concentration is increased, performance as a colored curable resin composition is deteriorated, such as deterioration of the pattern shape. Resulting in. On the other hand, by using a colorant having high coloring power, a dark color filter pattern can be produced, but the lightness is lowered. In addition, there is a method of expressing a dark color by using a thick color filter, but when the film is thickened, when applied to a liquid crystal display device, color mixture of light occurs between adjacent pixels.

  Japanese Patent Application Laid-Open No. 2011-084726 (Patent Document 1) discloses C.I. which is a polyhalogenated zinc phthalocyanine pigment. I. A colored curable composition for a color filter using Pigment Green 58 and a polymerizable compound having an ethylenically unsaturated compound modified with ethylene oxide is described.

JP 2011-084726 A

  In the above-mentioned colored curable composition known from the past, high brightness and pattern shape may not be sufficiently compatible. When the pattern shape is poor, when the inorganic film is laminated on the pattern, the inorganic film may be cracked or the inorganic film may be peeled off. The present invention relates to a colored curable resin composition capable of forming a color filter having high brightness and excellent pattern shape, a color filter formed from the colored curable resin composition, and a display device including the color filter The purpose is to provide.

  The present invention provides the following colored curable resin composition, color filter, and display device.

[1] Including a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
The colorant (A) is C.I. I. Pigment Green 59,
The polymerizable compound (C) is at least one (meth) acrylate (c1) selected from the group consisting of ethylene oxide-modified dipentaerythritol penta (meth) acrylate and ethylene oxide-modified dipentaerythritol hexa (meth) acrylate. A colored curable resin composition comprising:

  [2] The colored curable resin composition according to [1], wherein the polymerizable compound (C) further contains a (meth) acryloyl group-containing compound (c2) other than the (meth) acrylate (c1).

  [3] The colored curable resin composition according to [1] or [2], wherein the content of the (meth) acrylate (c1) is 20% by mass or more in 100% by mass of the polymerizable compound (C). object.

  [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 according to the present invention, it is possible to provide a color filter having high brightness and excellent pattern shape, and a display device including the color filter.

It is a schematic sectional drawing which shows the coloring pattern which has a forward taper shape. It is a schematic sectional drawing which shows the coloring pattern which has a reverse taper shape.

<Colored curable resin composition>
The colored curable resin composition according to the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). I. Pigment Green 59, and the polymerizable compound (C) is at least one selected from the group consisting of ethylene oxide-modified dipentaerythritol penta (meth) acrylate and ethylene oxide-modified dipentaerythritol hexa (meth) acrylate. Contains (meth) acrylate (c1). C. I. According to the colored curable resin composition according to the present invention including a specific combination of CI Pigment Green 59 and (meth) acrylate (c1), it is possible to form a color filter that achieves both high brightness and excellent pattern shape. It becomes.

  Hereinafter, although each component is demonstrated in detail, the compound illustrated as each component in this specification can be used individually or in combination of multiple types unless there is particular notice.

[1] Colorant (A)
In the colored curable resin composition according to the present invention, the colorant (A) is C.I. I. Pigment Green 59 is included. C. in the colorant (A) I. The content of Pigment Green 59 is usually 10 to 100% by mass in 100% by mass of the colorant (A), and preferably 30 to 100% by mass from the viewpoint of effectively achieving both high brightness and excellent pattern shape. %, More preferably 40 to 100% by mass, still more preferably 45 to 100% by mass. As will be described later, the colorant (A) is C.I. I. Other colorants other than CI Pigment Green 59 can be included. I. The content of Pigment Green 59 may be 90% by mass or less, 100% by mass or less, 70% by mass or less, and 60% by mass in 100% by mass of the colorant (A). % Or less.

  The colorant (A) is C.I. I. Other colorants other than CI Pigment Green 59 can be included. Other colorants include C.I. I. It may be a pigment other than CI Pigment Green 59, a dye, or both of them. Other colorants may be used alone or in combination of two or more. Examples of other pigments include organic pigments and inorganic pigments, and compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).

C. I. As other pigments other than Pigment Green 59, for example,
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16, 60;
C. I. Pigment Green 7, 36, 58, etc. I. Green pigments other than Pigment Green 59;
C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
Etc.

  Among them, C.I. I. The pigment other than CI Pigment Green 59 is preferably a yellow pigment. Among the yellow pigments, the other pigments are C.I. in contrast with the same color filter thickness and the same colorant concentration. I. In combination with Pigment Green 59, better brightness can be obtained. I. Pigment Yellow 138, 139, 150, 185 and the like are preferable. I. More preferably, it includes CI Pigment Yellow 138.

  C. in the green colorant from the viewpoint of effectively achieving both high brightness and excellent pattern shape. I. It is preferable to increase the content of Pigment Green 59. Specifically, C.I. I. The content of Pigment Green 59 is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% in 100% by mass of the green colorant. It is at least mass%, most preferably 100 mass%.

  The other colorant may be a dye. Known dyes can be used as the dye, and examples include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include compounds classified as those having a hue other than pigment in the color index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (color dyeing company). It is done. Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye Examples thereof include dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

  The colorant (A) is C.I. I. When other colorants other than CI Pigment Green 59 are included, the content of the other colorants is from 100% by mass of the colorant (A) from the viewpoint of effectively achieving both high brightness and excellent pattern shape. Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more, More preferably, it is 30 mass% or more (for example, 40 mass% or more).

  The total content of the colorant (A) in the colored curable resin composition is usually 10 to 60% by mass in 100% by mass of the solid content of the colored curable resin composition, but it has high brightness and an excellent pattern shape. From the viewpoint of satisfying both, the solid content of the colored curable resin composition is preferably 100 to 50% by mass, more preferably 15 to 50% by mass, and more preferably 20 to 50% by mass. In the present specification, the “solid content of the colored curable resin composition” refers to all components other than the solvent (E) among the components contained in the colored curable resin composition.

  The various pigments used in the preparation of the colored curable resin composition are preferably in the state of a dispersion that is uniformly dispersed in a solvent. The pigment preferably has a uniform particle size. The dispersion can be obtained by mixing a pigment and a solvent. If necessary, a pigment dispersant may be mixed. By carrying out a dispersion treatment by containing a pigment dispersant, it is possible to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solvent.

  Commercially available surfactants can be used as the pigment dispersant, including silicone, fluorine, ester (including polyester), cationic, anionic, nonionic, amphoteric, polyester, polyamine, Examples of the surfactant include acrylic. Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Ajisper (registered trademark) (Ajinomoto Fine Techno Co., Ltd.), Disperbyk (Bic Chemie Co., Ltd.) and the like. Only one pigment dispersant may be used, or two or more pigment dispersants may be used in combination.

  When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in a uniform dispersion state tends to be obtained.

  It does not specifically limit as a solvent which comprises a pigment dispersion liquid, The solvent similar to the below-mentioned solvent (E) which can be contained in a colored curable resin composition is mentioned. Among them, the solvents are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy- 1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxy Must be butyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, etc. Preferred. Two or more solvents may be used in combination.

  Although the usage-amount of a solvent is not specifically limited, The density | concentration of the solid content in a pigment dispersion liquid is preferably 3-20 mass%, More preferably, it is the quantity used as 5-18 mass%.

  Various pigments used in the preparation of the colored curable resin composition include rosin treatment, surface treatment using a pigment derivative or pigment dispersant into which an acidic group or basic group is introduced, a polymer compound, if necessary Grafting to the pigment surface by etc., atomization treatment by sulfuric acid atomization method, etc., washing treatment with organic solvent or water to remove impurities, removal treatment by ion exchange method of ionic impurities etc. It may be.

[2] Resin (B)
The colored curable resin composition of the present invention contains a resin (B). The colored curable resin composition can contain one or more resins as the resin (B). The resin (B) is preferably an alkali-soluble resin. Alkali-soluble refers to the property of being dissolved in a developer which is an aqueous solution of an alkali compound. Examples of the resin (B) include the following resins [K1] to [K6].

  Resin [K1]: At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as “(a)”). ] And a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter sometimes referred to as “(b)”. ) And a copolymer.

  Resin [K2]: (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) [hereinafter referred to as “(c)” There is. ] And a copolymer.

Resin [K3]: Copolymer of (a) and (c).
Resin [K4]: A resin obtained by reacting (b) with a copolymer of (a) and (c).

Resin [K5]: A resin obtained by reacting (a) with a copolymer of (b) and (c).
Resin [K6]: A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

Specifically, as (a),
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, 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 (meth) acrylic acids containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) (meth) acrylic acid.

  Especially, it is preferable that (a) is (meth) acrylic acid, maleic anhydride, etc. from a viewpoint of copolymerization reactivity or a solubility viewpoint to aqueous alkali solution.

  In the present specification, “(meth) acryl” represents at least one selected from the group consisting of acryl and methacryl. The same applies to notations such as “(meth) acryloyl” and “(meth) acrylate”.

  (B) is a polymerization having a cyclic ether structure 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 (oxolane ring)) and an ethylenically unsaturated bond. Refers to a chemical compound. (B) is preferably a monomer having a C2-C4 cyclic ether structure and a (meth) acryloyloxy group.

  As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter, referred to as “(b1)”. ], A monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as “(b2)”. ] A monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as “(b3)”. ] Etc. are mentioned.

  (B1) is a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter referred to as “(b1-1)”. ] Monomer (b1-2) having a structure obtained by epoxidizing unsaturated alicyclic hydrocarbon [hereinafter, 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.), and represented by the following formula (I) Examples thereof include compounds and compounds represented by the following 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 ¹ and X ² are, independently of one another, a single ^{bond, * - R c -, *} - R c -O -, * - R c -S-, or * represents a -R ^c -NH-. R ^c 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 ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group constituting R ^c include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5- Examples thereof include a diyl group and a hexane-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) group, or * —CH ₂ CH ₂ —O— group. More preferably a single bond or a * —CH ₂ CH ₂ —O— group.

  Specific examples of the compound represented by the formula (I) include compounds represented by the following formula (I-1) to the following 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) More preferred are formula (I-1), formula (I-7), formula (I-9), and formula (I-15).

  Specific examples of the compound represented by the formula (II) include compounds represented by the following formula (II-1) to the following 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) More preferred are formula (II-1), formula (II-7), formula (II-9), and formula (II-15).

  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. In the case of mixing, the mixing ratio is the formula (I): formula (II) [molar ratio], preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, still more preferably 20: 80-80: 20.

  The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. Preferred examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

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

Specific examples of (c) are:
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 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 ] decane-8- Ile (meth) acrylate [in this technical field, it is called "dicyclopentanyl (meth) acrylate" as a common name. It may also be called “tricyclodecyl (meth) acrylate”. ], Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate [in this technical field, it is called "dicyclopentenyl (meth) acrylate" as a common name. ], Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meth) acrylic acid esters such as (meth) 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 [2.2 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, etc. Bicyclounsaturated 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.

  Among these, from the viewpoint of copolymerization reactivity and heat resistance, (c) is benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo. [2.2.1] hept-2-ene and the like are preferable. Moreover, since it is excellent in the developability at the time of pattern formation, (c) has more preferable benzyl (meth) acrylate and tricyclodecyl (meth) acrylate.

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].
A structural unit derived from (a); 2-50 mol% (more preferably 10-45 mol%),
A structural unit derived from (b), particularly a structural unit derived from (b1); 50 to 98 mol% (more preferably 55 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.

  Resin [K1] is described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document. It can be produced with reference to the cited references.

  Specifically, there is a method in which a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent, and the like are charged into a reaction vessel and stirred, heated, and kept warm in a deoxygenated atmosphere. Can be mentioned. 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. Examples of the polymerization initiator include azo compounds (such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide). It is done. The solvent is not particularly limited as long as it dissolves each monomer, and a solvent (E) 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 (E) 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].
A structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%),
A structural unit derived from (b), in particular a structural unit derived from (b1); 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 in the same manner as described for the production method of resin [K1]. Specifically, a predetermined amount of (a), (b) (particularly (b1)) 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. The method of doing is mentioned. 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 structural unit derived from (a); 2-55 mol% (more preferably 10-50 mol%),
Structural unit derived from (c); 45 to 98 mol% (more preferably 50 to 90 mol%).

  Resin [K3] can be produced in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (b) has an oxirane ring of (b1) having a C2-C4 cyclic ether structure (b). It can manufacture by adding to the carboxylic acid and / or carboxylic anhydride which it has. Specifically, first, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the resin [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).
A structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%),
Structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol%).

  Next, a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer has a C2-C4 cyclic ether structure (b1), particularly (b1). React the oxirane ring. Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with nitrogen to air, and (b) (particularly (b1)), carboxylic acid or carboxylic anhydride A reaction catalyst (such as tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (such as hydroquinone) in a flask and reaction at 60 to 130 ° C. for 1 to 10 hours. Resin [K4] can be obtained.

  The amount of (b) used, in particular (b1), 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 structure is high and unreacted (b) hardly remains, (b1) is preferable as (b) used in the resin [K4], and (b1-1) is more preferable.

  It is preferable that the usage-amount of the said reaction catalyst is 0.001-5 mass% with respect to the total amount of (a), (b) (especially (b1)) and (c). It is preferable that the usage-amount of the said polymerization inhibitor is 0.001-5 mass% with respect to the total amount of (a), (b) and (c).

  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.

  Resin [K5] obtains a copolymer of (b) (particularly (b1)) and (c) 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) (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
A structural unit derived from (b), in particular a structural unit derived from (b1); 5-95 mol% (more preferably 10-90 mol%),
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%).

  Furthermore, under the same conditions as in the production method of the resin [K4], the cyclic ether structure derived from (b) of the copolymer of (b) (particularly (b1)) and (c), The resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride having the resin. The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b) (particularly (b1)). Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, (b1) is preferable as (b) used in 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 the hydroxy group generated by the reaction of the cyclic ether structure 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.

  Of the resins [K1] to [K6], a preferable resin as the resin (B) is [K1] or [K2]. Resin (B) may consist of 1 type of resin, and may contain 2 or more types of resin.

  The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the solubility of the unexposed area in the developer is high, and the residual film ratio and hardness of the resulting pattern tend to be high. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The solution acid value of the resin (B) is preferably 5 to 180 mg-KOH / g, more preferably 10 to 100 mg-KOH / g, and further preferably 12 to 50 mg-KOH / g. 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, for example, by titrating with an aqueous potassium hydroxide solution.

  The content of the resin (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% in the solid content of 100% by mass of the colored curable resin composition. % By mass. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

[3] Polymerizable compound (C)
The polymerizable compound (C) is a compound that can be polymerized by an active radical generated from the polymerization initiator (D) by light irradiation or the like. In the colored curable resin composition of the present invention, the polymerizable compound (C) is at least selected from the group consisting of ethylene oxide-modified dipentaerythritol penta (meth) acrylate and ethylene oxide-modified dipentaerythritol hexa (meth) acrylate. Contains one (meth) acrylate (c1). (Meth) acrylate (c1) has the following formula:

It is a (meth) acrylate compound represented by these. In said formula, X represents an acryloyl group or a methacryloyl group each independently. Y represents a hydrogen atom, an acryloyl group or a methacryloyl group. a to f are integers of 1 or more, and a + b + c + d + e + f + g, which is the sum of a to f, is an integer of 6 to 24. The total of a to f is preferably 6 to 18. The ethylene oxide-modified dipentaerythritol penta (meth) acrylate is a compound in which Y is a hydrogen atom in the above formula, and the ethylene oxide-modified dipentaerythritol hexa (meth) acrylate is a compound in which Y is an acryloyl group or a methacryloyl group in the above formula. It is a certain compound. The polymerizable compound (C) may contain, as (meth) acrylate (c1), only a compound in which Y is a hydrogen atom in the above formula, or only a compound in which Y is an acryloyl group or a methacryloyl group. Or both of them may be included.

  The colorant (A) is C.I. I. According to the colored curable resin composition of the present invention that includes CI Pigment Green 59 and the polymerizable compound (C) includes (meth) acrylate (c1), a color filter that achieves both high brightness and excellent pattern shape. Can be formed.

  (Meth) acrylate (c1) is, for example, a process of ring-opening addition of ethylene oxide to dipentaerythritol and a terminal hydroxyl group derived from ethylene oxide introduced by ring-opening addition by reacting (meth) acryloyl chloride or (meth) acrylic acid. And a step of introducing a (meth) acryloyl group; synthesizing ethylene oxide-modified (meth) acrylic acid by ring-opening addition of ethylene oxide to (meth) acrylic acid, followed by esterification with dipentaerythritol It can be manufactured by a method or the like.

  The polymerizable compound (C) can further contain a polymerizable compound other than the (meth) acrylate (c1). The weight average molecular weight of the other polymerizable compound is preferably 3000 or less. The colored curable resin composition of the present invention may contain one or more other polymerizable compounds in addition to (meth) acrylate (c1). The other polymerizable compound preferably includes a compound having a polymerizable ethylenically unsaturated bond, and more preferably a (meth) acryloyl group (for example, (meth) acryloyloxy) as the polymerizable ethylenically unsaturated bond. Group) containing (meth) acryloyl group-containing compound (c2).

  Among them, the (meth) acryloyl group-containing compound (c2) is preferably a polymerizable compound having three or more (meth) acryloyl groups in the molecule, and specific examples thereof include trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) Acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethyl Glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (Meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate and the like. Of these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.

  The content of the polymerizable compound (C) is preferably 10 to 150 parts by mass, more preferably 50 to 120 parts by mass with respect to 100 parts by mass of the resin (B) in the colored curable resin composition. .

  From the viewpoint of effectively achieving both high brightness and excellent pattern shape, the content of (meth) acrylate (c1) in the polymerizable compound (C) is preferably high. Specifically, the content of (meth) acrylate (c1) is usually 20% by mass, preferably 50% by mass, more preferably 70% by mass or more, in 100% by mass of the polymerizable compound (C). More preferably, it is 80% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

[4] Polymerization initiator (D)
The colored curable resin composition of the present invention contains a polymerization initiator (D). The colored curable resin composition can contain one or more polymerization initiators as the polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and starting polymerization, and a known polymerization initiator can be used.

  Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acyl phosphine oxide compounds. Two or more polymerization initiators (D) may be used in consideration of sensitivity, formability of a precise pattern shape, and the like. The polymerization initiator (D) is advantageous for precisely creating a pattern shape having sensitivity and a desired line width, and therefore preferably contains an oxime compound such as an O-acyl oxime compound.

  The O-acyl oxime compound is a compound having a structure represented by the following formula (d). Hereinafter, * represents a bond.

  Examples of the O-acyl oxime compound include a compound represented by the following formula (d1) (hereinafter sometimes referred to as “compound (d1)”) and a compound represented by the formula (d2) (hereinafter referred to as “compound ( d2) ”) and a compound represented by the formula (d3) (hereinafter sometimes referred to as“ compound (d3) ”). .

In formulas (d1) to (d3),
R ^d1 has an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, and a substituent. Represents an optionally substituted alkyl group having 1 to 15 carbon atoms, or an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, which may have a substituent. The included methylene group (—CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms,
R ^d3 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms,
R ^d4 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms; The methylene group (—CH ₂ —) contained in the aromatic hydrocarbon group may be replaced by —O—, —CO— or —S—, and the methine group (—CH < ) May be replaced with —PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the alkyl group may be replaced with —O— or —CO—.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d1 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like. A phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

The aromatic hydrocarbon group represented by R ^d1 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, and more preferably substituted at the γ-position. Examples of the substituent include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group An alkyl group having 1 to 15 carbon atoms such as a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom;

The alkyl group as the substituent preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms. The alkyl group as the substituent may be linear, branched, or cyclic, or may be a group that combines a linear group and a cyclic group. The methylene group (—CH ₂ —) contained in the alkyl group as the substituent may be replaced with —O— or —S—. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and is preferably substituted with a fluorine atom.

Examples of the alkyl group as a substituent for the aromatic hydrocarbon group represented by R ^d1 include groups represented by the following formulas. In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d1 include a group represented by the following formula. In the formula, * represents a bond.

As the aromatic hydrocarbon group which may have a substituent represented by R ^d1 , a group represented by the following formula is preferable.

In the formula, R ^d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and the hydrogen atom contained in R ^d6 may be substituted with a halogen atom. m2 represents an integer of 1 to 5.

Examples of the alkyl group represented by R ^d6 include the same groups as the alkyl groups exemplified as the substituent for the aromatic hydrocarbon group represented by R ^d1 . R ^d6 has preferably 2 to 7 carbon atoms, more preferably 2 to 5 carbon atoms. The alkyl group represented by R ^d6 may be linear, branched, or cyclic, and is preferably linear.

Examples of the halogen atom that may substitute the hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and fluorine is particularly preferable. In addition, 2 or more and 10 or less of hydrogen atoms contained in R ^d6 are preferably substituted with halogen atoms, and 3 or more and 6 or less are preferably substituted with halogen atoms. The substitution position of the R ^d6 O— group is preferably the ortho position or the para position, and particularly preferably the para position. M2 is preferably 1 to 2, particularly preferably 1.

The number of carbon atoms in the heterocyclic group represented by R ^d1 is preferably 3-20, more preferably 3-10, and even more preferably 3-5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.

The heterocyclic group represented by R ^d1 may have one or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent that the aromatic hydrocarbon group represented by R ^d1 may have.

The number of carbon atoms of the alkyl group represented by R ^d1 is preferably 1-12. ^Examples of the alkyl group represented by R ^d1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, A tetradecyl group, a pentadecyl group, etc. are mentioned. These alkyl groups may be linear, branched, or cyclic, and may be a group in which a linear group and a cyclic group are combined. In the alkyl group represented by R ^d1 , the methylene group (—CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —, The hydrogen atom may be substituted with an OH group or an SH group.

R ^d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear (linear or branched) or cyclic, and may be linear, branched, or cyclic. And a group in which a cyclic group is combined. In the alkyl group for R ^d5 , the methylene group (—CH ₂ —) may be replaced by —O— or —CO—.

Specific examples of the alkyl group which may have a substituent represented by R ^d1 include groups represented by the following formulas. * Represents a bond.

Further, as represented by R ^d1, the number of carbon atoms of the group formed by combining an alkanediyl group derived from an alkyl group represented by an aromatic hydrocarbon group and the R ^d1 is preferably 7-33, more Preferably it is 7-18, More preferably, it is 7-12. The combined group may have one or more substituents, and the substituent is the same as the group exemplified as the substituent that the aromatic hydrocarbon group or the alkyl group may have. The group of is mentioned. Represented by the R ^d1, as the group which is a combination of an alkanediyl group derived from an alkyl group represented by an aromatic hydrocarbon group and the R ^d1, an aralkyl group, specifically, the following formula The group represented by these can be mentioned. In the formula, * represents a bond.

Among them, R ^d1 is preferably an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent, and an aromatic hydrocarbon group which may have a substituent. Is more preferable.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d2 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

The number of carbon atoms of the heterocyclic group represented by R ^d2 is preferably 3-20, more preferably 3-10, and even more preferably 3-5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.

The number of carbon atoms in the alkyl group represented by R ^d2 is preferably from 1 to 7, more preferably from 1 to 5, more preferably from 1 to 3. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. The alkyl group may be linear, branched, or cyclic, or may be a group that combines a chain group and a cyclic group.

R ^d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, still more preferably a chain alkyl group having 1 to 3 carbon atoms, and a methyl group. Particularly preferred.

The aromatic hydrocarbon group represented by R ^d3 preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, and a phenyl group and a naphthyl group are more preferable.

The aromatic hydrocarbon group represented by R ^d3 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl. An alkyl group having 1 to 15 carbon atoms such as a group and a decyl group; an alkenyl group having 1 to 15 carbon atoms such as an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a nonenyl group, and a decenyl group; Is mentioned.

The aliphatic hydrocarbon group which the aromatic hydrocarbon group represented by R ^d3 may have more preferably 1 to 7 carbon atoms, and the aliphatic hydrocarbon group is linear or branched Either a chain or a ring may be used, or a group obtained by combining a chain group and a cyclic group may be used. The methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group may be replaced with —O—, —CO— or —S—, and the methine group (—CH <) is represented by —N— <May be replaced.

Examples of the aliphatic hydrocarbon group that the aromatic hydrocarbon group represented by R ^d3 may have include groups represented by the following formulas. In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d3 include groups represented by the following formulas. In the formula, * represents a bond.

The number of carbon atoms of the heterocyclic group represented by R ^d3 is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group. Further, the heterocyclic group represented by R ^d3 may have one or more substituents, and the substituent includes an aromatic hydrocarbon group represented by R ^d1. Examples thereof include the same groups as those exemplified as the good substituent.

Among them, R ^d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms). The number of groups is preferably 2 or more and 5 or less.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d4 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is more preferable. Moreover, the aromatic hydrocarbon group represented by R ^d4 may have one or more substituents. Examples of the substituent include the same groups as the substituent that the aromatic hydrocarbon group represented by R ^d1 may have.

The number of carbon atoms of the aliphatic hydrocarbon group represented by R ^d4 is preferably 1-13, more preferably 2-10, more preferably from 4 to 9. Examples of the aliphatic hydrocarbon group represented by R ^d4 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Alkyl groups such as tridecyl, tetradecyl, and pentadecyl; ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, butadecenyl Groups, and alkenyl groups such as a pentadecenyl group. These aliphatic hydrocarbon groups may be chain (linear or branched), cyclic, or a combination of a chain group and a cyclic group. In the aliphatic hydrocarbon group for R ^d4 , the methylene group (—CH ₂ —) may be replaced by —O—, —CO— or —S—, and the methine group (—CH <) is represented by — PO ₃ <may be substituted, and a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.

Examples of the aliphatic hydrocarbon group which may have a substituent represented by R ^d4 include groups represented by the following formulas. In the formula, * represents a bond.

R ^d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and still more preferably a branched chain having no substituent. It is a chain alkyl group.

  Examples of the compound (d1) include a compound represented by the following formula (d1), specifically, a compound represented by the following formula (d1-1) to a compound represented by the following formula (d1-67). . In Tables 1 to 7, * represents a bond.

Among them, the compound represented by formula (d1-3) to the compound represented by formula (d1-6), the compound represented by formula (d1-18) to the compound represented by formula (d1-52), A compound represented by the formula (d1-55), a compound represented by the formula (d1-56), a compound represented by the formula (d1-60), and a compound represented by the formula (d1-61) are preferable.
More preferably, a compound represented by formula (d1-3) to a compound represented by formula (d1-6), a compound represented by formula (d1-18) to a compound represented by formula (d1-41) And
More preferably, a compound represented by the formula (d1-24), a compound represented by the formula (d1-36) to a compound represented by the formula (d1-40),
Particularly preferred is a compound represented by formula (d1-24).

  Compound (d1) can be produced, for example, by the production method described in JP-T-2014-500852.

Compound (d2) is
R ^d1 may have a substituent, an alkyl group having 1 to 15 carbon atoms,
R ^d2 is an alkyl group having 1 to 10 carbon atoms,
An aromatic hydrocarbon group having 6 to 18 carbon atoms in which R ^d3 may have a substituent,
A compound in which R ^d4 is an ^optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms is preferred,
More preferably,
R ^d1 represents a methyl group, an ethyl group or a propyl group;
R ^d2 represents a methyl group, an ethyl group or a propyl group;
R ^d3 represents a phenyl group substituted with a methyl group;
A compound in which R ^d4 is a methyl group, an ethyl group or a propyl group;
More preferably,
In this compound, R ^d1 and R ^d2 are methyl groups, R ^d3 is an o-tolyl group, and R ^d4 is an ethyl group.

Compound (d3) is
R ^d1 may have a substituent, an alkyl group having 1 to 15 carbon atoms,
A compound in which R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms is preferred,
More preferably,
In this compound, R ^d1 is a hexyl group and R ^d2 is a phenyl group.

  Examples of such O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-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, N-acetoxy-1- [ -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02, OXE03 (manufactured by BASF) and N-1919 (ADEKA) may be used. When these O-acyloxime compounds are used, a color filter excellent in litho performance tends to be obtained.

  The alkylphenone compound is a compound having a partial structure represented by the following formula (d4) or a partial structure represented by the following formula (d5). In these partial structures, the benzene ring may have a substituent.

  Examples of the compound having a structure represented by the formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) ) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, and the like. It is done. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.

  Examples of the compound having a structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy ) Phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.

  In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d4).

  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 (for example, see JP-B-48-38403, JP-A-62-174204, etc.), the phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Among these, a compound represented by the following formula or a mixture thereof is preferable.

  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) etheni ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Furthermore, as the polymerization initiator (D), 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, Examples include 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 (D1) (particularly amines) described later.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 25 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part, More preferably, it is 10-20 mass parts. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter tends to be improved.

[5] Polymerization initiation assistant (D1)
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is used in combination with the polymerization initiator (D).

  Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Of these, thioxanthone compounds are preferred. Two or more polymerization initiation assistants (D1) may be used in combination.

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

  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, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

  The content of the polymerization initiation assistant (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part. When the content of the polymerization initiation assistant (D1) is within the above range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

[6] Thiol compound (T)
The colored curable resin composition of the present invention may contain a thiol compound (T). The colored curable resin composition can contain one or more thiol compounds as the thiol compound (T). The thiol compound (T) is particularly preferably used when the polymerization initiator (D) is an oxime compound such as an O-acyloxime compound and / or a biimidazole compound. The thiol compound (T) is a compound having at least one sulfanyl group (—SH) in the molecule. The thiol compound (T) is preferably a compound having one sulfanyl group in the molecule.

  The compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanyl. Pyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino- 2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamidine -6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6 -Propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2- Sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2- Methyl-4H-1,2,4-triazo Lu-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1 , 3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2- Sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2 -Sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro Ro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4- Triazole, 4-amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine, etc. Is mentioned.

  Compounds having two or more sulfanyl groups in the molecule include 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), tri Methylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris Mud carboxyethyl tris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate) and 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

  The content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polymerization initiator (D). It is. When the content of the thiol compound (T) is within the above range, sensitivity tends to be high and developability tends to be good.

[7] Solvent (E)
The colored curable resin composition of the present invention preferably contains a solvent (E). The colored curable resin composition can contain one or more solvents as the solvent (E). As the solvent (E), ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), Examples include ketone solvents (solvents containing —CO—) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

  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, and γ-butyrolactone.

  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, include phenetol and methyl anisole and the like.

  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, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate and the like.

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

  It is preferable that a solvent (E) contains the organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less from the point of applicability | paintability and drying property. Among them, the solvent (E) is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3 It preferably contains at least one selected from the group consisting of -methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide, propylene glycol monomethyl ether acetate, propylene glycol monomethyl Ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1- More preferably contains at least one selected from methanol and the group consisting of ethyl 3-ethoxypropionate.

  The content of the solvent (E) in the colored curable resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and the color density does not become insufficient when a color filter is formed, so that the display characteristics tend to be good.

[8] Leveling agent (F)
The colored curable resin composition of the present invention can contain a leveling agent (F). The colored curable resin composition can contain one or more leveling agents as the leveling agent (F). Examples of the leveling agent (F) 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 in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: 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 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

  Examples of the fluorosurfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  The content of the leveling agent (F) is usually 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 in the colored curable resin composition. Preferably they are 0.005 mass% or more and 0.05 mass% or less. This content does not include the content of the pigment dispersant.

[9] Antioxidant (G)
From the viewpoint of improving the heat resistance and light resistance of the colorant (A), the colored curable resin composition preferably contains an antioxidant. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, and the like can be used. Two or more antioxidants may be used.

  Examples of phenolic antioxidants include Irganox 1010 (Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox 1076. (Irganox 1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corp.), Irganox 1330 (Irganox 1330: 3, 3 ′, 3 ″, 5 , 5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Corporation), Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy Benzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Corp.), Irganox 3790 (Irganox 3790: 1,3,5-Tris ((4 -T-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by BASF Corporation), Irganox 1035 (Irganox 1035: thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox 1135 (Irganox 1135: benzenepropanoic acid, 3, 5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Corp.), Iruga Knox 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF Corp.), Irganox 3125 (Irganox 3125, manufactured by BASF Corp.), Irganox 565 (Irganox 565: 2) , 4-bis (n-octylthio) -6- (4-hydroxy 3 ′, 5′-di-t-butylanilino) -1,3,5-triazine, manufactured by BASF Corporation), ADK STAB AO-80 (ADK STAB) AO-80: 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10 -Tetraoxaspiro (5,5) undecane (manufactured by ADEKA Corporation), Sumilizer BHT (Sumilizer B T, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumizer GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, Co., Ltd.) ) And Vitamin E (manufactured by Eisai Co., Ltd.).

  Examples of phosphorus antioxidants include Irgafos 168 (Irgafos 168: Tris (2,4-di-t-butylphenyl) phosphite, manufactured by BASF Corp.), Irgafos 12 (Irgafos 12: Tris [2-[[2 , 4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (manufactured by BASF Corporation), Irgaphos 38 ( Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corporation), Adeka Stub 329K (manufactured by ADEKA Corporation), Adeka Stub PEP36 ( (Manufactured by ADEKA), ADK STAB PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (Clari Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE) and Sumilizer GP (Sumilizer GP: 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] dioxaphosphine (Manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkyl mercaptopropionate compounds of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. Is mentioned.

[10] Other components In the colored curable resin composition of the present invention, if necessary, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an aggregation inhibitor, an organic acid In addition, one or more additives such as an organic amine compound and a curing agent can be contained.

  Moreover, the colored curable resin composition which concerns on this invention can contain a C2-C4 cyclic ether structure containing component. The C2-C4 cyclic ether structure-containing component is not particularly limited as long as it is a compound having a C2-C4 cyclic ether structure (for example, an oxirane ring, an oxetane ring, a tetrahydrofuran ring, etc.). It may be a monomer having a cyclic ether structure of ˜4, or a copolymer having a cyclic ether structure of 2 to 4 carbon atoms. Further, for example, the resin (B) may also serve as a C2-C4 cyclic ether structure-containing component.

  Examples of the filler include glass, silica, and alumina. Examples of the polymer compound other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  As adhesion promoters, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Note that 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is an example of a component having a cyclic ether structure having 2 to 4 carbon atoms.

  Examples of ultraviolet absorbers include benzotriazole compounds such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole; benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone Compound; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2- (4,6-diphenyl-1,3,5-triazine- 2-yl) -5-hexyloxyphenol and other triazine compounds; Examples of the aggregation inhibitor include sodium polyacrylate.

Organic acids are used to adjust developability. Specifically,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
And aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid.

As an organic amine compound,
n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine Monoalkylamines such as n-undecylamine and n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di- dialkylamines such as n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol ;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkane diols such as 2, 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanol such as 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanol such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, aminobenzoic acid such as p-diethylaminobenzoic acid; and the like.

  Examples of the curing agent include a compound that can react with the carboxy group in the resin (B) when heated to crosslink the resin (B), a compound that can be polymerized alone to cure the colored pattern, and the like. , Epoxy compounds, oxetane compounds and the like. The epoxy compound as a hardening | curing agent corresponds to the above-mentioned C2-C4 cyclic ether structure containing component. Only 1 type may be used for a hardening | curing agent and it may use 2 or more types together.

  Epoxy compounds include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, and alicyclic compounds. Epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, aliphatic resins other than epoxy resins and brominated derivatives thereof, fats Examples include cyclic or aromatic epoxy compounds, epoxidized products of butadiene (co) polymers, epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylate, triglycidyl isocyanurate, and the like. It is done. Examples of commercially available epoxy resins include orthocresol novolac type epoxy resins, “Sumiepoxy (registered trademark) ESCN-195XL-80” (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored curable resin composition of the present invention contains an epoxy compound, an oxetane compound or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Good. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

As polyvalent carboxylic acid,
Phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ', 4,4'-benzophenone tetra Aromatic polycarboxylic acids such as carboxylic acids;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid Alicyclic polycarboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid; and the like.

As polyvalent carboxylic acid anhydride,
Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride ;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride and nadic anhydride;
And ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerol tristrimellitic anhydride.

  As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. As the epoxy resin curing agent, trade name “Adeka Hardener (registered trademark) EH-700” (manufactured by ADEKA), trade name “Rikacid (registered trademark) HH” (manufactured by Shin Nippon Rika), trade name “MH-700” (manufactured by Shin Nippon Rika Co., Ltd.) and the like.

  Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium. Onium salts such as hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate Examples include rates.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and, if necessary, a solvent (E), a thiol compound ( T), a leveling agent (F), a polymerization initiation assistant (D1), an antioxidant (G), and other components may be mixed.

<Color filter and manufacturing method thereof, color filter and display device>
Examples of the method for producing a colored pattern from 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. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter according to the present invention. The color filter according to the present invention is typically used as a green pixel.

  As a substrate, glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the above substrate In addition, an aluminum, silver, silver / copper / palladium alloy thin film or the like is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

  The formation of each color pixel by the photolithography method can be performed by a known or commonly used apparatus or conditions, and can be manufactured as follows, for example. First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained. Examples of the coating method include spin coating, slit coating, and slit and spin coating.

  30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. Further, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 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 coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

  Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use 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. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

  For exposure, the entire exposure surface can be irradiated with parallel rays uniformly, and accurate alignment between the photomask and the substrate on which the colored composition layer is formed can be performed. Therefore, an exposure apparatus such as a mask aligner and a stepper Is preferably used.

  A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. 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, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  Since the thickness of the obtained color filter affects adjacent pixels, it is preferably as thin as possible. In particular, when the film is thick, the light from the light source may leak through the pixels of two or more colors when the liquid crystal panel is manufactured. May be lost. The film thickness of the color filter is, for example, preferably 3 μm or less, and more preferably 2.8 μm or less. Although the minimum of the film thickness of a color filter is not specifically limited, Usually, it is 1 micrometer or more and may be 1.5 micrometers or more.

  The color filter according to the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

<Synthesis Example 1: Preparation of resin solution (B1)>
In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was passed to replace the nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 38 parts of acrylic acid, 289 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8 and / or 9-yl acrylate, and 125 parts of propylene glycol monomethyl ether acetate The solution was added dropwise over 5 hours. On the other hand, a mixed solution prepared by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the solution is kept at the same temperature for 4 hours, then cooled to room temperature, and a resin solution containing a B-type viscosity (23 ° C.) of 125 mPas, a solid content of 37.0% by mass, and a solution acid value of 27 mg-KOH / g. (B1) was obtained. The weight average molecular weight Mw of the resin contained in the resin solution (B1) was 9200, and the molecular weight distribution was 2.08.

  The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin contained in the resin solution (B1) were measured using the GPC method under the following conditions. The ratio (Mw / Mn) between the weight average molecular weight in terms of polystyrene and the number average molecular weight obtained under the following conditions was defined as the molecular weight distribution.

Apparatus; HLC-8120GPC (manufactured by Tosoh Corporation),
Column; TSK-GELG2000HXL,
Column temperature; 40 ° C
Solvent; THF,
Flow rate: 1.0 mL / min,
Test liquid solid content concentration; 0.001 to 0.01% by mass,
Injection volume: 50 μL,
Detector; RI,
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation).

<Synthesis Example 2: Preparation of pigment dispersion (A1)>
C. I. Pigment Green 59 14.0 parts Acrylic pigment dispersant 1.9 parts Propylene glycol monomethyl ether acetate 84.1 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A1). It was.

<Synthesis Example 3: Preparation of pigment dispersion (A2)>
C. I. Pigment Green 58 14.0 parts Acrylic pigment dispersant 1.9 parts Propylene glycol monomethyl ether acetate 84.1 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A2). It was.

<Synthesis Example 4: Preparation of pigment dispersion (A3)>
C. I. Pigment Yellow 138 15.0 parts Acrylic pigment dispersant 4.5 parts Propylene glycol monomethyl ether acetate 80.5 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A3). It was.

<Examples 1-5 and Comparative Examples 1-5>
(1) Preparation of colored curable resin composition The components described in Table 8 were mixed so as to have the blending amounts described in Table 8 to obtain a colored curable resin composition. The unit of the amount of each component in Table 8 is “parts by mass”. Details of each component are as follows.

[1] Pigment dispersion (A1): Pigment dispersion (A1) obtained in Synthesis Example 2
[2] Pigment dispersion (A2): Pigment dispersion (A2) obtained in Synthesis Example 3
[3] Pigment dispersion (A3): Pigment dispersion (A3) obtained in Synthesis Example 4
[4] Resin solution (B1): Resin solution (B1) obtained in Synthesis Example 1
[5] Polymerizable compound (C1): ethoxylated dipentaerythritol hexamethacrylate (EO 6 mol) (trade name “M-DPH-6E” manufactured by Shin-Nakamura Chemical Co., Ltd.),
[6] Polymerizable compound (C2): Dipentaerythritol hexaacrylate (trade name “A-9550” manufactured by Shin-Nakamura Chemical Co., Ltd.),
[7] Polymerization initiator (D1):

A compound represented by
[8] Polymerization initiator (D2): 2,2 ′, 4-tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4,5-diphenyl-1,1′-biimidazole (CHEMBRIDGE INTERNATIONAL CORPORATION product name "TCDM"),
[9] Thiol compound (T1): 2-mercaptobenzothiazole (trade name “Sunseller M” manufactured by Sanshin Chemical Industry Co., Ltd.)
[10] Additive: 3-Methacryloxypropyltrimethoxysilane (trade name “KBM-503” manufactured by Shin-Etsu Silicone Co., Ltd.)
[11] Leveling agent (F1): polyether-modified silicone oil (trade name “Tore Silicone SH8400” manufactured by Toray Dow Corning Co., Ltd.),
[12] Solvent (E1): Propylene glycol monomethyl ether acetate.

(2) Preparation of colored coating film A colored curable resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C for 3 minutes. After cooling, the substrate coated with this colored curable resin composition was irradiated with light at an exposure amount of 80 mJ / cm ² (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Irradiated. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a colored coating film.

(3) Film thickness measurement About the colored coating film obtained by said (2), the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 9.

(4) Chromaticity Evaluation The color coating film obtained in (2) above was measured for spectroscopy using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the characteristic function of the C light source was used. Then, xy chromaticity coordinates (x, y) and tristimulus values (Y) in the XYZ color system of CIE were measured. It shows that the brightness is so high that (Y) is large. The results are shown in Table 9.

(5) Creation of colored pattern and evaluation of shape of colored pattern On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the thickness of the colored curable resin composition after post-baking is 2.7 μm. Thus, after apply | coating with a spin coat method, it prebaked at 100 degreeC for 3 minute (s), and formed the composition layer. After cooling, the distance between the substrate on which the composition layer is formed and the quartz glass photomask is set to 80 μm, and exposure is performed at 50 mJ / cm ^{2 in} an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Light was irradiated in an amount (based on 365 nm). A photomask having a 50 μm line and space pattern was used. The composition layer after the light irradiation was developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 60 seconds, washed with water, A colored pattern was obtained by post-baking at 30 ° C. for 30 minutes. About the obtained coloring pattern, when the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Japan Vacuum Technology Co., Ltd.), it confirmed that it was 2.7 micrometers.

  About the obtained coloring pattern, the shape was observed using the scanning electron microscope (S-4000; Hitachi High-Technologies Corporation make), and it evaluated according to the following evaluation criteria. The results are shown in Table 9.

A: The colored pattern shape is a forward tapered shape as shown in FIG.
B: The colored pattern shape is an inversely tapered shape as shown in FIG.

  In Examples 1-5 and Comparative Examples 1-5, the chromaticity coordinates (x, y) of the colored coating film are unified. In Examples 1 to 5, it was possible to achieve both high brightness and a good colored pattern shape. On the other hand, in Comparative Examples 1-2, the lightness was insufficient, and in Comparative Examples 3-5, the coloring pattern became a reverse taper shape.

  According to the colored curable resin composition of the present invention, it is possible to provide a color filter having high brightness and excellent pattern shape, and a display device including the color filter.

Claims (5)

A colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D);
The colorant (A) is C.I. I. Pigment Green 59,
The polymerizable compound (C) is at least one (meth) acrylate (c1) selected from the group consisting of ethylene oxide-modified dipentaerythritol penta (meth) acrylate and ethylene oxide-modified dipentaerythritol hexa (meth) acrylate. A colored curable resin composition comprising:   The colored curable resin composition according to claim 1, wherein the polymerizable compound (C) further contains a (meth) acryloyl group-containing compound (c2) other than the (meth) acrylate (c1).   The colored curable resin composition according to claim 1 or 2, wherein the content of the (meth) acrylate (c1) is 20% by mass or more in 100% by mass of the polymerizable compound (C).   The color filter formed from the colored curable resin composition of any one of Claims 1-3.   A display device comprising the color filter according to claim 4.