TW201512270A - Coloring curable resin composition - Google Patents

Abstract

The present invention provides a coloring curable resin composition, which comprises: a compound represent by formula (A-1), a resin (B), a photopolymerizable compound (C), a photo polymerization initiator (D) and a solvent (E). (in formula (A-1), X<SP>-</SP> represents an anion including a boron atom or an aluminum atom, A represent the group represented by formula (A-VI-1) or formula (A-VI-2), * represents a bonding to a carbon atom.).

Description

Colored curable resin composition

The present invention relates to a colored curable resin composition.

The colored curing resin composition which is formed in a color filter such as a solid-state imaging device such as a liquid crystal display device, and the coloring of the compound represented by the formula (A-III-1) is described in International Publication No. 2012/053211. A curable resin composition.

The present invention provides the following [1] to [6].

[1] A colored curable resin composition comprising: a compound represented by the formula (AI), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E); [In the formula (AI), X ^- represents an anion containing a boron atom or an aluminum atom, and A represents a group represented by the formula (A-VI-1) or the formula (A-VI-2). * indicates a bond with a carbon atom.

R ¹ to R ¹⁸ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms or a halogen atom.

R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto.

R ²¹ and R ²² each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto.

R ²³ and R ²⁴ each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto.

In R ¹⁹ to R ²⁶ , the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ^26a , -OH, -OR ^26a , -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, - CO ₂ R ^26a , -SO ₃ H, -SO ₃ R ^26a or -SO ₂ NHR ^{28a are} substituted.

R ^26a represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OR ^27a (wherein R ^27a represents a saturated hydrocarbon group having 1 to 10 carbon atoms), a halogen atom or an alkali metal phenylsulfonate.

R ^28a represents a hydrogen atom, -R ^26a , -CO ₂ R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -R ^26a or -OR ^27a ].

[2] The colored curable resin composition according to [1], which further comprises a blue pigment.

[3] The colored curable resin composition according to [1] or [2], which further comprises an antioxidant.

[4] A coating film formed of the colored curable resin composition according to any one of [1] to [3].

[5] A color filter comprising the color-curable resin composition according to any one of [1] to [3].

[6] A display device comprising the color filter according to [5].

According to the colored curable resin composition of the present invention, a color filter excellent in heat resistance can be obtained.

The colored curable resin composition of the present invention contains a compound represented by the formula (A-I) (hereinafter referred to as a compound (A-I)) as a colorant (A). The compound (A-I) contains its tautomer.

[In the formula (AI), X ^- represents an anion containing a boron atom or an aluminum atom.

R ¹ to R ¹⁸ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms or a halogen atom.

R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto.

R ²¹ and R ²² each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto.

R ²³ and R ²⁴ each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto.

In R ¹⁹ to R ²⁶ , the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ^26a , -OH, -OR ^26a , -SO ₃ ^- -, -SO ₃ Na, -CO ₂ H, -CO ₂ R ^26a , -SO ₃ H, -SO ₃ R ^26a or -SO ₂ NHR ^28a substituted.

R ^26a represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OR ^27a (wherein R ^27a represents a saturated hydrocarbon group having 1 to 10 carbon atoms), a halogen atom or an alkali metal phenylsulfonate.

R ^28a represents a hydrogen atom, -R ^26a or -CO ₂ R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -R ^26a or -OR ^27a . ]

R ¹ to R ¹⁸ , R ^26a and R ^27a , as a saturated hydrocarbon group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, tert-butyl Base, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5-dimethylhexyl, 1,6-Dimethylheptyl, 2-ethylhexyl and 1,1,5,5-tetramethylhexyl and the like.

R ¹ to R ¹⁸ are preferably a hydrogen atom and a saturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.

R ¹⁹ to R ^{26 are} an aromatic hydrocarbon group having 6 to 10 carbon atoms, for example, a phenyl group or a naphthyl group.

As -OR ^27a , for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosyloxy base.

As -CO ₂ R ^26a , for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl and eicosyloxycarbonyl.

Examples of -SO ₃ R ^26a include a methanesulfonyloxy group, an ethanesulfonyloxy group, a hexanesulfonyloxy group, a decanesulfonyloxy group, and the like.

As -SO ₂ NHR ^28a , for example, amidoxinyl, methanesulfonyl, ethanesulfonyl, propanylsulfonyl, isopropanylsulfonyl, butanesulfonyl, isobutaneamine Sulfonyl, pentamaminesulfonyl, isoamylamine sulfonyl, neopentylamine sulfonyl, cyclopentylamine sulfonyl, hexylamine sulfonyl, cyclohexylamine sulfonyl, Heptylamine sulfonyl, cycloheptylamine sulfonyl, octylamine sulfonyl, 2-ethylhexylamine sulfonyl, 1,5-dimethylhexylsulfonyl, cyclooctane Aminesulfonyl, decylamine sulfonyl, decylamine sulfonyl, tricyclodecylamine sulfonyl, methoxypropane sulfonyl, ethoxypropane sulfonyl, propoxypropane Aminesulfonyl, isopropoxypropanylsulfonyl, hexyloxypropanylsulfonyl, 2-ethylhexyloxypropanylsulfonyl, methoxyhexaneaminesulfonyl, 3-benzene Alkyl-1-methylpropanamine sulfonyl group and the like.

As the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As the alkali metal of the alkali metal phenylsulfonate, for example, sodium, potassium or the like.

In the formula (AI), at least one of R ¹⁹ to R ²⁶ is preferably -R ^26a , and the alkyl group having 1 to 4 carbon atoms is more desirable.

As The group shown is, for example, the following group.

The group represented by the formula (A-VI-1) is, for example, the following group.

The group represented by the formula (A-VI-2) is, for example, the following group.

X ^- represents an anion containing a boron atom or an aluminum atom. As X ^-, from the point of more improving the heat resistance, it is desirable to include a boron atom in the anion.

As the boron-containing anion and the aluminum-containing anion, for example, an anion represented by the formula (4).

In the formula (4), W ¹ and W ² each independently represent a substituent having two substituents derived by releasing a proton from a monovalent proton-donating substituent. M represents a boron atom or an aluminum atom. ]

As a group having two substituents derived by releasing a proton from a monovalent proton-donating substituent, for example, a compound having at least two monovalent proton-donating substituents (hydroxyl group, carboxyl group, etc.) is supplied from two protons. The sexual substituents give rise to the proton group.

The compound is preferably a catechol which may have a substituent, a 2,3-dihydroxynaphthalene which may have a substituent, a 2,2'-bisphenol which may have a substituent, a 3-hydroxy group which may have a substituent -2-naphthoic acid, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, a binaphthol which may have a substituent, and a salicyl having a substituent An acid, a benzilic acid which may have a substituent or a mandelic acid which may have a substituent.

The above-mentioned preferable compound is, for example, a halogen atom, a halogenated alkyl group, a hydroxyl group, an amine group, a nitro group, an alkoxy group or the like as a substituent.

As the aforementioned salicylic acid which may have a substituent, for example, salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4 - bromodelic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-t-butylsalicylic acid, 3,5- Dibromosalicylic acid, 3,5-di Chlorosalicylic acid, 3,5,6-trichlorosalicylic acid, 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid) And 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid), and the like.

Examples of the diphenylglycolic acid which may have a substituent are as follows.

The bitter almond acid which may have a substituent, for example, is as follows.

In the formula (4), W ¹ and W ² each independently represent an aromatic hydrocarbon group having 6 to 10 carbon atoms and having COO ^- and O ^- - as a substituent.

The anion represented by the formula (4) is an anion represented by the following formula, for example, an anion (BC-1) to an anion (BC-24) having each substituent shown in Table 1, and a formula (BC-) 25) Anion (BC-25) to anion (BC-28) and the like shown in the formula (BC-28), respectively.

[wherein, M represents a boron atom or an aluminum atom. ]

[In the formula (BC-25) to the formula (BC-28), M represents a boron atom or an aluminum atom. ]

As an anion represented by the formula (4), anion (BC-1), anion (BC-2), anion (BC-3), anion (BC-25), anion (BC-26), anion (BC-27) Preferably, the anion (BC-1), the anion (BC-2), and the anion (BC-25) are more desirable, and the anion (BC-1) and the anion (BC-2) are more desirable.

The compound (A-I) can be produced by mixing a compound represented by the formula (A-II) (hereinafter referred to as a compound (A-II)) with a salt of an anion or an alkali metal represented by the formula (4). As the alkali metal, for example, lithium, sodium, potassium, and the like.

[In the formula (A-II), R ¹ to R ⁸ , R ¹⁹ to R ²² and A each have the same meanings as described above. ]

The mixture of the anion and the alkali metal salt represented by the formula (4) and the compound (A-II) can be dissolved in the solvent and can be carried out without being dissolved.

As a solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, acetonitrile, ethyl acetate, toluene, methanol, Ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, water and chloroform.

Among them, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, methanol, ethanol, isopropanol and water are preferred. More ideal.

When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added.

The mixing temperature of the anion and the alkali metal salt represented by the formula (4) and the compound (A-II) is preferably from 0 ° C to 150 ° C, more preferably from 10 ° C to 120 ° C, still more preferably from 20 ° C to 100 ° C. .

The mixing time is preferably from 1 hour to 72 hours, more preferably from 2 hours to 24 hours, and even more preferably from 3 hours to 12 hours.

Mixing the reaction with a solvent that is compatible with water The compound is further stirred for 1 to 3 hours as needed, and then the precipitate is obtained by filtration to obtain a compound (A-I). The obtained compound (A-I) can be washed with ion-exchanged water as needed.

In the case of using a solvent which is incompatible with water, the reaction mixture is mixed with ion-exchanged water, and further stirred for 1 to 3 hours as needed, and then the organic layer is obtained by liquid separation to obtain a solution containing the compound (AI). . The solution can be washed with ion-exchanged water as needed. The compound (A-I) can be obtained by removing the solvent from the solution containing the compound (A-I).

Further, the compound (A-I) may be dissolved in a solvent such as acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone or chloroform, and purified by recrystallization.

The colored curable resin composition of the present invention comprises a compound (A-I), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

The colored curable resin composition of the present invention preferably further contains a leveling agent (F) and an antioxidant (H), and more preferably further contains an antioxidant (H).

The colored curable resin composition of the present invention may further contain a polymerization initiation aid (D1).

In the present specification, the compounds which are the respective components are exemplified, and may be used singly or in combination of plural kinds, without particular limitation.

<Colorant (A)>

The colored curable resin composition of the present invention contains the compound (A-I) as a colorant (A).

For the coloring agent (A), the compound (A-I) may be used alone, and for coloring, that is, for adjusting the spectral characteristics, other dyes (A1), pigments (P) or a mixture thereof may be further included.

As the dye (A1), for example, a dye such as an oil-soluble dye, an acid dye, or a basic dye may be either a direct dye or a mordant dye. The above acid dye may be an amine salt or a sulfonamide derivative.

As the dye (A1), for example, a dye which is classified into a dye compound and a dyeing note (color dyeing company) in a color index (published by the dyeing and colorist association) is used. Moreover, according to chemical structures, such as azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, and secondary Base dyes, azo methine dyes, squarylium dyes, acridine dyes, styrene dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, it is preferred to use an organic solvent-soluble dye as the dye (A1).

Specifically, as the dye (A1), for example, CI Solvent Yellow-4 (hereinafter, the description of the CI Solvent Yellow is omitted, and only the number is described. Regarding the other dyes, the description of the common portion is omitted for the dyes whose names are common to the names). 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI solvent red 45, 49, 125, 130, 218; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 4, 5, 7, 34, 35 and other CI solvent dye; CI acid yellow 1, 3, 7, 9, 11, 17 , 23, 25, 29, 34, 36, 38, 40, 42, 54, 55, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35 , 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150 , 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277 , 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 17 , 19 30, 102; CI Acid Blue 18, 29, 42, 59, 60, 62, 70, 72, 74, 82, 87, 92, 100, 102, 113, 117, 120, 126, 130, 131, 142, 151 , 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335 CI acid green 16, such as 16, 58, 63, 65, 80, 104, 105, 106, 109; CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141; CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56 , 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90 , 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158 , 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200 , 201, 202, 203, 2 07, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 Such as CI direct dye; CI disperse yellow 54, 56 and other CI disperse dyes; CI alkaline red 1, 10; CI basic blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; CI alkaline green 1; iso-CI basic dye; CI active yellow 2, 46, 116; CI active orange 16; CI active red 36; iso-CI reactive dye; CI medium yellow (CI Mordant yellow) 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI medium red 1, 2, 4, 9, 12, 14, 17, 18, 19 , 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86 , 88, 90, 94, 95; CI medium orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI medium purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI Medium blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 77, 83, 84; CI media green 4, 10, 15, 26, 29, 33, 34, 35, 41, 43 53 and the like C.I. mordant dyes;. C. I. Vat Green (C.I.vat green) 1 and the like C.I. vat dyes and the like.

Among them, blue dyes, purple dyes and red dyes are preferred.

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

As the pigment (P), there is no particular limitation, and conventional pigments can be used, for example, those classified as pigments in the color index (published by the Colorists and Colorists Association).

As the pigment (P), for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, Yellow pigments such as 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI pigments orange 13, 13, 36, 38, 40, 42, 43, 51, 55, Orange pigments such as 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216 , red pigments such as 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 23, 29, Purple pigments such as 32, 36, 38; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

The pigment (P), more preferably an anthraquinone pigment or a dioxazine pigment, is more preferably at least one selected from the group consisting of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23. By including the above-mentioned pigment, the optimization of the transmission spectrum is facilitated, and the heat resistance, light resistance, and chemical resistance of the color filter are improved.

The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative introduced with an acidic group or a basic group, or the like, by a polymer compound, as needed Grafting treatment on the surface of the pigment, micronization treatment by a sulfuric acid micronization method, or removal by an organic solvent or water for removing impurities, or removal by ionic exchange of an ionic impurity. deal with. The particle size of the pigment is preferably uniform.

As the pigment (P), a pigment dispersion liquid in which a pigment is uniformly dispersed in a solvent can be used.

The pigment dispersion can be obtained by mixing a pigment and a pigment dispersant in a solvent. In the case of mixing the above two kinds of pigments, the above-mentioned mixing may be carried out separately or in combination of plural kinds.

The pigment dispersant may be a cationic, anionic, nonionic or amphoteric dispersant, for example, a polyester dispersant such as a polyester, a polyamine or an acrylic. These pigment dispersants may be used alone or in combination of two or more. As a pigment dispersing agent, for example, the trade name KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoei Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Corporation), AJISPER (flavor It is manufactured by Fine-Techno Co., Ltd., Disperbyk (manufactured by BYK Co., Ltd.), and the like.

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

The content of the compound (A-I) is preferably from 1% by mass to 100% by mass, and more preferably from 10% by mass to 100% by mass, based on the total amount of the coloring agent (A).

The content of the colorant (A) is ideal for the total amount of solid components. It is 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and still more preferably 5% by mass or more and 50% by mass or less. When the content of the colorant (A) is in the above range, desired spectral and color concentrations can be obtained.

In the present specification, the "total amount of solid components" means the total amount of components from which the solvent (E) is removed from the colored curable resin composition of the present invention. The total amount of the solid components and the content of each component thereof can be measured, for example, by a known analytical means such as a liquid chromatography or a gas chromatograph.

<Resin (B)>

The resin (B) is not particularly limited, and is preferably an alkali-soluble resin (B).

The alkali-soluble resin (B) (hereinafter referred to as "resin (B)") is a structure containing a monomer (a) derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Copolymer of the unit.

As such a resin (B), for example, the following resin [K1] to resin [K6] and the like.

The resin [K1] is selected from the group consisting of at least one of a group of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter referred to as "(a)") and a ring having a carbon number of 2 to 4 a copolymer of an ether structure and an ethylenically unsaturated bond monomer (b) (hereinafter referred to as "(b)"); a resin [K2] (a), (b) and copolymerizable with (a) a copolymer of the monomer (c) (but different from (a) and (b)) (hereinafter referred to as "(c)"); a copolymer of the resin [K3] (a) and (c); a resin [K4] in (a) and (c), a resin obtained by reacting (b), a copolymer of (b) and (c) a resin, and a resin obtained by reacting (a); Resin [K6] A copolymer of (b) and (c), which reacts (a) with a carboxylic anhydride.

As (a), specifically, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, and Base maleic acid, methyl fumaric acid, methylene succinic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrogen Unsaturated dicarboxylic acids such as phthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; methyl- 5-northene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxyl -5-Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1 a bicyclic unsaturated compound containing a carboxyl group such as hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, Methylene succinic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6- Unsaturated dicarboxylic anhydrides such as carboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono [2-(methyl) propylene methoxyethyl ester], phthalic acid mono [2-(methyl) An unsaturated mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid having two or more valences such as propylene methoxyethyl ester; and a hydroxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid; Unsaturated acrylates of carboxyl groups, and the like.

Among these, from the point of the copolymerization reactivity and the solubility of the obtained resin to the alkaline aqueous solution, acrylic acid, methacrylic acid, maleic anhydride or the like is preferable as (a).

(b) means a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an alkene. A polymerizable compound of a sexually unsaturated bond.

(b) It is preferred to use a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The labels "(meth)acryloyl) and "(meth)acrylate" have the same meaning.

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), having an oxycyclobutane group and an ethylenically unsaturated bond The monomer (b2) (hereinafter referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(b3)"), and the like.

(b), for example, a monomer (b1-1) having a structure in which an aliphatic or unsaturated hydrocarbon having a linear or branched chain is epoxidized (hereinafter referred to as "(b1-1)") A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b1-2)").

(b1-1), for example, glycidyl (meth)acrylate, β-methylepoxypropyl (meth)acrylate, β-ethylepoxypropyl (meth)acrylate, ring Oxypropyl vinyl ether, o-vinylbenzyloxypropyl ether, m-vinylbenzyloxypropyl ether, p-vinylbenzyl Epoxypropyl ether, α-methyl-o-vinylbenzyloxypropyl ether, α-methyl-m-vinylbenzyloxypropyl ether, α-methyl-p-ethylene Benzomethylepoxypropyl ether, 2,3-bis(epoxypropyloxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5- Bis(epoxypropyloxymethyl)styrene, 2,6-bis(goxypropyloxymethyl)styrene, 2,3,4-tris(epoxypropyloxymethyl)benzene Ethylene, 2,3,5-tris(epoxypropyloxymethyl)styrene, 2,3,6-tris(epoxypropyloxymethyl)styrene, 3,4,5-tri ( Epoxypropyloxymethyl)styrene, 2,4,6-tris(epoxypropyloxymethyl)styrene, and the like.

(b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by DAICEL), (meth)acrylic acid 3, 4 -Epoxycyclohexylmethyl ester (for example, CYCLOMER A400; manufactured by DAICEL), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMER M100; manufactured by DAICEL), and formula (II) a compound, a compound represented by the formula (III), and the like.

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

X ^a and X ^b represents a single ^{bond, -R c -, * - R} c -O -, * - R c -S- or * -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates a bond with O. ]

As the alkyl group having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl and the like.

An alkyl group in which a hydrogen atom is substituted with a hydroxyl group, such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1 -methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

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.

As the alkanediyl group having 1 to 6 carbon atoms, for example, methylene, ethyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane -1,5-diyl, hexane-1,6-diyl and the like.

As X ^a and X ^b , it is preferably, for example, a single bond, a methylene group, an ethyl group, a —CH ₂ —O— and a —CH ₂ CH ₂ —O—, more preferably, for example, a single bond, *-CH. ₂ CH ₂ -O- (* indicates a bond with O).

The compound represented by the formula (II) is, for example, a compound represented by any one of the formulae (II-1) to (II-15). Wherein formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) The compound shown is more preferably a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (III) is, for example, a compound represented by any one of the formulae (III-1) to (III-15). Wherein formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) to formula (III-15) The compound shown is more preferably a compound represented by the formula (III-1), the formula (III-7), the formula (III-9) or the formula (III-15).

The compound represented by the formula (II) and the compound represented by the formula (III) may be used singly or in combination of the compound represented by the formula (II) and the compound of the formula (III). In the case where these are used in combination, the content of the compound represented by the formula (II) and the compound represented by the formula (III) is preferably from 5:95 to 95:5, more preferably 10, based on moles. 90 to 90:10, more ideally 20:80 to 80:20.

As (b2), a monomer having an oxycyclobutane group and a (meth) propylene fluorenyloxy group is more preferable. As (b2), for example, 3-methyl-3-methylpropenyloxymethyloxycyclobutane, 3-methyl-3-propenyloxymethyloxetane Alkane, 3-ethyl-3-methylpropenyloxymethyloxycyclobutane, 3-ethyl-3-propenyloxymethyloxycyclobutane, 3-methyl-3-methylpropene醯oxyethyloxycyclobutane, 3-methyl-3-propenyloxyethyloxycyclobutane, 3-ethyl-3-methylpropenyloxyethyloxycyclobutane, 3- Ethyl-3-propenyloxyethyloxycyclobutane or the like.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofuran methyl acrylate (for example, Viscoat #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methyl methacrylate, and the like.

(b), the reliability of heat resistance and chemical resistance of the obtained color filter can be further improved, and (b1) is preferable. In addition, it is more preferable that it is (b1-2) from the point which the storage stability of the coloring curable resin composition is favorable.

As (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and tert-butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, Cyclohexyl methacrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (meth) acrylate (in the technical field, It is a conventional name for "dicyclopentanyl (meth) acrylate", and there is a case called "tricyclodecyl (meth) acrylate.), trimethyl (meth) acrylate [5.2.1.0 ^{2, 6} Terpene-8-yl ester (referred to in the technical field as "dicyclopentenyl (meth)acrylate" as a conventional name), dicyclopentyloxyethyl (meth)acrylate, (methyl) Isodecyl acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propynyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (A) (meth) acrylate such as benzyl acrylate; (methyl) Hydroxy-containing (meth) acrylates such as 2-hydroxyethyl enoate and 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, and methylene a dicarboxylic acid diester such as diethyl succinate; 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-A Bicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[ 2.2.1] a bicyclic unsaturated compound such as hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimine, N-succinimido-3-maleimidobenzoate, N-ammonium imino group- 4-Maleic iminobutyrate, N-succinimide-6-maleimidohexanoate, N-succinimide-3-maleimidopropionic acid Dicarbonylimine derivatives such as esters, N-(9-acridinyl) maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, ethylene Toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, different Pentadiene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth)acrylate, and trimethyl (meth)acrylate [5.2.1.0 ^2,6 ]癸 are preferable. Alk-8-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, bicyclo[2.2.1]hept-2-ene.

In the resin [K1], the ratio of the structural unit derived therefrom, in all the structural units constituting the resin [K1], the structural unit derived from (a); 2 to 60 mol%

Construction unit from (b); 40 to 98 mole % is more desirable, again from the structural unit of (a); 10 to 50 mole %

The structural unit from (b); 50 to 90 mol% is more desirable.

When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the development property when a colored pattern is formed, and the solvent resistance of the obtained color filter tend to be good.

Resin [K1], for example, the method described in the reference "Experimental method for polymer synthesis" (Otsuka Ryokan, Ltd., 1st edition, 1st edition, 1st issue, March 1, 1972), and the method described in the document It can be manufactured by citing literature.

As a specific manufacturing method of the resin [K1], for example, (a) and (b) are predetermined The amount, the polymerization initiator, and the solvent are fed into the reaction vessel, and the oxygen is replaced by nitrogen gas to form an oxygen-removing environment, and the method is heated and kept warm while stirring. In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and a general user in the field can be used. As a polymerization initiator, for example, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), an organic peroxide (over The benzophenone oxide is a solvent (E) which is a solvent (E) which will be described later as a solvent of the colored curable resin composition of the present invention.

Further, as the obtained copolymer, the solution after the reaction may be used as it is, or a solution which is concentrated or diluted may be used, or a method of reprecipitation or the like may be used as a solid (powder) take-out. In the polymerization, the solvent used in the colored curable resin composition of the present invention is used as a solvent, and the solution after the reaction is directly used in the preparation of the color-curable resin composition of the present invention, thereby simplifying the present invention. A manufacturing step of the colored curing resin composition.

In the resin [K2], the ratio of the structural unit derived therefrom, in all the structural units constituting the resin [K2], the structural unit derived from (a); 2 to 45 mol%

Construction unit from (b); 2 to 95 mol%

Constructive unit from (c); 1 to 65 mol% is more desirable, again from the structural unit of (a); 5 to 40 mol%

Construction unit from (b); 5 to 80 mol%

The structural unit from (c); 5 to 60 mol% is more desirable.

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the development property when a colored pattern is formed, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter are obtained. Good tendency.

The resin [K2] can be produced in the same manner as the method for producing the resin [K1], except that the amount of (c) is used in addition.

In the resin [K3], the proportion of the structural unit derived therefrom, in all the structural units constituting the resin [K3], the structural unit derived from (a); 2 to 60 mol%

Construction unit from (c); 40 to 98 mole % is ideal, with structural units from (a); 10 to 50 mole %

The structural unit from (c); 50 to 90 mol% is more desirable.

The resin [K3] can be produced in the same manner as described in the method for producing the resin [K1].

Resin [K4], by obtaining a copolymer of (a) and (c), adding (b) a cyclic ether having 2 to 4 carbon atoms to (a) having a carboxylic acid and/or Manufactured by carboxylic anhydride.

First, the copolymers of (a) and (c) are produced in the same manner as described in the method for producing the resin [K1]. In this case, the proportion of the structural unit derived therefrom, for example, the same ratio as the exemplified resin [K3] is preferable.

Then, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms which is contained in (b).

Following the manufacture of the copolymers of (a) and (c), the atmosphere in the flask was taken from nitrogen. Substituting air, (b), a reaction catalyst of a carboxylic acid and/or a carboxylic acid anhydride with a cyclic ether (for example, tris(dimethylaminomethyl)phenol, etc.), and a polymerization inhibitor (for example, hydroquinone, etc.) The resin [K4] can be produced by, for example, reacting at 60 to 130 ° C for 1 to 10 hours in a flask.

The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, to (a) 100 moles. By this range, the balance between the storage stability of the colored curable resin composition, the development property at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be improved. Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily left, the (b) used for the resin [K4] is preferably (b1), more preferably (b1-1).

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

The reaction conditions such as the feeding method, the reaction temperature, and the time are appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization. In addition, similarly to the polymerization conditions, the feeding method and the reaction temperature are appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization.

The resin [K5] was obtained in the same manner as in the above-described method for producing the resin [K1] as a first step, and a copolymer of (b) and (c) was obtained. Similarly to the above, the obtained copolymer may be directly used as a solution after the reaction, or a solution obtained by concentration or dilution, or a method of reprecipitation or the like as a solid (powder).

The ratio of the structural units derived from (b) and (c) to the copolymers constituting the foregoing The total number of moles of all structural units, respectively, is the structural unit from (b); 5 to 95% by mole

Constructive unit from (c); 5 to 95 mol% is more desirable, again from the structural unit of (b); 10 to 90 mol%

The structural unit from (c); 10 to 90 mol% is more desirable.

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) which the copolymer of (b) and (c) has, by the carboxylic acid possessed by (a) Or a carboxylic anhydride reaction, the resin [K5] can be obtained.

The amount of (a) used in the reaction with the aforementioned copolymer is preferably from 5 to 80 moles for (b) 100 moles. Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily left, the (b) used for the resin [K5] is preferably (b1), more preferably (b1-1).

The resin [K6] is a resin which is reacted with a resin [K5] and then reacted with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride.

As a carboxylic acid anhydride, for example, maleic anhydride, methyl maleic anhydride, methylene succinic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic 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 and the like. The amount of the carboxylic anhydride to be used is preferably from 0.5 to 1 mol per 1 mol of the use of (a).

As the resin (B), specifically, for example, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxytricyclo[5.2 .1.0 ^2,6 ]Resin/(meth)acrylic acid copolymer resin [K1]; (meth)acrylic acid propyl propyl ester / (meth) methacrylate acrylate / (meth) acrylate copolymer , (meth)acrylic acid propyl propyl ester / styrene / (meth) acrylic acid copolymer, (meth)acrylic acid 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester / (A) Acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylic acid/vinyltoluene (meth)acrylate Copolymer, resin such as 3-methyl-3-(meth)acryloxymethyloxycyclobutane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate Resin such as /(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer [ K3]; a (meth)acrylic acid methacrylate/(meth)acrylic acid copolymer addition resin (meth)acrylic acid propyl propyl ester, (Trimethyl decyl methacrylate / styrene / (meth) acrylate copolymer addition of (meth) acrylate propyl propyl resin, tricyclodecyl (meth) acrylate / (methyl) a resin such as a benzyl acrylate/(meth)acrylic acid copolymer addition resin such as a glycidyl (meth)acrylate; [K4]; a tricyclodecyl (meth)acrylate/(meth)acrylic acid ring The oxypropyl ester copolymer reacts a (meth)acrylic acid-reactive resin with a tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate copolymer to react (meth)acrylic acid. Resin such as resin [K5]; reacting tetrahydrophthalic anhydride with trimethyl decyl (meth) acrylate/glycidyl methacrylate copolymer to react (meth)acrylic acid Resin such as resin [K6].

The resin (B) is preferably selected from the group consisting of a resin [K1] and a resin [K2]. And one of the groups of the resin [K3], more preferably one selected from the group consisting of the resin [K2] and the resin [K3]. In the case of these resins, the coloring curable resin composition is excellent in developability. From the viewpoint of the adhesion of the colored pattern to the substrate, the resin [K2] is more preferable.

The weight average molecular weight of the converted polystyrene of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is increased, the residual film ratio is also high, and the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B) is desirably from 50 to 170 mg-KOH/g, more desirably from 60 to 150 mg-KOH/g, still more desirably from 70 to 135 mg-KOH/g. Here, the value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B) in acid value is obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid components. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenically unsaturated bond, etc., and is preferably ( Methyl) acrylate compound.

As a polymerizable compound having one ethylenically unsaturated bond, such as C Nonylphenyl carbitol, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbamide, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc. (a), (b) and (c) above.

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(methyl). Acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol. Alcohol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentenol octa (meth) acrylate, tripentyltetraol hexa (meth) acrylate, tetraxin Pentaerythritol deca (meth) acrylate, tetrapentaerythritol 九 (meth) acrylate, tris(2-(methyl) propylene methoxyethyl) isocyanate, ethylene glycol modified neopentyl alcohol Tetrakis (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified neopentyl alcohol tetra (meth) acrylate, propylene glycol modified dipentaerythritol (meth) acrylate, caprolactone modified neopentyl alcohol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc., of which dipentaerythritol (Meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid component.

The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably from 20:80 to 80:20, more preferably from 35:65, on a weight basis. 80:20.

When the content of the polymerizable compound (C) is in the above range, the residual film ratio and the color resistance of the color filter tend to be improved when the colored pattern is formed.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid or the like by the action of light or heat, and a conventional polymerization initiator can be used.

As the polymerization initiator (D), for example, an O-indenyl hydrazine compound, a phenylalkyl ketone compound, a diimidazole compound, a triazine compound, a mercaptophosphine oxide compound, or the like can be mentioned.

The above O-indenyl ruthenium compound is a compound having a structure represented by the formula (d1). Hereinafter, * indicates a bond.

As the aforementioned O-indenyl hydrazine compound, for example, N-benzylideneoxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzylideneoxy-1 -(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropane-1 -keto-2-imine, N-acetoxy-1-[9-ethyl -6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2 -methyl-4-(3,3-dimethyl-2,4-dioxolanylmethyloxy)benzylidenyl}-9H-indazol-3-yl]ethane-1- Imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1- Imine, N-benzylideneoxy-1-[9-ethyl-6-(2-methylbenzimidyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1 - keto-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF Corporation, or N-1919 (made by ADEKA)) can be used. Wherein the O-indenyl hydrazine compound is selected from the group consisting of N-benzylideneoxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzylideneoxy- 1-(4-Phenylnonylphenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropane- At least one of the groups of 1-keto-2-imine is preferred, and N-benzylideneoxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imide is more ideal. In the case of these O-fluorenyl ruthenium compounds, there is a tendency for a color filter having high luminance to be obtained.

The phenylalkyl ketone compound is a compound having a structure represented by the formula (d2) or a structure represented by the formula (d3). In these configurations, the benzene ring may have a substituent.

As a compound having a structure represented by the formula (d2), for example, 2-methyl-2-(N-morpholinyl)-1-(4-methylnonylphenyl)propan-1-one, 2-dimethyl Amino-1-(4-morpholinylphenyl)-2-benzylidenebutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)- 1-[4-(4-morpholinyl)phenyl]butan-1-one Wait. Commercial products such as Irgacure 369, 907, and 379 (manufactured by BASF Corporation) can be used.

As a compound having the structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2- Oligomers of hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Polymer, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, a compound having a partial structure represented by the formula (d2) is preferable as the phenylalkyl ketone compound.

The above bisimidazole compound is a compound represented by the formula (d5).

[In the formula (d5), R ^13b to R ^18b represent an aromatic group having 6 to 10 carbon atoms which may have a substituent. ]

As the aryl group having 6 to 10 carbon atoms, for example, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group or the like is preferable, and a phenyl group is preferable.

Examples of the substituent include a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and the like. The halogen atom is preferably a chlorine atom, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkoxy group having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or the like is preferably a methoxy group.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (refer to Japanese Patent Laid-Open No. Hei 6-75372, Japan JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorobenzene) -4,4',5,5'-tetrakis(alkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra Dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (refer to Japanese Special Public Show) An imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with alkoxy group is disclosed in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. Wait. Among them, a compound represented by the following formula and a mixture thereof are preferred.

As the aforementioned triazine compound, for example, 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-piperidin-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

As the aforementioned mercaptophosphine oxide compound, for example, 2,4-6 trimethylbenzene Formyldiphenylphosphine oxide and the like.

Further, as the polymerization initiator (D), for example, a benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; diphenyl ketone, o-benzidine Methyl benzoate, 4-phenyldiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (t-butyl) a diphenyl ketone compound such as oxycarbonyl)diphenyl ketone or 2,4,6-trimethyldiphenyl ketone; 9,10-phenanthrenequinone, 2-ethyl hydrazine, camphor quinone Isoammonium compound; 10-butyl-2-chloroacridone, diphenylethylenedione, methyl phenylglyoxylate, titanocene, and the like.

These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of a phenylalkyl ketone compound, a triazine compound, a mercaptophosphine oxide compound, an O-mercapto fluorene compound, and a diimidazole compound. More preferably, it is a polymerization initiator containing an O-indenyl ruthenium compound.

The content of the polymerization initiator (D) is preferably from 0.1 to 40 parts by mass, more preferably from 1 to 30 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C).

<Polymerization Initiator (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a polymerizable compound which initiates polymerization by a polymerization initiator. In the case of containing a polymerization initiation aid, it is usually used in combination with the polymerization initiator (D).

As a polymerization initiation aid (D1), for example, an amine compound, an alkoxy group a compound, a thioxanthone compound, a carboxylic acid compound, and the like.

As the aforementioned amine compound, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamine Isoamyl benzoate, dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-double (Dimethylamino)diphenyl ketone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-double ( Ethylmethylamino)diphenyl ketone or the like, of which 4,4'-bis(diethylamino)diphenyl ketone is more preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

As the alkoxyfluorene compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 , 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the aforementioned thioxanthone compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthiaxanone, 2,4-dichlorothiazepine Ketone, 1-chloro-4-propoxythioxanthone and the like.

As the carboxylic acid compound, for example, phenylmercaptoacetic acid, methylphenylmercaptoacetic acid, ethylphenylmercaptoacetic acid, methylethylphenylmercaptoacetic acid, dimethylphenylmercaptoacetic acid, methoxyphenylmercaptoacetic acid , dimethoxyphenyl-mercaptoacetic acid, chlorophenyl-mercaptoacetic acid, dichlorophenyl-mercaptoacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthalene Oxyacetic acid, etc.

When the polymerization initiation aid (D1) is used, the content thereof is 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). It is intended to be 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with high sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (a solvent containing -O- in the molecule but not containing -COO-), an ether ester solvent (including -COO- and in the molecule) -O-solvent), ketone solvent (solvent containing -CO- but not -COO- in the molecule), alcohol solvent (solvent containing OH but not -O-, -CO- and -COO-) , an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, and the like.

As the ester solvent, for example, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, C Butyl acrylate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexanol Acetate, γ-butyrolactone, and the like.

As an ether solvent, for example, 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 Alcohol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, Tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, Diethylene glycol dibutyl ether, anisole, phenyl ether, Methyl anisole and the like.

As the ether ester solvent, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy Ethyl 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, dipropylene glycol single Methyl ether acetate and the like.

As a ketone solvent, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone , cyclopentanone, cyclohexanone, isophorone and the like.

As the alcohol solvent, for example, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin or the like can be mentioned.

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

As the guanamine solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-pyrrolidone or the like.

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

Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol are preferred. Monobutyl 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, N-pyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate Ester, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N-pyrrolidone.

The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the colored curable resin composition, in other words, the solid content of the colored curable resin composition, It 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 improved, and when the color filter is formed, the color density is not insufficient, and the display characteristics tend to be improved.

<Leveling agent (F)>

As the leveling agent (F), for example, a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

The polyoxo-based surfactant is, for example, a surfactant having a siloxane chain in the molecule. Specifically, for example, Toray Silicone DC3PA, with SH7PA, with DC11PA, with SH21PA, with SH28PA, with SH29PA, with SH30PA, with SH8400PA (trade name: 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, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

The fluorine-based surfactant is, for example, a surfactant having a fluorocarbon chain in the molecule. Specifically, for example, Fluorad (registered trademark) FC430, FC431 (Sumitomo 3M (share) system), Megafac (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same F554, same R30, same RS -718-K (DIC system), Eftop (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, same S382, same SC101 With SC105 (Asahi Glass Co., Ltd.) and E5844 (Dakin Fine Chemicals Co., Ltd.).

The polyfluorene-based surfactant having a fluorine atom is, for example, a surfactant having a siloxane chain and a fluorocarbon chain in the molecule. Specifically, for example, Megafac (registered trademark) R08, BL30, F475, F477, and F443 (DIC).

When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less based on the total amount of the coloring curable resin composition. More preferably, it is 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent (F) is in the above range, the flatness of the color filter can be made good.

<Antioxidant (H)>

From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferred to use two or more kinds of antioxidants alone or in combination. The antioxidant is not particularly limited as long as it is generally used in the industry, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like can be used.

As the phenolic antioxidant, for example, Irganox 1010 (neopentitol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], BASF (manufactured by BASF), Irganox 1076 (octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), Irganox 1330 (3,3',3",5 , 5',5"-hexa-t-butyl-a, a', a"-(mesitylene-2,4,6-triyl)tri-p-cresol, BASF (manufactured by BASF), Irganox 3114 (1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)- Triketone, BASF (manufactured by BASF), Irganox 3790 (1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl)-1,3,5 - Triazine-2,4,6-(1H,3H,5H)-trione, BASF (manufactured by BASF), Irganox 1035 (thio-diethylidene double [3-(3,5-di-third) 4-hydroxyphenyl)propionate], BASF (manufactured by BASF), Irganox 1135 (phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyl, C7- C9 side chain alkyl ester, BASF (manufactured by BASF), Irganox 1520L (4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF), Irganox 3125 (BASF) ), Irganox 565 (2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-t-butylanilino)-1,3,5-triazine, BASF (share) system, ADEKASTAB AO-80 (3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propenyloxy)-1, 1-dimethylethyl)-2,4,8,10-tetraoxy Spiral (5,5) undecane, ADEKA (manufactured by ADEKA), Sumilizer BHT (Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumitomo Chemical Co., Ltd.) ), Cyanox 1790 (made by CYTEC) and vitamin E (made by EISAI).

As the phosphorus-based antioxidant, for example, Irgafos 168 (tris(2,4-t-butylphenyl)phosphite, manufactured by BASF), Irgafos 12 (three [2-[[2,4,8, 10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd., Irgafos 38 (double ( 2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, BASF (manufactured by BASF), ADEKASTAB 329K (made by ADEKA), ADEKASTAB PEP36 (made by ADEKA), ADEKASTAB PEP-8 (made by ADEKA), Sandstab P-EPQ (made by Clariant), Weston 618 (made by GE), Weston619G (manufactured by GE), Ultranox 626 (manufactured by GE), and Sumilizer GP (6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4, 8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin (manufactured by Sumitomo Chemical Co., Ltd.).

As the sulfur-based antioxidant, for example, a dialkylthiodipropionate compound such as dilauryl thiodipropionate, dimyristyl or distearyl, and tetrakis[methylene(3-dodecylsulfide) A β-alkylthiol propionate compound of a polyol such as propionate]methane or the like.

<Other ingredients>

The colored curable resin composition of the present invention may contain a conventionally known additive such as a filler, another polymer compound, an adhesion promoter, a photosetter, or a chain transfer agent, as needed.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention may be prepared by mixing a coloring agent (A) such as a compound (AI), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). And a leveling agent (F), a polymerization initiation aid (D1), and other components used as needed.

When the pigment (P) is contained, it is preferably mixed with a part or all of the solvent (E) in advance, and is preferably dispersed in a bead mill or the like until the average particle diameter of the pigment is 0.2 μm or less. At this time, a part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. By using the obtained pigment dispersion, mixing The remaining component is a predetermined concentration, and the intended color-curable resin composition can be prepared.

The dye of the colorant (A) is preferably dissolved in a part or all of the solvent (E) to prepare a solvent. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.

The mixed color-curable resin composition is preferably filtered with a filter having a pore diameter of about 0.1 to 10 μm.

<Method of Manufacturing Color Filter>

A method of producing a colored pattern from the colored curable resin composition of the present invention is, for example, a lithography method, an inkjet method, a printing method, or the like. Among them, the lithography method is ideal. The lithography method is a method in which the colored curable resin composition is applied onto a substrate and dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the lithography method, the colored coating film of the cured product of the colored composition layer can be formed by using no mask and/or no image formation during exposure. The colored pattern and the colored coating film thus formed are the color filters of the present invention.

The film thickness of the produced color filter is not particularly limited and may be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, more preferably 0.1 to 20 μm, still more preferably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with cerium oxide, polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used. A resin plate such as ethylene glycol or the like, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. On the substrates, additional color filter layers, resin layers, and transistors can be formed. Circuits, etc.

The formation of the pixels of the respective colors by the lithography method can be carried out by conventional or conventional devices and conditions. For example, it is made in the following manner.

First, a colored curable resin composition is applied onto a substrate, and dried by heating (pre-baking) and/or drying under reduced pressure to remove volatile components such as a solvent and drying the mixture to obtain a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, a slit, and a spin coating method.

The temperature at the time of heat drying is preferably from 30 ° C to 120 ° C, more preferably from 50 ° C to 110 ° C. Further, as the heating time, it is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

In the case of performing vacuum drying, it is preferred to carry out the temperature range of 20 ° C to 25 ° C at a pressure of 50 Pa to 150 Pa.

The film thickness of the coloring composition layer is not particularly limited, and may be appropriately adjusted depending on the purpose of the color filter.

Then, the composition layer is colored and exposed by a photomask for forming a desired coloring pattern. The pattern on the reticle is not particularly limited, and a pattern corresponding to the purpose of the purpose is used.

As the light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm is blocked by a filter that blocks the wavelength region, and light near 436 nm, around 408 nm, and around 365 nm is selectively taken out using a band pass filter that takes out the wavelength regions. Specifically, as the light source, for example, a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, or the like.

In order to uniformly illuminate the parallel light rays on the entire exposed surface, it is preferable to perform accurate alignment of the photomask with the substrate on which the coloring composition layer is formed, and to use an exposure apparatus such as a photomask alignment machine and a stepper.

The exposed coloring composition layer is developed in contact with the developing liquid to form a colored pattern on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved in the developing solution and removed. As the developing solution, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of the basic compound is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Furthermore, the developing solution may also contain a surfactant.

The development method may be any of a paddle method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at any angle during development.

It is desirable to perform water washing after development.

Furthermore, it is preferable to perform post-baking in the obtained coloring pattern. The post-baking temperature is preferably from 150 ° C to 250 ° C, more preferably from 160 ° C to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

By using the colored curable resin composition of the present invention, in particular, a color filter excellent in heat resistance can be produced. As the color filter, a color filter used as a display device (liquid crystal display device, organic EL device, electronic paper, etc.) or a solid-state imaging device can be used.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. In the case of content or amount % and parts are quality benchmarks without special restrictions.

In the following, the structure of the compound was confirmed by mass analysis (LC; Agilent Model 1200, MASS; Agilent LC/MSD type).

Synthesis Example 1

2.00 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 50 parts of methanol to dissolve it. Further, 15.41 parts of 2,6-dihydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.09 parts of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at 65 ° C for 8.5 hours. After the mixture was cooled to room temperature, the precipitate was obtained by vacuum filtration, and washed with 237 parts of ion-exchanged water to obtain 10.90 parts of the compound of formula (BC-1-Na).

Synthesis Example 2

5.1 parts of Basic Blue 7 (Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 parts of water, and a solution in which 3.4 parts of the compound (BC-1-Na) was dissolved was added while stirring. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to give 8.0 parts of a dye of the formula (A-I-1) of a blue crystal.

Synthesis Example 3

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was poured in an appropriate amount to obtain a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was fed, and the mixture was heated to 85 ° C while stirring. Then, in the flask, using a drip pump, about 10 parts of propylene glycol monomethyl ether acetate was dissolved in 19 parts of methacrylic acid, and 3,4-epoxytricyclo(5.2.1.0) was prepared in about 5 hours. a mixture of ^2,6 ]decane-8-yl ester and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (in proportion, with a molar ratio of 50: 50) (product name "E-DCPA", manufactured by DAICEL Co., Ltd.) 171 parts of the solution was dropped. On the other hand, using another drip pump, about 2 hours, 120 parts of propylene glycol monomethyl ether acetate was dissolved in the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile). 26 parts of the solution was dropped into the flask. After completion of the dropwise addition of the polymerization initiator, the same temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a solution of the copolymer resin (B-1) having a solid content of 43.5%. The obtained resin (B-1) had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value of 53 mg-KOH/g in terms of solid content, and had the following structural unit.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin-converted polystyrene was carried out by the GPC method under the following conditions.

Device: HLC-8120GPC (Tosoh)

Column: TSK-GELG200HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0 mL/min

Solid content concentration of the tested liquid: 0.001 to 0.01 mass

Injection volume: 50μL

Detector: RI

Standard materials for calibration: TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (made by Tosoh)

The ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the converted polystyrene obtained above is a molecular weight distribution.

Synthesis Example 4

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 250.4 parts of propylene glycol monomethyl ether acetate was taken, and the temperature was raised to 120 ° C while stirring with nitrogen. Then, 37.4 parts of methacrylic acid, 61.3 parts of benzyl methacrylate, 18.5 parts of glycidyl methacrylate, and monomethacrylate having a tricyclodecane skeleton (Hitachi Chemical Co., Ltd.) To the monomer mixture composed of 19.2 parts of FA-513M), 6.13 parts of a third butyl hydroperoxide (PERBUTYL O, manufactured by Nippon Oil & Fats Co., Ltd.) was added. This was poured into a funnel over 2 hours, dropped into a flask, and further stirred at 120 ° C for 2 hours to carry out aging. Then, the flask was replaced with air, and 0.9 parts of tris-dimethylaminomethylphenol (DMP-30) and 0.145 parts of hydroquinone were added to the above aged solution in 10.6 parts of acrylic acid, and the reaction was continued at 120 ° C for 6 hours. A solution of a copolymer (resin (B-2)) having a solid content of 38.4% by mass and an acid value of 122 mg-KOH/g was obtained. The obtained resin (B-2) had a weight average molecular weight Mw of 10,700 and a molecular weight distribution of 2.18.

The weight average molecular weight and the molecular weight distribution were measured by the same method as the resin (B-1).

[Preparation of coloring curable resin composition]

Example 1

Coloring agent (A): 24 parts of the dye represented by the formula (AI-1); alkali-soluble resin (B): resin (B-2) (converted solid content) 60 parts; polymerizable compound (C): two new Pentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 40 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylmercaptophenyl) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 10 parts; solvent (E): propylene glycol monomethyl ether acetate 413 parts Solvent (E): 413 parts of ethyl lactate; and leveling agent (F): polyether modified eucalyptus oil (Torav Silicone SH8400; East 0.2 parts by Lido Corning Co., Ltd.; and mixed to obtain a colored curable resin composition.

Example 2

Colorant (A): CI Pigment Blue 15:6 (pigment) 4.48 parts; acrylic pigment dispersant 1.76 parts; propylene glycol monomethyl ether acetate 29.8 parts; mixed, and fully dispersed using a ball mill, and then Coloring agent (A): 10 parts of the dye represented by the formula (AI-1); alkali-soluble resin (B): resin (B-2) (converted solid content) 60 parts; polymerizable compound (C): dioxane Tetraol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 40 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylmercaptophenyl) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 10 parts; solvent (E): propylene glycol monomethyl ether acetate 300 parts; Solvent (E): 250 parts of ethyl lactate; and leveling agent (F): Polyether modified eucalyptus oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 parts; together, to obtain a colored curable resin composition .

Comparative example 1

Coloring agent (A): 26 parts of the dye represented by the formula (A-III-1); alkali-soluble resin (B): resin (B-1) (converted solid content) 53 parts; polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD) (registered trademark) DPHA; Nippon Chemical Co., Ltd.) 16 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylmercaptophenyl)octane-1-one- 2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 4 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; solvent (E): 4- 480 parts of hydroxy-4-methyl-2-pentanone; and leveling agent (F): polyether modified eucalyptus oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts; mixed to obtain color hardening property Resin composition.

[Production of color filter]

The colored curable resin composition was applied onto a 2 Å square glass substrate (#1737; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, exposure was carried out using an exposure machine (TME-150RSK; TOPCON) to expose the exposure amount (365 nm reference) at 150 mJ/cm ² in an atmosphere. Also, no mask is used. The colored composition layer after the exposure was placed in an oven, and baked at 180 ° C for 20 minutes to prepare a color filter (film thickness: 2.8 μm).

[Heat resistance evaluation]

The coating film of the colored curable resin composition was heated at 230 ° C for 20 minutes, and the color difference (ΔEab*) before and after heating of the coating film was used, and a color measuring machine (OSP-SP-200; Olympus) was used. The company system) performs the measurement. The coating film obtained in each of Examples 1 and 2 was subjected to the above heat resistance evaluation, and the color difference (ΔEab*) was 9.7 and 5.7, respectively.

Further, as a result of the same heat resistance evaluation as in Comparative Example 1, the color difference (ΔEab*) was 12.1. It is known that the color filter formed of the colored curable resin composition of the present invention has excellent heat resistance.

Industrial availability

According to the colored curable resin composition of the present invention, a color filter excellent in heat resistance can be provided. As the color filter, a color filter used as a display device (liquid crystal display device, organic EL device, electronic paper, etc.) or a solid-state imaging device can be used.

Claims (6)

A colored curable resin composition comprising: a compound represented by the formula (AI), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E); [In the formula (AI), X ^- represents an anion containing a boron atom or an aluminum atom, and A represents a group represented by the formula (A-VI-1) or the formula (A-VI-2); * represents a bond with a carbon atom; key; R ¹ to R ¹⁸ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms or a halogen atom; and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atom to which the bond is bonded; R ²¹ and R ²² each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or represent a nitrogen atom bonded thereto; Rings formed together; R ²³ and R ²⁴ each independently represent a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto; R ²⁵ and R ²⁶ independently represents a hydrogen atom, -R ^26a or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a ring formed together with the nitrogen atoms bonded thereto; and in R ¹⁹ to R ²⁶ , the aromatic hydrocarbon group The hydrogen atom contained may be a halogen atom, -R ^26a , -OH, -OR ^26a , -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ^26a , -SO ₃ H, -SO ₃ R ^26a or -SO ₂ NHR ^{28a is} substituted; R ^26a represents a saturated hydrocarbon group having 1 to 10 carbon atoms; the hydrogen atom contained in the saturated hydrocarbon group may be -OR ^27a (wherein R ^27a represents a carbon number of 1 to 10 saturation) hydrocarbon ), A halogen atom or a substituted phenyl sulfonic acid alkali metal salt; R ^28a represents a hydrogen atom, -R ^26a, -CO ₂ R ^26a, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, the hydrogen atoms contained in the aromatic hydrocarbon group, Can be replaced by -R ^26a or -OR ^27a ]. The colored curable resin composition according to claim 1, further comprising: a blue pigment. The colored curable resin composition according to claim 1 or 2, further comprising: an antioxidant (H). A coating film formed by the color hardening resin composition as described in claim 1 or 2. A color filter formed of the color hardening resin composition as described in claim 1 or 2. A display device comprising: the color filter according to claim 5 of the patent application.