KR101972613B1 - Dyes and colored curable resin composition - Google Patents

Abstract

The present invention relates to a dye represented by the following formula (I).

Description

DYES AND COLORED CURABLE RESIN COMPOSITION [0002]

The present invention relates to a dye and a colored curable resin composition.

As a colored curable resin composition for a color filter contained in a liquid crystal display device or a solid-state image sensing device, a compound represented by the following formula (A-III-1) is described in US 8,282,862 B1.

The present invention provides the following [1] to [7].

[1] A dye represented by the following formula (I):

In the above formula (I), each of R ^1A to R ^8A independently represents a hydrogen atom, a halogen atom, a hydroxy group or an alkyl group having 1 to 20 carbon atoms (oxygen atom may be interposed between carbon atoms constituting the alkyl group)

R ^9A to R ^12A each independently represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (the oxygen atom may be inserted between the carbon atoms constituting the alkyl group) R ^9A and R ^10A may be combined with each other to form a ring together with the nitrogen atom to which they are bonded, and R ^11A and R ^12A may be combined to form a ring together with the nitrogen atom to which they are bonded,

A represents a heteroaromatic group which may have a substituent,

Two of R ¹ to R ⁴ are each independently a group represented by the following formula (i), and the remaining two are each independently an alkyl group having 1 to 20 carbon atoms (an oxygen atom is inserted between the carbon atoms constituting the alkyl group , And "

(In the above formula (i), n represents an integer of 1 to 8, and * represents the number of bonds (bonds) with a nitrogen atom)

R ⁵ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxy group or an alkyl group having 1 to 20 carbon atoms (oxygen atom may be interposed between carbon atoms constituting the alkyl group)

R ¹⁷ is a group represented by the following formula (ii).

(In the above formula (ii), R ¹⁸ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * indicates the number of bonds with carbon atoms)

[2] A colorant (A) comprising the dye according to [1] above,

The resin (B)

The polymerizable compound (C)

The polymerization initiator (D)

And a coloring curable resin.

[3] The colored curable resin composition according to [2], wherein the colorant (A) further comprises at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye.

[4] The colored curable resin composition according to the above [2] or [3], further comprising a colorless metallic complex (F).

[5] A coating film formed from the colored curable resin composition according to any one of [2] to [4] above.

[6] A color filter formed from the colored curable resin composition according to any one of [2] to [4].

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

The present invention is a colored curable resin composition comprising a dye represented by the formula (I) and a dye represented by the formula (I).

A dye represented by the following formula (I) [hereinafter sometimes referred to as a dye (A1)] also includes tautomers thereof.

In the above formula (I), each of R ^1A to R ^8A independently represents a hydrogen atom, a halogen atom, a hydroxy group or an alkyl group having 1 to 20 carbon atoms (oxygen atom may be interposed between carbon atoms constituting the alkyl group)

R ^9A to R ^12A each independently represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (the oxygen atom may be inserted between the carbon atoms constituting the alkyl group) R ^9A and R ^10A may be combined with each other to form a ring together with the nitrogen atom to which they are bonded, and R ^11A and R ^12A may be combined to form a ring together with the nitrogen atom to which they are bonded,

A represents a heteroaromatic group which may have a substituent,

Two of R ¹ to R ⁴ are each independently a group represented by the following formula (i), and the remaining two are each independently an alkyl group having 1 to 20 carbon atoms (an oxygen atom is inserted between the carbon atoms constituting the alkyl group , And "

(In the above formula (i), n represents an integer of 1 to 8, and * represents the number of bonds with a nitrogen atom)

R ⁵ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxy group or an alkyl group having 1 to 20 carbon atoms (oxygen atom may be interposed between carbon atoms constituting the alkyl group)

R ¹⁷ is a group represented by the following formula (ii).

(In the above formula (ii), R ¹⁸ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * indicates the number of bonds with carbon atoms)

In the formula (I), examples of the halogen atom include a fluorine atom, a chlorine atom and an iodine atom.

In the formula (I), the alkyl group having 1 to 20 carbon atoms may be any of linear, branched and cyclic.

Examples of the alkyl group include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, , A straight chain alkyl group having 1 to 20 carbon atoms such as a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group;

A methylpentyl group, a 4-methylpentyl group, a 1-ethylbutyl group, a 2-ethylpentyl group, an isobutyl group, an isobutyl group, an isopentyl group, Propylphenyl group, 3-ethylpentyl group, 3-methylpentyl group, 3-methylpentyl group, 3-methylpentyl group, 3-methylpentyl group, Methylpropyl group, a 1-methylbutyl group, a 2-methylheptyl group, a 3-methylheptyl group, a 1- , 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, Butyl group, a 1,1-dimethylpropyl group, a 1,1-dimethylbutyl group, a 1,2-dimethyl (1-methylbutyl) Dimethylbutyl group, a 1-ethyl-2-methylpropyl group, a 1,1-dimethylpentyl group, a 1,2-dimethylpentyl group, a 1,3-dimethyl Pentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, Dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 1-ethyl-1-methylbutyl, Ethyl-3-methylbutyl group, a 2-ethyl-3-methylbutyl group, a 1,1-dimethylhexyl group, a 1,2-dimethylhexyl group, Dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4- Dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl group, 4,5-dimethylhexyl group, Ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2-ethyl-1-methylpentyl group, Ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, Propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, (1-methylethyl) -3-methylbutyl group, a 1,1-diethylbutyl group, a 1,2-diethylbutyl group A branched alkyl group having from 3 to 20 carbon atoms, e.g.

A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 2-methylpentyl group, a 2-methylhexyl group, a 2,5-dimethylpentyl group, and a 2,6-dimethylhexyl group. have.

As the halogen atom represented by R ^1A to R ^8A , a fluorine atom or a chlorine atom is preferable.

As the alkyl group represented by R ^1A to R ^8A , an alkyl group having 1 to 10 carbon atoms is preferable, and a group represented by the following formula is more preferable. In the following formula, * represents the number of bonds with carbon atoms.

The alkyl group represented by R ^1A to R ^8A may have an oxygen atom inserted between the carbon atoms constituting the alkyl group.

Examples of the group in which an oxygen atom is inserted between the carbon atoms constituting the alkyl group include groups represented by the following formulas. In the following formula, * represents the number of bonds with carbon atoms. Among them, in the alkyl group having 1 to 10 carbon atoms, a group in which an oxygen atom is inserted between the carbon atoms constituting the alkyl group is preferable. In the alkyl group having 1 to 6 carbon atoms, an oxygen atom The inserted group is more preferable.

As R ^1A to R ^8A , a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a hydrogen atom or a methyl group is preferable.

The alkyl group in R ^9A to R ^12A may have an oxygen atom inserted between the carbon atoms constituting the alkyl group. Examples of the group in which an oxygen atom is inserted between the carbon atoms constituting the alkyl group include the same groups as those in R ^1A to R ^8A .

In R ^9A to R ^12A , the alkyl group having 1 to 20 carbon atoms may be substituted with an amino group or a halogen atom.

Examples of the alkyl group substituted with an amino group or a halogen atom include groups represented by the following formulas. In the following formulas, * represents the number of bonds with the nitrogen atom.

As the alkyl group in R ^9A to R ^12A , an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

In the aryl group which may have a substituent, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and iodine; A haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; An alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; A hydroxy group; Sulfamoyl group; And an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group, and the like. Of these, a halogen atom, a hydroxyl group, a methoxy group, and a sulfamoyl group can be exemplified.

In the aryl group which may have a substituent, examples of the aryl group include an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group, preferably a phenyl group.

Examples of the aryl group which may have a substituent include groups represented by the following formulas. In the following formulas, * represents the number of bonds with the nitrogen atom.

^Examples of the ring formed by combining R ^9A and R ^10A and R ^11A and R ^12A together with the nitrogen atom to which they are bonded include a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring, and the like.

As R ^9A to R ^12A , a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms are preferable, and a hydrogen atom, a methyl group, an ethyl group and a phenyl group are more preferable.

A represents a heteroaromatic group which may have a substituent.

Examples of the heteroaromatic group include an aromatic ring having 4 to 8 carbon atoms and having a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaromatic group may be either a single ring or a multiple ring. In the heteroaromatic group, the nitrogen atom, the oxygen atom and the sulfur atom may contain two or more, respectively, or a combination thereof.

Specific examples of the heteroaromatic group include pyrrole, imidazole, thiazole, oxazole, furan, thiophene, triazole, pyrazole, isoxazole, isothiazole, pyridine, pyrazine, pyridazine, pyrimidine, , Indole, benzofuran, benzothiophene, benzimidazole, benzthiazole, quinoline, isoquinoline, quinazoline, quinoxaline, etc., and an aromatic group having a nitrogen atom is preferable. As the aromatic group having a nitrogen atom, a sulfur atom or an oxygen atom may be further contained, and a group having a 5-membered ring and a 5-membered ring are preferable.

Examples of the substituent in the heteroaromatic group include a halogen atom such as a fluorine atom, a chlorine atom and iodine; A haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; An alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; A hydroxy group; An amino group; An alkylamino group; Dialkylamino group; And preferred examples thereof include an alkyl group, an amino group, an alkylamino group and a dialkylamino group. Examples of the alkyl group in the alkylamino group and the dialkylamino group include an alkyl group having 1 to 4 carbon atoms.

As A, there can be mentioned the following formulas (A-1) to (A-10), among which groups represented by the formula (A-1) are preferable.

[R ^1a to R ^25a represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group) or an aryl group which may be substituted , * Represents the number of bonds with carbon atoms.]

Examples of the alkyl group and the aryl group in R ^1a to R ^25a include the same groups as the alkyl group and the aryl group in R ^9A to R ^12A , respectively.

Specific examples of the group represented by the formula (A-1) include the following groups.

Two of R ¹ to R ⁴ are groups represented by the formula (i). It is preferable that R ¹ and R ³ are groups represented by the formula (i).

Examples of the group represented by the formula (i) include those represented by the following formulas (i-1) to (i-6) (I-1) is particularly preferable.

[* Represents the number of bonds with nitrogen atom]

As the alkyl group represented by R ¹ to R ⁴ , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.

As the alkyl group represented by R ⁵ to R ¹⁶ , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.

As the group represented by R ⁵ to R ¹⁶ , a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is particularly preferable.

In the formula (ii), examples of the alkyl group represented by R ¹⁸ include a methyl group, an ethyl group, a propyl group and a butyl group, and a methyl group and an ethyl group are preferable.

As the alkoxy group represented by R ¹⁸ , a methoxy group and an ethoxy group are exemplified, and an ethoxy group is preferable.

Examples of the group represented by the formula (ii) include groups represented by the following formulas (ii-1) to (ii-6), and from the viewpoint of solubility, Is particularly preferable, among which groups represented by the formula (ii-5) are particularly preferable.

[* Represents the number of bonds with carbon atoms]

Specific examples of the dyes represented by the formula (I) include dyes represented by the following formulas.

Hereinafter, a method for producing a dye represented by the formula (I) will be described.

The process for producing the dye represented by the formula (I) includes a process comprising reacting a dye represented by the following formula (1-a)

A salt of an anion and a metal cation represented by the following formula (1-b)

In a solvent.

The dye represented by the formula (1-a) or the anion represented by the formula (1-b) can be synthesized according to the description of WO-A-2012-53211. As the anion represented by the formula (1-b), commercially available products can be used.

Examples of the metal cation which forms a salt include alkali metal cations such as lithium cation, sodium cation and potassium cation.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran , Dioxane, water and chloroform.

Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, methanol, ethanol, isopropanol and water are preferable and water is more preferable.

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

The dye represented by the formula (1-a) and the salt of the anion represented by the formula (1-b) and the salt of the metal cation may be either dissolved in the above-mentioned solvent or may be carried out without dissolution .

The mixing temperature of the dye represented by the formula (1-a) and the salt represented by the above formula (1-b) is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, Lt; 0 > C to 100 [deg.] C.

The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 48 hours, and further preferably 3 hours to 24 hours.

When a solvent compatible with water is used, the reaction solution obtained by the above mixing may be stirred for 1 to 3 hours, if necessary, and then filtered to extract the compound represented by the formula (I) as a solid have.

In the case of using a solvent which is incompatible with water, the dye represented by the formula (I) can be extracted as a solid by precipitating crystals by adding water to the reaction solution, and then by filtration.

The colored curable resin composition of the present invention comprises a colorant (A) containing a dye represented by the formula (I), a resin (B), a polymerizable compound (C) and a polymerization initiator (D). If necessary, a solvent (E), a colorless metal complex (F) and the like may be included.

≪ Colorant (A) >

The colorant (A) further includes at least one dye (A2) (hereinafter sometimes referred to as a dye (A2)) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye, including the dye .

The anthraquinone dye may be a known material. As the anthraquinone dyes,

C.I. Solvent Yellow 117 (hereinafter abbreviated as C.I. Solvent Yellow, and only numbers are given), 163, 167, 189,

C.I. Solvent Orange 77, 86,

C.I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,

C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,

C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 112, 122, 128, 132, 136, 139,

C.I. Solvent Green 3, 28, 29, 32, 33,

C.I. Acid Red 80,

C.I. Acid Green 25, 27, 28, 41,

C.I. Acid Violet 34,

C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112

C.I. Disperse Yellow 51,

C.I. Disperse Violet 26, 27,

C.I. Disperse Blue 1, 14, 56, 60,

C.I. Direct Blue 40,

C.I. Modern Red 3, 11,

C.I. Modern Blue 8

And the like.

The anthraquinone dyes are preferably dissolved in an organic solvent, and blue, violet and red anthraquinone dyes are more preferable.

More preferred anthraquinone dyes include compounds represented by the following formulas (3-1) to (3-11).

The anthraquinone dyes are more preferably the compounds represented by formulas (3-4) and (3-11). With these anthraquinone dyes, it is possible to form a coating film or pattern having a high contrast, and also to form a coating film or a pattern with less occurrence of foreign matter and excellent in light resistance.

A tetraazaporphyrin dye is a compound having a tetraaza porphyrin skeleton in a molecule. When the tetraazaporphyrin dye is an acidic dye or a basic dye, it may form a salt with any cation or anion.

Specific examples of the tetraazaporphyrin dyes include compounds represented by the following formulas (2-1) to (2-38).

As the tetraazaporphyrin dye, tetraazaporphyrin dyes having copper as a central metal are preferable, and tetraazaporphyrin dyes represented by formulas (2-1), (2-2), (2-8) (2-15), (2-16) and (2-28) to (2-32) are more preferable, and compounds represented by the formula (2-29) are more preferable.

A composition containing the tetraazaporphyrin dye can form a coating film or a pattern with high contrast, and the generation of foreign matter is also small.

The content of the dye (A1) is preferably 0.5 to 100 mass%, more preferably 0.5 to 80 mass%, and still more preferably 40 to 80 mass% with respect to the total amount of the colorant (A).

The content of the dye (A2) is preferably 0 to 99.5% by mass, more preferably 0.5 to 20% by mass with respect to the total amount of the colorant (A).

The colorant (A) may further contain other dyes, pigments (P), or a mixture thereof in order to control coloring, that is, to adjust spectral characteristics, in addition to the dyes (A1) and (A2).

Dyes other than the dye (A1) and the dye (A2) include dyes such as oil soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes and sulfonamide derivatives of acid dyes , Compounds classified as dyes in the color index (published by The Society of Dyers and Colourists), and known dyes described in dyeing notes (Shisensha). According to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, Reel dyes, coumarin dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Solvent Red 45, 49, 125, 130, 218;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56;

C.I. Solvent Blue 4, 5, 37, 67, 70, 90;

C.I. Solvent Green 1, 4, 5, 7, 34, 35, etc. C.I. Solvent dyes,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 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;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 215, 198, 206, 211, 215, 216, 217, 218, 219, 288, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 276, 268, 270, 274, 277, 280, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Violet 6B, 7, 9, 17, 19, 30, 102;

C.I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;

C.I. C.I., such as Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, Acid dyes,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138, 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C.I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 198, 199, 200, 201, 202, 203, 207, 209, 210, 202, 203, 207, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, Direct dyes,

C.I. Disperse Yellow 54, C.I. Disperse dyes,

C.I. Basic Red 1, 10;

C.I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

C.I. Basic Green 1; C.I. Basic dyes,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. Reactive red 36; C.I. Reactive dyes,

C.I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. 43, 38, 39, 41, 43, 43, 43, 43, 42, 43, , 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 , 74, 77, 83, 84;

C.I. CI. 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, Modern dyes,

C.I. C.I. Bat dyes,

And the like.

Among them, a blue dye, a violet dye and a red dye are preferable.

These dyes may be used alone, or two or more dyes may be used in combination.

The pigment (P) is not particularly limited, and known pigments can be used, and pigments classified as pigments in the color index (The Society of Dyers and Colourists) are cited.

As the pigment, 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, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments such as Pigment Green 7, 36, and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Pigment black 1, pigment black 7, and the like.

The pigment (P) is preferably a phthalocyanine pigment and a dioxazine pigment, and more preferably C.I. Pigment Blue 15: 6 and Pigment Violet 23. By including the above-described pigment, the transmission spectrum can be easily optimized, and the heat resistance, light resistance, and chemical resistance of the color filter can be improved.

The content of the colorant (A) is preferably 5 mass% or more and 70 mass% or less, more preferably 5 mass% or more and 60 mass% or less, further preferably 5 mass% or more and 50 mass% % Or less. If the content of the colorant (A) is within the above range, desired spectral or color density can be obtained.

In the present specification, the "total amount of solid content" refers to the total amount of components excluding the solvent (E) from the colored curable resin composition. The total amount of the solid content and the content of each component in the total amount can be measured by known analytical means such as liquid chromatography or gas chromatography.

≪ Resin (B) >

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) [hereinafter sometimes referred to as " resin (B) ") is a copolymer of a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride ≪ / RTI >

Examples of such a resin (B) include the following resins [K1] to [K6].

(A) (hereinafter sometimes referred to as "(a)") selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a cyclic ether having 2 to 4 carbon atoms And a monomer (b) having an ethylenically unsaturated bond (hereinafter occasionally referred to as "(b)");

(A) and (b), and a monomer (c) copolymerizable with (a), which is different from (a) and (b) ≪ / RTI >

Resin [K3] Copolymer of (a) and (c);

Resin [K4] Resin (b) is reacted with a copolymer of (a) and (c);

Resin [K5] Resin (a) is reacted with a copolymer of (b) and (c);

Resin [K6] Resin (a) is reacted with a copolymer of (b) and (c) and the carboxylic acid anhydride is further reacted.

(a) specifically include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 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-tetrahydrophthalic anhydride , Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride;

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate, mono [2- ]ester;

and? - (hydroxymethyl) acrylic acid, and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoints of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

(b) can be obtained by reacting a polymerizable compound having an ethylenic unsaturated bond with a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of oxirane rings, oxetane rings and tetrahydrofuran rings) It says.

(b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

(b) include a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an ethylenically unsaturated bond and a tetrahydrofuryl group, and the like.

(b) is preferably a monomer having an oxiranyl group and an ethylenically unsaturated bond in that the reliability of the obtained color filter can be further improved, such as heat resistance, chemical resistance and the like.

(meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate [referred to in the art as "dicyclopentanyl (meth) acrylate" (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (Meth) acrylate], dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (Meth) acrylic acid esters such as pargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

(Meth) acrylic acid esters having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 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- Cyclohexylbicyclo [2.2.1] hept-2-ene, 5,6- 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclounsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene are preferred.

In the present specification, the term "(meth) acrylic acid" means at least one member selected from the group consisting of acrylic acid and methacrylic acid. Quot ;, " (meth) acryloyl ", and " (meth) acrylate "

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) A resin [K1] such as a (meth) acrylic acid copolymer; (Meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / Vinyltoluene copolymer, and a resin [K2] such as 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; A resin such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) ]; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (meth) ) Resin, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting a (meth) acrylic acid with a copolymer; A resin such as a resin obtained by further reacting a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride, and the like .

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Ohtsu Takayuki, First Edition, First Edition, issued March 1, 1972, Can be prepared by reference to the literature.

The resin (B) is preferably one kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], more preferably a resin [K2] It is one kind selected from the group. When these resins are used, the colored curable resin composition is excellent in developing property. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K2] is more preferable.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the coloring 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 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. The acid value is a value measured as an amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration using, for example, an aqueous solution of potassium hydroxide.

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total amount of 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 tends to be improved.

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound capable of polymerizing with an active radical and / or an acid generated from the polymerization initiator (D), such as a compound having a polymerizable ethylenically unsaturated bond, ) Acrylic acid ester compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate , N-vinylpyrrolidone, and the above-mentioned (a), (b) and (c).

Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Acrylate, tetrapentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, (Meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra Propylene glycol-modified dipentaerythritol hexa (meth) acrylate, capro (Meth) acrylate such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa The rate is preferred.

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

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

The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is preferably 20:80 to 80:20, more preferably 35: : 65 to 80:20.

When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a color pattern and the chemical resistance of the color filter tend to be improved.

≪ Polymerization initiator (D) >

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

Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, imidazole compounds, triazine compounds and acylphosphine oxide compounds.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3- cyclopentylpropan- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3- Dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ ) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- Yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxime compound is preferably an N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan- 1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine Benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable. If these O-acyloxime compounds are used, a color filter of high brightness tends to be obtained.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- -Benzylbutan-1-one, 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan- Hydroxy-2-methyl-1- [4- (2-hydroxy-2-methyl- -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan- ?,? - diethoxyacetophenone, and benzyl dimethyl ketal.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- ) -4,4 ', 5,5'-tetraphenylbiimidazole (see JP-A 6-75372, JP-A 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'- (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis 4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open No. 62-174204, Imidazole compounds in which the phenyl group at the 5,5'-position is substituted by a carboalkoxy group (see JP-A No. 7-10913).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) -1,3,5-triazine, ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

The polymerization initiator (D) is preferably a polymerization initiator comprising at least one member selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a nonimidazole compound , And more preferably an O-acyloxime compound.

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

≪ Solvent (E) >

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. An ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester solvent (Including a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule and containing no -COO-), an alcohol solvent (containing OH in the molecule, -O-, CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, 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.

Examples of the ether solvent 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 monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydrofuran , 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, A brush, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Cyclopentanone, cyclohexanone, isophorone, and the like.

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

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.

These solvents may be used alone 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 monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, Ethyl propionate, and N-methyl pyrrolidone are more preferred.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 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 is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color characteristic is not insufficient when the color filter is formed, and the display characteristics tend to be good.

≪ Colorless metal complex (F) >

The colored curable resin composition of the present invention may contain a colorless metallic complex (F).

Examples of the colorless metallic complex (F) include a zinc complex represented by the following chemical formula (10).

In the above formula (10), each of R ⁸¹ to R ⁸⁴ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxy group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁸¹ to R ⁸⁴ in the formula (10) include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- . Specific examples of the zinc complex represented by the formula (10) include complexes having the substituents shown in Table 1 below. Among them, from the viewpoint of heat resistance, a complex having a group represented by (10) -18 is preferable.

The content of the colorless metallic complex is preferably 0.1 mass% or more and 30 mass% or less, more preferably 0.5 mass% or more and 15 mass% or less, with respect to the colorant (A).

≪ Other components >

The colored curable resin composition of the present invention may contain additives known in the art such as a polymerization initiator, a leveling agent (H), an antioxidant, a filler, another polymer compound, an adhesion promoter, a light stabilizer, May be included.

Examples of the leveling agent (H) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

As the antioxidant, any antioxidant generally used industrially is not particularly limited, and phenol antioxidants, phosphorus antioxidants, and sulfur-based antioxidants can be used.

≪ Process for producing colored curable resin composition >

The colored curable resin composition of the present invention can be prepared by mixing the dye (A1), the resin (B), the polymerizable compound (C) and the polymerization initiator (D) as the colorant (A). The dye (A2), the colorless metal complex (F), the solvent (E), the leveling agent (H), the antioxidant (J) and other components may be mixed as necessary.

The pigment in the case of containing the pigment (P) is preferably mixed with part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less . At this time, a part or the whole of the pigment dispersant and the resin (B) may be blended if necessary. The desired coloring curable resin composition can be prepared by mixing the remaining components in the thus obtained pigment dispersion to a predetermined concentration.

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

The colored curable resin composition after mixing is preferably filtered with a filter having a pore diameter of about 0.01 to 10 mu m.

<Manufacturing Method of Color Filter>

Color filters formed from the tinted curable compositions of the present invention also fall within the scope of the present invention. The color filter can be obtained by a method including a step of applying a colored curable composition to a substrate and then drying to prepare a colored composition layer and further curing the obtained colored composition layer.

Examples of the method for producing the colored pattern in the color filter include a photolithographic method, an inkjet method, a printing method, and the like. Among them, a photolithographic method is preferable. The photolithographic method is a method in which the above-mentioned colored curable resin composition is applied to a substrate, followed by drying to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed.

In the photolithographic method, a colored coating film which is a cured product of the colored composition layer can be formed by not using and / or not developing a photomask at the time of exposure. A colored coating film including a coloring pattern is also one of the color filters of the present invention.

The film thickness of the color filter is not particularly limited and can be appropriately adjusted according to the purpose or use, and is usually 0.1 to 30 탆, preferably 0.1 to 20 탆, more preferably 0.5 to 6 탆.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass and soda lime glass whose surface is coated with silica, resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate, silicon, Aluminum, silver, silver / copper / palladium alloy thin film, or the like is formed. A separate color filter layer, a resin layer, a transistor, a circuit, or the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus or condition. For example, it can be produced as follows.

First, a colored curable resin composition is coated on a substrate, followed by drying by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.

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

The temperature for heating and drying is preferably 30 to 120 占 폚, more preferably 50 to 110 占 폚. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

In the case of performing the reduced-pressure drying, it is preferable that the drying is carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

The film thickness of the coloring composition layer is not particularly limited and may be suitably selected in accordance with the intended thickness of the color filter.

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited and a pattern according to the intended use is used.

As a light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm may be cut using a filter that cuts the wavelength region, or light of about 436 nm, around 408 nm, and around 365 nm may be selectively extracted using a bandpass filter for extracting these wavelength regions Or the like. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate the entire exposure surface with a parallel light beam or accurately align the photomask with the substrate on which the coloring composition layer is formed.

The colored composition layer after exposure is brought into contact with a developing solution to develop a colored pattern on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer.

As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant. The developing method may be any of a puddle method, a dipping method and a spraying method. Further, the substrate may be inclined at an arbitrary angle at the time of development.

After development, it is preferable to wash with water.

In addition, post-baking is preferably performed on the obtained coloring pattern. The post-baking temperature is preferably 150 ° C to 250 ° C, more preferably 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, a color filter with particularly high brightness can be produced. The color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited by these Examples. In the examples,% and parts representing the content or amount are based on mass unless otherwise specified.

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

Synthesis Example 1

The following reaction was carried out in a nitrogen atmosphere. 32.2 parts of potassium thiocyanate and 160.0 parts of acetone were added to a flask equipped with a stirrer, a cooling tube and an agitator, and the mixture was stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Kasei Corporation) was added dropwise over 10 minutes. After completion of dropwise addition, the mixture was stirred at room temperature for 2 hours. Subsequently, the reaction mixture was allowed to cool, and 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Subsequently, the reaction mixture was allowed to cool, and 34.2 parts of 30% sodium hydroxide aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 31.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under reflux. Subsequently, the reaction mixture was allowed to cool to room temperature, then, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes. Then, the organic layer and the water layer were separated. After the aqueous layer was discarded by separating operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, followed by washing with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was distilled off with an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 캜 to obtain 49.9 parts of a compound represented by the following formula (B-I-1). Yield 51%

Synthesis Example 2

The following reaction was carried out in a nitrogen atmosphere. 9.9 parts of a compound represented by the formula (BI-1), 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kashiwa Co., Ltd.) After 20.0 parts of toluene was added, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 ° C to 100 ° C for 3 hours. Subsequently, the reaction mixture was cooled to room temperature and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes. Then, the organic layer and the water layer were separated. After the aqueous layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was distilled off with an evaporator to obtain a bluish green solid. The resulting bluish-purple solid was purified by column chromatography. The purified violet solid was dried under reduced pressure at 60 캜 to obtain 17.2 parts of a compound represented by the following formula (A-II-1). Yield 85%

Identification of the compound represented by the formula (A-II-1)

(Mass analysis) Ionization mode = ESI +: m / z = 619.3 [M-Cl] ⁺

                        Exact Mass: 654.3

Synthesis Example 3

(D-1) was prepared by dissolving 0.65 part of the compound represented by the formula (A-II-1) in 100 parts of water. On the other hand, a solution (d-2) was prepared by dissolving 1.0 part of the compound represented by the formula (A-II-3) in 50 parts of water.

The solution (d-1) was added to the solution (d-2) at a temperature of 20 ° C to 30 ° C over 1 hour, and then stirred for 24 hours.

The precipitate produced by the stirring was filtered, washed with 1000 parts of water and dried under reduced pressure at 60 ° C for 24 hours to obtain 1.3 parts of a compound represented by the formula (I-1).

Example 1

Colorant (A): 20 parts of a dye represented by the formula (I-1);

Colorant (A): 6 parts of a dye represented by the formula (3-11);

Alkali-soluble resin (B): 53 parts of resin (B-2) (in terms of solid content);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD (R) DPHA; (Manufactured by Nippon Kayaku Co., Ltd.);

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure (registered trademark) OXE-01; Manufactured by BASF; O-acyloxime compound) 4.1 parts;

Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 380 parts of 4-hydroxy-4-methyl-2-pentanone;

Leveling agent (H): Polyether-modified silicone oil (TORAY Silicone SH8400; 0.12 part by Toray Dow Corning Co., Ltd.);

Antioxidant (J): 6-tert-butyl-4- [3 - [(2,4,8,10-tetra-butyldibenzo [d, f] [1,3,2] dioxaphospepine -6-yl) oxy] propyl] -2-methylphenol [Sumilizer (R) GP; (Manufactured by Sumitomo Chemical Co., Ltd.) 0.2 part

And

Zinc complex (F): 6.1 parts of a complex of the formula (10) having a substituent shown in (10) -18 of Table 1

Were mixed to obtain a colored curable resin composition.

Example 2

Colorant (A): 18 parts of a dye represented by the formula (I-1);

Alkali-soluble resin (B): 50 parts of resin (B-2) (in terms of solid content);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD (R) DPHA; (Manufactured by Nippon Kayaku Co., Ltd.);

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure (registered trademark) OXE-01; Manufactured by BASF; O-acyloxime compound] 4.1 parts;

Solvent (E): 150 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 400 parts of 4-hydroxy-4-methyl-2-pentanone;

Leveling agent (H): Polyether modified silicone oil (TORAY Silicone SH8400; 0.12 part by Toray Dow Corning Co., Ltd.);

Antioxidant (J): 6-tert-butyl-4- [3 - [(2,4,8,10-tetra-butyldibenzo [d, f] [1,3,2] dioxaphospepine -6-yl) oxy] propyl] -2-methylphenol [Sumilizer (R) GP; (Manufactured by Sumitomo Chemical Co., Ltd.) 0.3 part

Were mixed to obtain a colored curable resin composition.

Example 3

Colorant (A): 20 parts of a dye represented by the formula (I-1);

Colorant (A): 6 parts of a dye represented by the formula (3-11);

Alkali-soluble resin (B): 53 parts of resin (B-2) (in terms of solid content);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD (R) DPHA; (Manufactured by Nippon Kayaku Co., Ltd.);

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure (registered trademark) OXE-01; Manufactured by BASF; O-acyloxime compound) 4.1 parts;

Solvent (E): 220 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;

Leveling agent (H): Polyether-modified silicone oil (TORAY Silicone SH8400; 0.1 part by Toray Dow Corning Co., Ltd.);

Antioxidant (J): 6-tert-butyl-4- [3 - [(2,4,8,10-tetra-butyldibenzo [d, f] [1,3,2] dioxaphospepine -6-yl) oxy] propyl] -2-methylphenol [Sumilizer (R) GP; (Manufactured by Sumitomo Chemical Co., Ltd.) 0.4 part

Were mixed to obtain a colored curable resin composition.

Comparative Example 1

Colorant (A): 26 parts of a dye represented by the formula (A-III-1);

Alkali-soluble resin (B): 53 parts of resin (B-1) (in terms of solid content);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD (R) DPHA; (Manufactured by Nippon Kayaku Co., Ltd.);

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure (registered trademark) OXE-01; Manufactured by BASF; O-acyloxime compound) 4 parts;

Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;

And

Leveling agent (H): Polyether-modified silicone oil (TORAY Silicone SH8400; Manufactured by Toray Dow Corning Co., Ltd.] 0.15 part

Were mixed to obtain a colored curable resin composition.

[Production of color filter]

The colored curable resin compositions of Example 1, Example 2, Example 3, or Comparative Example 1 were applied by spin coating onto a square glass substrate (# 1737; manufactured by Corning) having a side of 2 inches on one side, And prebaked for 3 minutes to form a coloring composition layer. After cooling, an exposure machine [TME-150 RSK; (Manufactured by Topcon Co., Ltd.) at an exposure amount of 150 mJ / cm 2 (based on 365 nm) in an air atmosphere. Further, no photomask was used. The colored composition layer after exposure was post baked at 180 캜 for 20 minutes in an oven to prepare a color filter (film thickness: 2.8 탆).

[Heat resistance evaluation]

The colored curable resin compositions of Example 1, Example 2, Example 3, or Comparative Example 1 were applied by spin coating onto a square glass substrate (Eagle XG; manufactured by Corning) having one side of 2 inches, Thereby forming a coating layer. The coating film was heated at 230 占 폚 for 20 minutes and the color difference? Eab * before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS).

The coating films obtained from the colored curable resin compositions of Example 1, Example 2 or Example 3 were each subjected to an evaluation of the heat resistance above, and as a result, the color differences (ΔEab *) were 4.2, 5.6 and 5.4, respectively.

The heat curable resin composition of Comparative Example 1 was subjected to the same heat resistance evaluation, and as a result, the color difference ([Delta] Eab *) was 8.1, indicating that the present dyes were excellent in heat resistance.

By using the colored curable resin composition containing the dye of the present invention, it is possible to provide a color filter excellent in heat resistance. The color filter is useful as a color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image pickup devices.

Claims (7)

A dye represented by the following formula (I):

In the above formula (I), each of R ^1A to R ^8A independently represents a hydrogen atom, a halogen atom, a hydroxy group or an alkyl group having 1 to 20 carbon atoms (oxygen atom may be interposed between carbon atoms constituting the alkyl group)
R ^9A to R ^12A each independently represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group) R ^9A and R ^10A may be combined with each other to form a ring together with the nitrogen atom to which they are bonded, and R ^11A and R ^12A may be combined to form a ring together with the nitrogen atom to which they are bonded,
A represents any one selected from the groups represented by the following formulas (A-1-1) to (A-1-10)

(* In the formulas (A-1-1) to (A-1-10) represents the number of bonds with carbon atoms)
Two of R ¹ to R ⁴ are each independently a group represented by the following formula (i), and the remaining two are each independently an alkyl group having 1 to 20 carbon atoms (an oxygen atom is inserted between the carbon atoms constituting the alkyl group , And &quot;

(In the above formula (i), n represents an integer of 1 to 8, and * represents the number of bonds (bonds) with a nitrogen atom)
R ⁵ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxy group or an alkyl group having 1 to 20 carbon atoms (oxygen atom may be interposed between carbon atoms constituting the alkyl group)
R ¹⁷ is a group represented by the following formula (ii).

(In the above formula (ii), R ¹⁸ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * indicates the number of bonds with carbon atoms) A colorant (A) comprising the dye according to claim 1,
The resin (B)
The polymerizable compound (C)
The polymerization initiator (D)
And a coloring curable resin. The colored curable resin composition according to claim 2, wherein the colorant (A) further comprises at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye. The colored curable resin composition according to claim 2 or 3, further comprising a colorless metallic complex (F). A coating film formed from the colored curable resin composition according to claim 2 or 3. A color filter formed from the colored curable resin composition according to claim 2 or 3. A display device comprising the color filter according to claim 6.