TW201307489A - Colored composition - Google Patents

Abstract

The present invention provides a colored composition comprising a pigment and a resin, wherein the pigment contains a compound of the formula (P) wherein Ra1, Ra2, Ra3 and Ra4 each independently represent a hydrogen atom, a bromine atom or a monovalent substituent, and at least one of them represents a bromine atom.

Description

Coloring composition

The present invention is directed to a color forming composition.

The coloring composition is used for manufacturing a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. As the red pigment used in such a coloring composition, CI Pigment Red 254 (a pigment containing a compound represented by the following formula) which is a diketopyrrolopyrrole pigment is known ["Color filter latest technology trend-constituting material" ‧Manufacturing ‧Evaluation ‧Overseas Trends ~” 25th and 26th pages (Jiu Baotian Taisheng et al.; Information Agency (shares) (JOHOKIKO) issued on May 31, 2005)].

In order to achieve high contrast of color filters, it is desired to develop new color-sensitive photosensitive compositions.

The present invention encompasses the following.

[1] A coloring composition containing a pigment and a resin, and the pigment contains a compound represented by the formula (P) [wherein, R ^a1 , R ^a2 , R ^a3 and R ^a4 each independently represent a hydrogen atom, a bromine atom or a monovalent substituent, and at least one represents a bromine atom].

[2] The colored composition according to [1], which further contains a dye.

[3] The coloring composition according to [2], wherein the dye is a dibenzopyran dye, an azo dye or a metal wrong salt dye.

[4] A color filter formed by the coloring composition according to any one of [1] to [3].

[5] A display device comprising the color filter of [4].

According to the present invention, a coloring composition which can produce a high contrast color filter can be provided.

The coloring composition of the present invention contains a pigment (A1) and a resin (B).

Pigment (A1) contains a compound represented by formula (P) [wherein, R ^a1 , R ^a2 , R ^a3 and R ^a4 each independently represent a hydrogen atom, a bromine atom or a monovalent substituent, and at least one represents a bromine atom].

Examples of the monovalent substituent of R ^a1 , R ^a2 , R ^a3 and R ^a4 include a halogen atom (which does not contain a bromine atom), a cyano group, -CF ₃ , -R ^a5 , -OR ^a5 , -SR ^A5 , -SOR ^a5 , -SO ₂ R ^a5 , -NR ^a6 COR ^a5 , -CONR ^a5 R ^a6 , -CONH ₂ .

R ^a5 represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a naphthyl group, and -CH ₂ - contained in the alkyl group may be -NR ^a7 -, -O-, -S-, -SO- or -SO ₂ - replaced.

R ^a6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and -CH ₂ - contained in the alkyl group may be substituted by -NR ^a7 -, -O-, -S-, -SO- or -SO ₂ - .

R ^a5 and R ^a6 may together form an alkanediyl group having 2 to 8 carbon atoms, and -CH ₂ - contained in the alkanediyl group may be via -NR ^a7 -, -O-, -S-, -SO- or - SO ₂ - substituted.

R ^a7 represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.

Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, an isopropyl group, an isobutyl group, a second butyl group, and an isopentyl group.

Examples of the alkanediyl group having 2 to 8 carbon atoms include an exoethyl group, a propionyl-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a butyl-1,3 group. - Diyl, pent-1,5-diyl, hex-1,6-diyl, hept-1,7-diyl, oct-1,8-diyl and the like.

The halogen atom (which does not contain a bromine atom) may, for example, be a fluorine atom, a chlorine atom or an iodine atom, and is preferably a chlorine atom.

Examples of -OR ^a5 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and the like.

Examples of -SR ^a5 include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group and the like.

Examples of -SOR ^a5 include a sulfinyl group, an sulfinyl group, a propylsulfinyl group, a sulfinyl group, a sulfinyl group, and the like.

Examples of -SO ₂ R ^a5 include a methylsulfonyl group, an ethylsulfonyl group, a propanesulfonyl group, a butasulfonyl group, a pentamsulfonyl group, and the like.

Examples of the -NR ^a6 COR ^a5 include an N-ethinylamino group, an N-propylmercaptoamine group, an N-benzylidenylamino group, and an N-methyl-N-ethinylamino group.

Among the -NR ^a6 COR ^a5 , R ^a5 and R ^a6 form a ring group, and examples thereof include a group represented by the following formula.

Examples of -CONR ^a5 R ^a6 include an N-methylaminocarbonyl group, an N,N-dimethylaminocarbonyl group, and an N,N-ethylmethylaminocarbonyl group.

Among the -CONR ^a5 R ^a6 , R ^a5 and R ^a6 form a ring group, and examples thereof include a group represented by the following formula.

At least one of R ^a1 , R ^a2 , R ^a3 and R ^a4 is a bromine atom, preferably at least one of R ^a1 and R ^a2 is a bromine atom, more preferably R ^a1 is a bromine atom and R ^a2 is bromine Atom or chlorine atom.

Preferably, R ^a3 and R ^a4 are each a hydrogen atom.

The compound represented by the formula (P) is, for example, a compound represented by the following formula.

The pigment (A1) may be a pigment containing only the compound represented by the formula (P), if necessary, It may also be a pigment which forms a solid solution together with other pigments and derivatives thereof.

In the pigment (A1), the content of the compound represented by the formula (P) is preferably from 1 to 100% by mass, more preferably from 20 to 100% by mass.

The pigment (A1) may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of a pigment surface by a polymer compound or the like, a sulfuric acid micronization method, or the like. The micronization treatment or the cleaning treatment by an organic solvent or water for removing impurities, the removal treatment of ionic impurities by an ion exchange method, or the like. Further, the pigment (A1) preferably has a uniform particle diameter.

The pigment (A1) can be dispersed by a pigment dispersant to form a pigment dispersion uniformly dispersed in a pigment dispersant solution.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include a product name KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), and Ajisper. (Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie 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 (A1). 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 is obtained.

The colored composition of the present invention may further contain a pigment other than the pigment (A1) (hereinafter sometimes referred to as "pigment (A2)").

Specific examples of the pigment (A2) include compounds classified into pigments by a color index (published by The Society of Dyers and Colourists). Specifically, 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 Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55 , 59, 61, 64, 65, 71, 73 and other orange pigments; 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.

Among them, preferred are yellow pigments, orange pigments, red pigments and violet pigments, more preferably yellow pigments, orange pigments and red pigments, and more preferably CI pigment yellows 138, 139, 150, CI pigment oranges 38, 71 and CI. Pigment red 177, 242, 254. These pigments may be used alone or in combination of two or more.

The pigment (A2) is the same as the pigment (A1), and it is preferred to carry out the above dispersion treatment.

The coloring composition of the present invention may further contain a dye (A3) together with the pigment (A1). The dye (A3) is not particularly limited, and a known dye can be used. For example, an oil-soluble dye, an acid dye, an amine salt of an acid dye, or a sulfonamide derivative of an acid dye can be mentioned. The dye (A3) is preferably an organic solvent soluble dye.

Examples of the dye (A3) include a dye classified as a dye by the Society Index (published by The Society of Dyers snd Colourists) or a known dye described in Dyeing Note (color dyeing company).

Specific examples include CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI solvent red 45, 49, 125, 130; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 35, 37, 59, 67; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.

Further, examples of the CI acid dye include CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 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, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183 , 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315 , 316, 339, 341, 345, 346, 349, 382, 383, 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 Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210 , 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI Acid Violet 6B, 7, 9, 17, 19; CI Acid Green 1, 3 , 5, 9, 16, 25 27,50,58,63,65,80,104,105,106,109 dyes.

Further, as the CI direct dye, 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 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Directly green, 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other dyes.

Further, as the CI medium dye, CI medium yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI medium red 1, 2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45, 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 blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; 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 green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. dye.

Further, examples of the dye (A3) include an azo dye, a metal salt dye, an anthraquinone dye, a triphenylmethane dye, a dibenzopyran dye, a cyanine dye, a naphthoquinone dye, a quinone imine dye, and a secondary dye. Methyl dye, methine azo dye, squaric acid dye, acridine dye, styrene dye, coumarin dye, quinoline dye, nitro dye and phthalocyanine dye, etc., preferably azo dye, metal errone Salt dye, dibenzopyran dye.

Among them, as the dye (A3), a dibenzopyran dye (A3a), a metal-salted salt dye (A3b), a metal-salted salt dye (A3c), and a metal-salted salt dye (A3d) are preferable.

The dibenzopyran dye (A3a) is a dye containing a compound having a dibenzopyran skeleton in the molecule. Examples of the dibenzopyran dye (A3a) include CI Acid Red 51, 52, 87, 92, 94, 289, and 388, CI Acid Violet 9, 30, and 102, and CI Basic Red 1 (Rhodamine 6G). ), 8, CI Alkaline Red 10 (Rhodamine B), CI Solvent Red 218, CI Medium Red 27, CI Reaction Sex Red 36 (Bangladesh Rose B), sulfonium rhodamine G, dibenzopyran dye disclosed in Japanese Patent Laid-Open Publication No. 2010-32999, and dibenzopyran dye disclosed in Japanese Patent No. 4492760 .

Among these, the dibenzopyran dye (A3a) is preferably a dye containing a compound represented by the formula (1) (hereinafter sometimes referred to as "compound (1)"). In the case of using the compound (1), the content of the compound (1) in the dibenzopyran dye (A3a) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass. the above. Particularly, as the dibenzopyran dye (A3a), it is preferred to use only the compound (1).

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; and R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H , -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ; R ⁶ and R ⁷ each independently represent a hydrogen atom Or an alkyl group having a carbon number of 1 to 6; m represents an integer of 0 to 5; when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different; a represents an integer of 0 or 1, and X represents a halogen. Atom; R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom; Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ ; ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may be bonded to each other to form a heterocyclic ring having a nitrogen atom of 3 to 10 member rings; R ¹¹ respectively It independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R1 to R ⁴ include a phenyl group, a tolylmethyl group, and a xylyl group. Mesityl, propylphenyl and butylphenyl.

a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ¹ to R ⁴ , and a hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ^{10 is} substituted. Among the substituents, at least one selected from the group consisting of -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ is preferred, and more preferably selected from the group consisting of At least one of the group consisting of -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ . As this case, -SO ₃ ^- Z ^{+ is} preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . When R ¹ to R ^{4 are} these groups, the coloring composition containing the compound (1) can form a color filter which is less likely to generate impurities and is excellent in heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. a linear alkyl group such as decyl, dodecyl, hexadecyl or eicosyl; a branched alkyl group such as isopropyl, isobutyl, isopentyl, neopentyl or 2-ethylhexyl a cycloalkyl group having a carbon number of 3 to 20, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

Further, a saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OH or a halogen atom, and -CH ₂ contained in the saturated hydrocarbon group - may be substituted by -O-, -CO-, -NH- or -NR ⁸ -.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ⁷ include the above-exemplified alkyl groups and having 1 to 6 carbon atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms represented by R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ .

As the above ⁺ N(R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60. When R ^{11 is} such a group, the coloring composition containing the compound (1) can form a color filter having less impurities.

m is preferably from 1 to 4, more preferably 1 or 2.

The dibenzopyran dye (A3a) is preferably a dye containing a compound represented by the formula (2) (hereinafter sometimes referred to as "compound (2)"). In the case of using the compound (2), the content of the compound (2) in the dibenzopyran dye (A3a) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass. the above. Especially as a dibenzopyran dye (A3a), preferably only Compound (2) was used.

[In the formula (2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; and R ²⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ ; m1 represents an integer of 0 to 5; when m1 is an integer of 2 or more, a plurality of R ²⁵ may be the same or different; a1 represents an integer of 0 or 1; X1 represents a halogen atom; R ²⁶ represents a monovalent saturated hydrocarbon group having a carbon number of 1 to 20; Z1 ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ ; and R ²⁷ independently represents a saturation of a monovalent carbon number of 1 to 20; Hydrocarbyl or benzyl].

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ²¹ to R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group represented by the above R ¹ to R ⁴ . The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

As a combination of R ²¹ to R ²⁴ , R ²¹ and R ²³ are preferably a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10, and a hydrogen atom contained in the aromatic hydrocarbon group. It may be substituted by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . More preferably, R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ^{26 is} substituted. When R ²¹ to R ^{24 are} these groups, the coloring composition containing the compound (2) can form a color filter excellent in heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group represented by R ⁸ to R ¹¹ .

-R ²⁶ in R ²¹ to R ²⁴ is preferably independently a hydrogen atom, a methyl group or an ethyl group. Further, and as -SO ₃ R ²⁶ in the -SO ₂ NHR ²⁶ R ^26, preferred is a branched alkyl group having a carbon number of 3 to 20, more preferably 6 to 12 carbon atoms of the branched chain alkyl group, and further More preferably, it is 2-ethylhexyl. When R ^{26 is} such a group, the coloring composition containing the compound (2) can form a color filter which produces less impurities.

Z1 ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ .

As the above ⁺ N(R ²⁷ ) ₄ , preferably at least two of the four R ²⁷ are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ²⁷ is preferably from 20 to 80, more preferably from 20 to 60. When R ^{27 is} such a group, the coloring composition containing the compound (2) can form a color filter which produces less impurities.

M1 is preferably from 1 to 4, more preferably 1 or 2.

The compound (2) is, for example, a compound represented by the formula (1-1) to the formula (1-22). Further, in the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably 2-ethylhexyl group. Among these, a sulfonium amidate of CI Acid Red 289, a quaternary ammonium salt of CI Acid Red 289, a sulfonamide of CI Acid Violet 102, or a quaternary ammonium salt of CI Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

As the dibenzopyran dye (A3a), a commercially available dibenzopyran dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Sino-foreign Chemical Co., Ltd., and "Rhodamin" manufactured by Tajika Chemical Industry Co., Ltd. can be used. 6G"). Further, a commercially available dibenzopyran dye can also be used as a starting material, and synthesis can be carried out by referring to Japanese Patent Laid-Open Publication No. 2010-32999.

The metal salt-salt dye (A3b) is a dye containing a dye molecule in a molecule which is mis-salted with a metal atom and a metal atom.

As the metal salt-salt dye (A3b), for example, CI solvent yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161, CI solvent orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, CI solvent red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243, CI Solvent Violet 2, 21, 21 : 1,46,49,58,61, CI solvent blue 137, CI solvent brown 28, 42, 43, 44, 53, 62, 63, CI acid yellow 58, 121, CI acid orange 74, 162, CI acid red 211. A metal salt-salt dye disclosed in Japanese Laid-Open Patent Publication No. 2010-170117 and Japanese Patent Laid-Open No. 2011-59673. These metal salt dyes (A3b) may be used singly or in combination of two or more.

Examples of the dye molecule (coordination) include an azo dye, a methine dye, and the like, and an azo dye is preferred.

Examples of the metal atom include chromium, cobalt, nickel, and the like, and chromium or cobalt is preferred.

As the above metal salt dye (A3b), a 1:1 metal salt salt dye having a bonding ratio of a metal atom to a dye molecule of 1:1 and a 1:2 type 2 metal salt salt dye having a ratio of 1:2 are mentioned. Preferably, it is a 1:2 metal salt salt dye.

The metal salt-salt dye (A3b) is preferably a compound represented by the formula (3) or a compound represented by the formula (4).

[In the formula (3), R ³¹ to R ⁴⁸ each independently represent a hydrogen atom, a halogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a phenyl group, -SO ₂ NHR ⁵¹ , -SO ₃ ^- , -COOR ⁵¹ or -SO ₂ R ⁵¹ ; R ⁴⁹ and R ⁵⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group or an amine group; and R ⁵¹ each independently represents a hydrogen atom and a hydrocarbon group having a carbon number of 1 to 10, which is a monovalent hydrocarbon group. -CH ₂ - contained in the hydrocarbon group may be substituted by -O- or -CO-; A ¹ ~ A ⁴ independently represent ^* -O-, ^* -O-CO-, ^* -CO-O-; ^* M bond bond; M represents Cr or Co; n represents an integer of 2 to 5; D ⁺ represents a hydrogen cation, a monovalent metal cation or a monovalent cation derived from a compound having a dibenzopyran skeleton.

[In the formula (4), R ⁵² to R ⁶⁰ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 8, a nitro group, -SO ₂ NHR ⁶² , -SO ₃ H or -SO ₂ CH _{3 .} ; R ⁶¹ each independently represent a hydrogen atom, methyl or ethyl; R ⁶² each independently represent a hydrogen atom, 1 to 8 carbon atoms of the monovalent aliphatic hydrocarbon group, having 2 to 15 carbon atoms, an alkoxy group, the alkyl group; A ⁵ And A ⁶ independently represent ^* -O-, ^* -O-CO-, ^* -CO-O-; ^* represents a bond with M1; M1 represents Cr or Co; n1 represents an integer from 0 to 2; D1 ⁺ Represents a hydrogen cation, a monovalent metal cation or a monovalent cation derived from a compound having a dibenzopyran skeleton.

Examples of the saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ³¹ to R ⁴⁸ , R ⁵² to R ⁶⁰ and R ⁶² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. a linear alkyl group such as heptyl or octyl; isopropyl, t-butyl, t-butyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5 a branched alkyl group such as dimethylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl or 1,1,5,5-tetramethylhexyl.

Preferably, at least one of R ³¹ to R ⁴⁸ is a nitro group. Preferably, at least one of R ⁵² to R ⁶⁰ is a nitro group. It is preferred to have a nitro group and the concentration of the compound tends to be high.

R ⁴⁹ and R ^{50 are} preferably a methyl group.

Examples of the hydrocarbon group having a valence of 1 to 10 carbon atoms of R ⁵¹ include an aliphatic hydrocarbon group having a carbon number of 1 to 10, an alicyclic hydrocarbon group having a carbon number of 3 to 10, and a carbon number of 6~. 10% of the aromatic hydrocarbon group and the combination of the carbon number of 4 to 10. Examples of the aliphatic hydrocarbon group having a carbon number of 1 to 10 include a linear alkane such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a decyl group. a branched alkyl group such as isopropyl, isobutyl, isopentyl, neopentyl or 2-ethylhexyl. Examples of the aromatic hydrocarbon group having a carbon number of 6 to 10 include a phenyl group and a naphthyl group. Examples of the alicyclic hydrocarbon group having a carbon number of 3 to 10 include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

The above hydrocarbon group substituted with -CH ₂ -O- or -CO- may, for example, be -R ⁷¹ -OR ⁷² , -R ⁷¹ -CO-OR ⁷² or -R ⁷¹ -O-CO-R ⁷² . R ⁷¹ is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ⁷² is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

The divalent aliphatic hydrocarbon group which has a carbon number of 1 to 8 of R ⁷¹ may, for example, be a methylene group, an exoethyl group, a propane-1,3-diyl group, a propionyl-1,2-diyl group or a butyl group-1. ,4-diyl, butyl-1,3-diyl, pent-1,5-diyl, hex-1,6-diyl, hept-1,7-diyl, oct-1,8-diyl Wait.

Examples of -R ⁷¹ -OR ⁷² include methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxy. Propyl, ethoxypropyl, propoxypropyl, 2-oxo-4-methoxybutyl, octyloxypropyl, 3-ethoxypropyl, 3-(2-ethylhexyl) Oxy)propyl and the like.

As -R ⁷¹ -CO-OR ⁷² , a methoxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, a propoxycarbonylmethyl group, and a propoxy group are mentioned. Alkylcarbonylethyl, butoxycarbonylmethyl, butoxycarbonylethyl and the like.

Examples of -R ⁷¹ -O-CO-R ⁷² include ethoxymethyloxymethyl, ethoxylated ethyl, ethylcarbonyloxymethyl, ethylcarbonyloxyethyl, propylcarbonyloxy. Methyl, propylcarbonyloxyethyl, butylcarbonyloxymethyl, butylcarbonyloxyethyl and the like.

Examples of the alkoxyalkyl group having 2 to 15 carbon atoms represented by R ⁶² include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, and a methoxypentyl group. , 1-ethoxypropyl, 2-ethoxypropyl, 1-ethoxy-1-methylethyl, 2-ethoxy-1-methylethyl, 1-isopropoxypropyl Base, 2-isopropoxypropyl, 1-isopropoxy-1-methylethyl, 2-isopropoxy-1-methylethyl, octyloxypropyl, 3-ethoxy Propyl, 3-(2-ethylhexyloxy)propyl and the like.

Examples of the monovalent metal cation represented by D ⁺ and D1 ⁺ include a lithium cation, a sodium cation, and a potassium cation. Examples of the monovalent cation derived from the compound having a dibenzopyran skeleton represented by D ⁺ and D1 ⁺ include a cation represented by the formula (5). In order to increase the brightness of the color filter formed from the coloring composition, as the above D ⁺ and D1 ⁺ , a monovalent cation derived from a compound having a dibenzopyran skeleton is preferable.

In the formula (5), R ⁶³ to R ⁶⁷ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.

Examples of the saturated hydrocarbon group having 1 to 6 carbon atoms represented by R ⁶³ to R ^{67 and} the saturated hydrocarbon group represented by the above R ³¹ to R ⁴⁸ include those having 1 to 6 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ⁶³ to R ⁶⁷ include a phenyl group, a tolylmethyl group, and a xylyl group. Base, propylphenyl and butylphenyl groups.

R ⁶³ to R ^{67 are} preferably each independently a hydrogen atom or an ethyl group.

The metal salt-salt dye (A3b) is more preferably a compound represented by the formula (6).

[In the formula (6), R ^a41 to R ^a58 independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8, a nitro group, a sulfo group, -SO ₂ R ⁷² or -SO ₂ NHR. ^A34 ; R ^a34 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ⁷¹ -OR ⁷² , -R ⁷¹ -CO-OR ⁷² , -R ⁷¹ -O-CO-R ⁷² or an aralkyl group having a carbon number of 7 to 10; R ⁷¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R ⁷² represents a carbon number of 1 to 8 An aliphatic hydrocarbon group; R ^a59 and R ^a60 each independently represent a hydrogen atom, a methyl group, an ethyl group or an amine group; M ² represents Cr or Co; and R ^a21 to R ^a24 independently represent a hydrogen atom and have a carbon number of 1 to 8 An aliphatic hydrocarbon group having a valence or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a hydroxyl group, -OR ⁷² , a sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom; R ^a25 and R ^a26 each independently represent a hydrogen atom or a methyl group; R ^a27 represents a stretch ethyl, prop-1,3-diyl or propane-1,2-diyl group; R ^a28 A hydrogen atom or an alkyl group having 1 to 4 carbon atoms; n represents an integer of 1 to 4; when n is 2 or more, a plurality of R ^a27 phases are The same or different from each other].

Examples of the aliphatic hydrocarbon group having a monovalent number of carbon atoms of 1 to 8 include the same groups as those of the above R ³¹ to R ⁴⁸ .

R ⁷¹ and R ^{72 have} the same meanings as described above.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a butylbenzene group. An aryl group such as a benzyl group or a naphthyl group; an aralkyl group such as a benzyl group, a diphenylmethyl group, a phenylethyl group or a 3-phenylpropyl group.

Examples of the cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms include 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group, and 2- Butylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, and the like.

From the tendency that heat resistance is high, at least one of R ^a41 to R ^a58 is preferably a nitro group.

Further, it is preferable that at least one of R ^a41 to R ^a45 and at least one of R ^a46 to R ^a50 are a sulfo group, -SO ₂ NHR ^a34 or -SO ₂ R ⁷² , more preferably -SO ₂ R ⁷² , and further Good for -SO ₂ CH ₃ .

In the case where the color concentration is high, R ^a21 to R ^{a24 is} preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an ethyl group.

As R ^a27 , an ethyl group and a propane-1,2-diyl group are preferred, and an ethyl group is more preferred.

As R ^a28 , a hydrogen atom is preferred.

n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4, and still more preferably 3.

As ^{- (R a27 -O) nR a28} , from the aspect of solubility for the organic solvent, the preferred is 2- (2-hydroxyethoxy) ethyl and 2- [2- (2-hydroxyethoxy Ethyloxy]ethyl, more preferably 2-[2-(2-hydroxyethoxy)ethoxy]ethyl.

Examples of the metal-stack salt dye (A3b) include compounds represented by the formula (A3b-1) to the formula (A3b-7). The compound represented by the formula (A3b-1) to the formula (A3b-5) corresponds to the compound represented by the formula (3), and the compound represented by the formula (A3b-6) corresponds to the compound represented by the formula (4). The compound represented by (A3b-7) corresponds to the compound represented by the formula (6).

The content of the pigment (A1) is preferably 1% by mass or more and 100% by mass or less based on the total amount of the pigment (A1) and the pigment (A2) and the dye (A3).

Further, the total amount of the pigment (A1) and the pigment (A2) and the dye (A3) is preferably from 10 to 60% by mass, more preferably from 20 to 45% by mass, based on the solid content of the coloring composition. Here, the solid content means the amount of the solvent (E) removed from the coloring composition. The solid content can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

The above azo dye (A3c) is a dye of the structure represented by the formula (A3c-I).

[In the formula (A3c-1), R ¹ to R ⁴ each independently represent a hydrogen atom, a C _{1 to 10} saturated aliphatic hydrocarbon group or a carboxyl group; and R ⁵ to R ¹² each independently represent a hydrogen atom, a halogen atom, and a C _{1 to 10} saturation. An aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxy group, a carboxyl group, a sulfo group, an aminesulfonyl group or an N-substituted aminesulfonyl group; and R ¹³ and R ¹⁴ each independently represent a hydrogen atom; , cyano, amine carbaryl or N-substituted amine mercapto].

Further, in the present invention, the colored photosensitive resin composition in which at least one of R ⁵ to R ¹² is an N-substituted amine sulfonyl group.

Further, the present invention is the above colored photosensitive resin composition in which at least one of R ⁵ to R ⁸ and at least one of R ⁹ to R ¹² is an N-substituted amine sulfonyl group.

Further, the present invention is the above colored photosensitive resin composition in which at least one of R ⁶ and R ⁷ and at least one of R ¹⁰ and R ¹¹ is an N-substituted sulfonamide group.

Further, in the present invention, the above N-substituted amine sulfonyl group is a -SO ₃ NHR ¹⁵ group, and R ¹⁵ represents a C _{1 to 10} saturated aliphatic hydrocarbon group, and a C _{1 to 10} saturated aliphatic group substituted by a C _1-8 alkoxy group. hydrocarbyl, C _{1 ~ 8} alkoxy, C _{6 ~ 20} aryl group, the colored photosensitive resin composition C _{7 ~ 20} aralkyl, or C _{2 ~ 10} acyl of.

Further, in the present invention, at least one of R ¹³ and R ¹⁴ is a -CON(R ¹⁶ )R ¹⁷ group, and R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, a C _{1 to 10} saturated aliphatic hydrocarbon group, and a C _1-8 alkane. the group substituted saturated C _{1 ~ 10} aliphatic hydrocarbon, C _{6 ~ 20} aryl group, the colored photosensitive resin composition C _{7 ~ 20} aralkyl, or C _{2 ~ 10} acyl of.

Preferred examples of the formula (A3c-I) include the formula (A3c-I-1) to (A3c-I-10).

Further, a preferred example of the formula (A3c-I) also includes as shown in the formula (A3c-II), at least one of R ⁵ to R ⁸ and at least one of R ⁹ to R ¹² are -SO ₂ NHR ¹⁵ groups, The remaining six compounds are hydrogen atoms.

Preferred examples of the formula (A3c-II) are the formulas (A3c-II-1) to (A3c-II-8).

The salt of the compound (A3c-I) may, for example, be a sulfonate when R ⁵ to R ¹² are a sulfo group and a carboxylate when R ⁵ to R ¹² are a carboxyl group. Further, the cation forming the salt is not particularly limited, and in view of solubility in a solvent, an alkali metal salt such as a lithium salt, a sodium salt or a potassium salt; an ammonium salt; and an amine salt such as an ethanolamine or an alkylamine are preferable. Salt organic amine salts and the like. In particular, an alkali metal salt (preferably a sodium salt) is useful in the case of being contained in a polarizing film substrate. Further, the organic amine salt is useful in the case of being contained in a resin-curable compound, and further because it is a non-metal salt, it is also useful in the field of importance in insulation.

The above azo dye (A3d) is a dye of the structure represented by the formula (A3d-I).

[In the formula (A3d-I), Z represents an oxygen atom or a sulfur atom; R ¹ ~ R ⁴ each independently represent a hydrogen atom, C _{1 ~ 10} saturated aliphatic hydrocarbon group, substituted of hydroxy C _{1 ~ 10} saturated aliphatic hydrocarbon group, the substituted C _{1 ~ 8} alkoxy, C _{1 ~ 10} saturated aliphatic hydrocarbon group, substituted by C _{1 ~ 8} of thioalkoxy group C _{1 ~ 10} saturated aliphatic hydrocarbon group, C _{6 ~ 20} aryl group, C _{7 ~ 20} aralkyl or C _{2 to 10} fluorenyl; R ⁵ to R ¹² each independently represent a hydrogen atom, a halogen atom, a C _{1 to 10} saturated aliphatic hydrocarbon group, a halogenated C _{1 to 10} saturated aliphatic hydrocarbon group, and a C _1-8 alkane. Oxy, carboxyl, sulfo, aminesulfonyl or N-substituted amine sulfonyl].

Further, in the present invention, the colored photosensitive resin composition in which at least one of R ⁵ to R ¹² is an N-substituted amine sulfonyl group.

Further, the present invention is the above colored photosensitive resin composition in which at least one of R ⁵ to R ⁸ and at least one of R ⁹ to R ¹² is an N-substituted amine sulfonyl group.

Further, the present invention is the above-mentioned colored photosensitive resin composition in which at least one of R ⁵ and R ⁸ and at least one of R ⁹ and R ¹² is an N-substituted amine sulfonyl group.

Further, in the present invention, the above N-substituted amine sulfonyl group is a -SO ₃ NHR ¹³ group, and R ¹³ represents a C _{1 to 10} saturated aliphatic hydrocarbon group, and a C _{1 to 10} saturated aliphatic group substituted by a C _1-8 alkoxy group. hydrocarbon group, C _{6 ~ 20} aryl group, the colored photosensitive resin composition C _{7 ~ 20} aralkyl, or C _{2 ~ 10} acyl of.

The compound (A3d~I) may be used alone or in combination of two or more.

When two or more kinds of compounds (A3d-I) are used in combination, the amount of dissolution (oil solubility) with respect to the organic solvent is larger than when one is used alone. Therefore, from the viewpoint of oil solubility, it is preferable to use a combination of two or more kinds of the compounds (A3d-I) as the dye of the liquid crystal display device. Examples of the combination of improving oil solubility include a compound having two N-substituted amine sulfonyl groups (A3d-I) (disulfonamide) and having one N-substituted amine sulfonyl group and one sulfo group. A combination of the compounds (A3d-I) (monosulfonamide). In such a combination, at least one of R ⁵ to R ⁸ and at least one of R ⁹ to R ¹² are an N-substituted amine sulfonyl group, the remainder being a hydrogen atom of disulfonamide, and R ⁵ to R ⁸ At least one of them is an N-substituted amine sulfonyl group, and a combination of at least one of R ⁹ to R ¹² is a sulfo group, and a monosulfonylamine remaining as a hydrogen atom is preferred.

Among the compounds (A3d-I) having an N-substituted amine sulfonyl group, at least one of R ⁵ to R ⁸ and at least one of R ⁹ to R ¹² represented by the formula (A3d-II) are preferred. A compound which is a -SO ₂ NHR ¹³ group and which is a hydrogen atom.

Preferred examples of the formula (A3d-I) include the formulas (A3d-I-1) to (A3d-I-13).

Preferred examples of the formula (A3d-II) are the formula (A3d-II-1)~(A3d-II-7)

The salt of the compound (A3d-I) may, for example, be a sulfonate when R ⁵ to R ¹² are a sulfo group and a carboxylate when R ⁵ to R ¹² are a carboxyl group. Further, the cation forming the salt is not particularly limited, and in view of solubility in a solvent, an alkali metal salt such as a lithium salt, a sodium salt or a potassium salt; an ammonium salt; and an amine salt such as an ethanolamine or an alkylamine are preferable. Salt organic amine salts and the like. In particular, an alkali metal salt (preferably a sodium salt) is useful in the case of being contained in a polarizing film substrate. Further, the organic amine salt is useful in the case of being contained in a resin-curable compound, and further because it is a non-metal salt, it is also useful in the field of importance in insulation.

The coloring composition of the present invention contains a resin (B). The resin (B) is not particularly limited, and is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

The resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)"), and cyclic ether having a carbon number of 2 to 4. A copolymer of a monomer (b) having a structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)").

Resin [K2] (a) and (b) and monomer (c) copolymerizable with (a) (wherein (a) and (b) are different) (hereinafter sometimes referred to as "(c)") Copolymer.

Copolymer [K3] Copolymer of (a) and (c).

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

Citrus [K5] A resin obtained by reacting the copolymer of (b) with (c) with (a).

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

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-p-vinylbenzoic acid, and maleic acid and antibutene. Acid, methyl maleic acid, methyl fumaric acid, itaconic 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, 1,4-cyclohexene dicarboxylic acid; methyl-5 -drop Aceene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2- a bicyclic unsaturated compound containing a carboxyl group such as a olefin or a 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3 -vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , an unsaturated dicarboxylic acid anhydride such as dimethyltetrahydrophthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene dicarboxylic anhydride); succinic acid mono[ Unsaturated mono- or more than two or more polycarboxylic acids such as 2-(methyl)propenyloxyethyl]ester and phthalic acid mono[2-(methyl)propenyloxyethyl]ester Alkyloxyalkylene esters; such as α-(hydroxymethyl)acrylic acid, unsaturated acrylates having a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity or solubility in an alkaline aqueous solution.

(b), for example, 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, a propylene oxide ring, and a tetrahydrofuran ring (butylene oxide ring)) a polymerizable compound having an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

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

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

(b1), for example, a monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)")), and having an unsaturated alicyclic hydrocarbon ring A monomer (b1-2) having an oxidized structure (hereinafter sometimes referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl vinyl ether. , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-divinyl Benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)benzene Ethylene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)benzene Ethylene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidyloxy) Methyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

Examples of (b1-2) include cyclohexene oxide ethylene and 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), (methyl). 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, Cyclomer M100; Daicel Chemical Industry) (Production), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formulae (I) and (II), R ^a and R ^b each independently 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 ¹ and X; ² each independently represents a single ^{bond, -R c -, * -R c} -O-, * -R c -S-, * -R c -NH-; R 3 represents alkyl having 1 to 6 carbon atoms, bis-yl; ^* Indicates the bond with O].

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

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

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

Examples of the alkanediyl group include a methylene group, an exoethyl group, a propionyl-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a penta-1,5-di group. Base, hex-1,6-diyl, and the like.

As X ¹ and X ² , a single bond, a methylene group, an exoethyl group, a ^* CH ₂ -O- ( ^* represents a bond bond with O), and ^* -CH ₂ CH ₂ -O are preferable. More preferably, a single bond or a ^* CH ₂ CH ₂ -O- group can be mentioned.

Examples of the compound represented by the formula (I) include a compound represented by the formula (I-1) to the formula (I-15). Preferably, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), the formula (I-11) to the formula (I- 15). More preferably, the formula (I-1), the formula (I-7), the formula (I-9), and the formula (I-15) can be enumerated.

The compound represented by the formula (II) includes a compound represented by the formula (II-1) to the formula (II-15). Preferably, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), the formula (II-11) to the formula (II) -15). More preferably, it is a formula (II-1), Formula (II-7), Formula (II-9), Formula (II-15).

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

The monomer (b2) having an oxypropylene group and an ethylenically unsaturated bond is more preferably a monomer having an oxypropylene group and a (meth)acryloxy group. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyl propylene oxide, 3-methyl-3-propenyloxymethyl propylene oxide, and 3-ethyl-3. -Methacryloxymethoxymethyl propylene oxide, 3-ethyl-3-propenyloxymethyl propylene oxide, 3-methyl-3-methylpropenyloxyethyl propylene oxide, 3 -methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-acryloxyethyl epoxide Propane, etc.

The monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrogen methacrylate Ester ester and the like.

(b) is preferably (b1) from the viewpoint of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, it is more preferably (b1-2) from the viewpoint of excellent storage stability of the coloring composition.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]non-8-yl (meth)acrylate (in this technique) In the field, the conventional name is called "dicyclopentanyl (meth)acrylate", and sometimes it is called "tricyclodecyl (meth)acrylate), and tricyclo(meth)acrylate [5.2. 1.0 ^2,6 ]decene-8-yl ester (known in the art as "dicyclopentenyl (meth)acrylate), dicyclopentyloxy (meth)acrylate) Ester, (meth)acrylic acid Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid (meth) acrylates such as benzyl ester; (hydroxy) (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; maleic acid a dicarboxylic acid diester such as ethyl ester, diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptane-2 - alkene, 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 - bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2- Alkene, 5-hydroxymethyl-5-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-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-double a bicyclic unsaturated compound such as (cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N -benzyl succinimide, N-butyl succinimide-3-succinimide benzoate, N-butyl succinimide-4-sandene Iminobutyrate, N-butylenediamine-6-methyleneimide hexanoate, N-butylenediamine-3-oxenimide propionate, Dicarbonyl ruthenium derivatives such as N-(9-acridinyl) maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl Toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene Alkene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl are preferred. A cis-butenylene imine, a bicyclo [2.2.1] hept-2-ene, and the like.

In the resin [K1], the ratio of the structural units derived from (a) and (b), respectively, is preferably in the following range from the total structural unit constituting the resin [K1].

Structural unit from (a): 2 to 50 mol% (more preferably 10 to 45 mol%)

Structural unit from (b): 50~98 mol% (more preferably 55~90 mol%)

When the ratio of the structural unit of the resin [K1] is in the above range, storage stability, developability, and solvent resistance of the obtained pattern tend to be excellent.

The resin [K1] can be, for example, the method described in the "Experimental Method for Polymer Synthesis" (the first printing of the first edition of the Otsuka Ryokan Institute of Chemicals, the first printing of March 1, 1972) and the literature. The cited documents are manufactured by reference.

Specific examples include a method in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are introduced into a reaction vessel, and the mixture is stirred, heated, and kept warm in a deoxidizing atmosphere. In addition, the polymerization initiator, solvent, and the like used herein are not particularly limited, and any of the usual users in the field can be used. For example, examples of the polymerization initiator include an chloro compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic. A peroxide (such as benzamidine peroxide) may be used as a solvent to dissolve each monomer, and a solvent (E) or the like which will be described later may be used as a solvent for the coloring composition.

Furthermore, the obtained copolymer may be directly used as a solution after the reaction, or a concentrated or diluted solution may be used, or a method such as reprecipitation may be used. Solid (powder) acquirer. In particular, since the solvent (E) described later is used as a solvent in the polymerization, the solution after the reaction can be used as it is, thereby simplifying the production steps.

In the resin [K2], the ratio of the structural units derived from (a), (b) and (c), respectively, is preferably in the following range from the total structural unit constituting the resin [K2].

Structural unit from (a): 4 to 45 mol% (more preferably 10 to 30 mol%)

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

Structural unit from (c): 1 to 65 mol% (more preferably 5 to 60 mol%)

When the ratio of the structural unit of the resin [K2] is in the above range, storage stability, developability, solvent resistance of the obtained pattern, heat resistance, and mechanical strength tend to be excellent.

The resin [K2] can be produced, for example, by the same method as the method described in the production method of the resin [K1].

Specific examples include a method in which a specific amount of (a), (b), and (c), a polymerization initiator, and a solvent are introduced into a reaction vessel, and the mixture is stirred, heated, and kept warm in a deoxidizing atmosphere. The obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or a solid (powder) obtainer by a method such as reprecipitation.

In the resin [K3], the ratio of the structural units derived from (a) and (c), respectively, is preferably in the following range among the total structural units constituting the resin [K3].

(a) 2 to 55 mol%, more preferably 10 to 50 mol%

(c) 45 to 98% by mole, more preferably 50 to 90% by mole

The resin [K3] can be described, for example, by a method of producing the resin [K1]. The method is the same as the method.

The resin [K4] can be obtained by adding (b) a cyclic ether having a carbon number of 2 to 4 to (a) a carboxylic acid and/or a carboxylic acid anhydride by obtaining a copolymer of (a) and (c). And manufacturing.

First, a copolymer of (a) and (c) is produced by the same method as the method described in the production method of the resin [K1]. In this case, the ratio of the structural units derived from (a) and (c), respectively, is preferably in the following range among the total structural units constituting the copolymer of (a) and (c).

(a) 5 to 50 mol%, more preferably 10 to 45 mol%

(c) 50 to 95% by mole, more preferably 55 to 90% by mole

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

After the copolymer of (a) and (c) is produced, the environment inside the flask is replaced by nitrogen to air, and the reaction catalyst of (b), a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris(dimethylamino) A resin [K4] can be obtained by charging a reaction such as a methyl phenol or a polymerization inhibitor (for example, hydroquinone) into a flask at a temperature of, for example, 60 to 130 ° C for 1 to 10 hours.

The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. When it is set to this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to be good. Since the reactivity of the cyclic ether is high and the unreacted (b) is hard to remain, it is preferably (b1), more preferably (b1-1), as the resin (K4).

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

The reaction conditions such as the input method, the reaction temperature, and the time can be appropriately adjusted in consideration of the heat generated by the production equipment or the polymerization. Further, in the same manner as the polymerization conditions, the amount of heat generated by the production equipment or the polymerization may be considered, and the input method or the reaction temperature may be appropriately adjusted.

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

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

Structural unit from (b): 5 to 95 mol% (more preferably 10 to 90 mol%)

Structural unit from (c): 5 to 95 mol% (more preferably 10 to 90 mol%)

Further, under the same conditions as in the production method of the resin [K4], the copolymer of (b) and (c) has a cyclic ether derived from (b), and (a) a carboxylic acid or a carboxylic anhydride The reaction can thereby produce the resin [K5].

The amount of (a) used in the reaction with the above copolymer is preferably from 5 to 80 moles per 100 moles of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is hard to remain, it is preferably (b1), more preferably (b1-1), as the resin (K5).

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

Examples of the carboxylic acid anhydride include maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5. ,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1] Hept-2-ene anhydride (bicycloheptylene dicarboxylic anhydride) and the like.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricycloacrylate [5.2.1.0]. Resin such as ^2,6 ]nonyl ester/(meth)acrylic copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid Glycidyl ester/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo(5.4- ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylbutylene Resin such as imine copolymer, 3-methyl-3-(meth)acryloxymethyl propylene oxide/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/ (Meth)acrylic acid copolymer, resin such as styrene/(meth)acrylic copolymer [K3]; addition of glycidol (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymer An ester resin, a resin of glycidyl (meth)acrylate added to a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, and tricyclodecyl (meth)acrylate/ Benzyl (meth) acrylate / (meth) acrylate copolymer a resin such as a resin of glycidyl (meth)acrylate [K4]; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid; a resin such as a copolymer of tricyclodecyl methacrylate/styrene/glycidyl (meth)acrylate and a resin reactive with (meth)acrylic acid [K5]; a tricyclodecyl (meth)acrylate/ A resin such as a resin obtained by reacting a copolymer of glycidyl (meth)acrylate with (meth)acrylic acid and a resin which reacts with tetrahydrophthalic anhydride, etc. [K6].

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

Among them, as the resin (B), a resin [K1], a resin [K2], and a resin [K3] are preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the solubility of the unexposed portion to the developer is high, and the residual film ratio or hardness of the obtained pattern tends to be high.

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 preferably from 50 to 180 mg-KOH/g, more preferably from 60 to 150 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the solid content of the coloring composition. When the content of the resin (B) is in the above range, the solubility of the unexposed portion to the developer tends to be high.

The colored composition of the present invention preferably contains a polymerizable compound (C). The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less. The polymerizable compound (C) is a polymerization initiator (D) which can be irradiated by light. The compound which is polymerized by the active radical or the like is not particularly limited, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond.

In particular, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol tris(methyl). ) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (methyl) Acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate, tris(2-(methyl) propylene methoxyethyl) isocyanurate, ethylene glycol modified pentaerythritol Tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, Ester-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like can be given.

The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass based on 100 parts by mass of the resin (B) in the coloring composition.

The coloring composition of the present invention preferably contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical or an acid by the action of light and/or heat to initiate polymerization of the polymerizable compound (C), and a known polymerization can be used. Starting agent. Examples of the polymerization initiator (D) include an O-indenyl hydrazine compound, an alkyl phenone compound, a biimidazole compound, and three. a compound, a fluorenylphosphine oxide compound, and the like. These polymerization initiators may be used alone or in combination of two or more.

The O-indenyl compound is a compound having a partial structure represented by the formula (d1). Hereinafter, ^* indicates a keying key.

As the O-indenyl ruthenium compound, for example, N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzylideneoxy group- 1-(4-Phenylthiophenyl)oct-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-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-dioxocyclopentylmethoxy) Benzamethylene}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6-(2-methylbenzhydryl) )-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can also be used.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In the partial structure represented by the formula (d2) or the partial structure represented by the formula (d3), the benzene ring may have a substituent.

As a compound having a partial structure represented by the formula (d2), for example, 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4- Polinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Polinyl)phenyl]-1-butanone and the like. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4] -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 a ketone oligomer, α,α-diethoxyacetophenone, benzoin dimethyl ketal or the like.

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

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, Japanese Patent No. An imidazole compound in which a phenyl group of the 4, 4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, see Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.).

As three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like.

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl phthalate; 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylcarbonyl peroxide) benzophenone a benzophenone compound such as 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloropurine Pyridone, benzoin, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (especially an amine) to be described later.

Further, as the polymerization initiator (D), an acid generator which generates an acid by the action of light and/or heat can be used. Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethyloxyphenylene. Methyl p-toluenesulfonate, 4-acetoxyphenylmethylbenzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate a salt, a diphenylsulfonium p-toluenesulfonate, a diphenylphosphonium hexafluoroantimonate or the like, or a nitrobenzyl tosylate or a benzoin tosylate. Above three The compound can also be used as an acid generator.

The content of the polymerization initiator (D) is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, based on the solid content of the coloring composition.

The coloring composition of the present invention may contain a polymerization starting aid (D1). In the case of containing the polymerization starting assistant (D1), it is usually used in combination with the polymerization initiator (D). The polymerization initiation aid (D1) is a compound for promoting polymerization of the polymerizable compound (C) which starts polymerization by the polymerization initiator (D), or a sensitizer.

Examples of the polymerization initiation assistant (D1) include an amine compound, an alkoxy fluorene compound, and 9-oxosulfuric acid. a compound, a carboxylic acid compound or the like. These polymerization initiators may be used singly or in combination of two or more.

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

As the alkoxy ruthenium compound, 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.

9-oxosulfur Examples of the compound include 2-isopropyl 9-oxosulfuric acid. 4-isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur And 1-chloro-4-propoxy 9-oxosulfur Wait.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthio group. Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine , naphthoxyacetic acid, and the like.

In the case where the polymerization initiator (D1) is used, the content thereof is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles, per mole of the polymerization initiator (D).

Further, the total content of the polymerization initiator (D) and the polymerization initiation aid (D1) is preferably from 1 to 35% by mass, more preferably from 5 to 25% by mass, based on the solid content of the coloring composition. Further preferably, it is 10 to 20% by mass.

The coloring composition of the present invention may contain a thiol compound (T). The thiol compound (T) is a compound having -SH in the molecule.

As a compound having one -SH in the molecule, for example, 2-sulfonyl group can be mentioned. Oxazole, 2-sulfonylthiazole, 2-sulfonylbenzimidazole, 2-sulfonylbenzothiazole, 2-sulfonylbenzone Oxazole, 2-sulfonyl nicotinic acid, 2-sulfonylpyridine, 2-sulfopyridin-3-ol, 2-sulfonylpyridine-N-oxide, 4-amino-6-hydroxy- 2-sulfonylpyrimidine, 4-amino-6-hydroxy-2-sulfonylpyrimidine, 4-amino-2-sulfonylpyrimidine, 6-amino-5-nitroso-2-thiourea Pyrimidine, 4,5-diamino-6-hydroxy-2-sulfonylpyrimidine, 4,6-diamino-2-sulfonylpyrimidine, 2,4-diamino-6-sulfonylpyrimidine 4,6-Dihydroxy-2-sulfonylpyrimidine, 4,6-dimethyl-2-sulfonylpyrimidine, 4-hydroxy-2-sulfonyl-6-methylpyrimidine, 4-hydroxy- 2-sulfonyl-6-propylpyrimidine, 2-sulfonyl-4-methylpyrimidine, 2-sulfopyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2 -thiol, 4,5-diphenylimidazole-2-thiol, 2-sulfonyl imidazole, 2-sulfonyl-1-methylimidazole, 4-amino-3-indolyl-5-sulfonate Mercapto-1,2,4-triazole, 3-amino-5-sulfonyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3- Thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfonyl-1H-1,2,4-triazole-3-thiol, 2-amino group -5-sulfonyl-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfonyl-1,3, 4-thiadiazole, (furan-2-yl) Methyl mercaptan, 2-sulfonyl-5-thiazolidinone, 2-sulfonylthiazoline, 2-sulfonyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole- 5-thiol, 2-quinoline thiol, 2-sulfonyl-5-methylbenzimidazole, 2-sulfonyl-5-nitrobenzimidazole, 6-amino-2-sulfonyl Benzothiazole, 5-chloro-2-sulfonylbenzothiazole, 6-ethoxy-2-sulfonylbenzothiazole, 6-nitro-2-sulfonylbenzothiazole, 2-sulfonate Benazinimidazole, 2-sulfonylnaphthylnaphthalene Oxazole, 3-sulfonyl-1,2,4-triazole, 4-amino-6-sulfonylpyrazolo[2,4-d]pyridine, 2-amino-6-sulfonylhydrazine , 6-sulfonyl hydrazine, 4-sulfonyl-1H-pyrazolo[2,4-d]pyrimidine, and the like.

Examples of the compound having two or more -SH in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylthio)benzene, and butanediol bis(3-sulfonylpropionic acid). Ester), butanediol bis(3-sulfonyl acetate), ethylene glycol bis(3-sulfonyl acetate), trimethylolpropane tris(3-sulfonyl acetate), Butanediol double (3- Sulfonylpropionate), trimethylolpropane tris(3-sulfonylpropionate), trimethylolpropane tris(3-sulfonylacetate), pentaerythritol tetrakis(3-sulfonyl) Propionate), pentaerythritol tetrakis(3-sulfonylacetate), trishydroxyethyltris(3-sulfonylpropionate), pentaerythritol tetrakis(3-sulfonylbutyrate), 1,4 - bis(3-sulfonylbutoxy)butane or the like.

The content of the thiol compound (T) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is in this range, the sensitivity tends to be high and the developability tends to be good.

The coloring composition of the present invention may contain a decane compound (S). The decane compound (S) is a compound having a group represented by the formula (S).

[In the formula (S), R ^s1 to R ^s3 independently of each other represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxy alkoxy group having 2 to 4 carbon atoms, at least two It represents an alkoxy group having 1 to 4 carbon atoms or an alkoxy alkoxy group having 2 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group and an ethoxy group are preferred.

Examples of the alkoxy alkoxy group having 2 to 4 carbon atoms include a methoxymethoxy group, an ethoxymethoxy group, a propoxymethoxy group, a methoxyethoxy group, and an ethoxyethoxy group. The base or the like is preferably a methoxyethoxy group.

Among R ^s1 to R ^s3 , two are alkoxy groups having 1 to 4 carbon atoms, and preferably any of R ^s1 to R ^s3 is an alkoxy group having 1 to 4 carbon atoms.

As the decane compound (S), methyl trimethoxy decane, methyl triethoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl triethyl醯oxydecane, (3-chloropropyl)trimethoxydecane, (3-chloropropyl)methyldimethoxydecane, (3-chloropropyl)methyldiethoxydecane, (3- Glycidoxypropyl)trimethoxydecane, (3-glycidoxypropyl)triethoxydecane, (3-glycidoxypropyl)methyldimethoxydecane, (3-sulfonate Mercaptopropyl)trimethoxydecane, (3-methacryloxypropyl)trimethoxydecane, (3-methacryloxypropyl)methyldimethoxydecane, [2- (3,4-epoxycyclohexyl)ethyl]trimethoxydecane, [N-2-(N-vinylbenzylaminoethyl)-3-aminopropyl]trimethoxydecane hydrochloride , (triaminopropyl)trimethoxynonane, (3-aminopropyl)trimethoxynonane, (3-aminopropyl)triethoxydecane, (3-aminopropyl)methyl Diethoxydecane, (3-aminopropyl)tris(2-methoxyethoxy)decane, [3-(2-aminoethyl)-3-aminopropyl Trimethoxy decane, [3-(2-aminoethyl)-3-aminopropyl"methyldimethoxydecane, (3-ureidopropyl)trimethoxynonane, (3-urea) Propyl)triethoxydecane, (N-Aminoethyl-3-aminopropyl)trimethoxynonane, (N-Aminoethyl-3-aminopropyl)dimethoxydecane (N-methyl-3-aminopropyl)trimethoxynonane, (N-phenyl-3-aminopropyl)trimethoxydecane, and the like.

The content of the decane compound (S) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on the solid content of the coloring composition. If the content of the decane compound (S) is in this range, there is a pattern peeling during development. Less tendency.

The coloring composition of the present invention preferably contains a solvent (E). The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it can be used from an ester solvent (a solvent containing -COO-), an ether solvent other than an ester solvent (a solvent containing -O-), an ether ester solvent (a solvent containing -COO- and -O-), and a ketone other than an ester solvent. A solvent (a solvent containing -CO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, etc. are selected and used.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ring Hexanol acetate, γ-butyrolactone, and the like.

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, and two. Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl b Ethyl ether, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, 3-ethoxypropane Methyl ester, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropane Methyl ester, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropanoate, 3-methoxyacetic acid Butyl ester, 3-methyl-3-methoxyacetic acid butyl ester, 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 methyl ether acetate, and the like.

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

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

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

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

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

Among the above solvents, from the viewpoints of coatability and drying property, an organic solvent having a boiling point of 1 atm of 120 ° C or more and 180 ° C or less is preferable. Among them, preferred are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Alcohol monoethyl ether, 3-methoxyacetic acid butyl ester, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, ring Hexanone More preferably, it is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, Ethyl 3-ethoxypropionate, cyclohexanone.

When two or more solvents are used, a solvent having a boiling point of 170 ° C or more and 250 ° C or less at 1 atm and a solvent having a boiling point of 120 ° C or more and less than 170 ° C may be used in combination. In this case, the content of the solvent having a boiling point of 170 ° C or more and 250 ° C or less at 1 atm is preferably 0.1% by mass or more and 10% by mass or less based on the solvent (E). By using such a solvent, the coating property of the coloring composition tends to be excellent.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass based on the coloring composition. In other words, the solid content of the coloring composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating becomes good, and the color density is insufficient when the color filter is formed, so that the display characteristics tend to be good.

The coloring composition of the present invention may further contain a surfactant (F). Examples of the surfactant (F) include 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.

Examples of the polyfluorene-based surfactant include a surfactant having a ruthenium oxygen bond. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by TORAY.DOWCORNING), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, SF4300, TSF4440, TSF4445, TSF-4446, TSF 4452, TSF 4460 (manufactured by Momentive Performance Materials Japan LLC), and the like.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specific examples include Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30, Megafac RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (made by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Institute of Precision Chemistry, etc.).

The polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a ruthenium oxygen bond or a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC).

These surfactants may be used alone or in combination of two or more.

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass based on the coloring composition. The upper portion is 0.1% by mass or less, and more preferably 0.01% by mass or more and 0.05% by mass or less. Wherein, the content of the above-mentioned surfactant (F) does not contain the content of the above-mentioned pigment dispersant. When the content of the surfactant (F) is in the above range, the flatness of the coating film can be improved.

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

The coloring composition of the present invention can be produced, for example, by the following method.

It is preferred to first mix the pigment (A1) with the solvent (E) and disperse it using a disperser until the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. When the coloring composition of the present invention contains the pigment (A2), the pigment (A1) and the pigment (A2) may be dispersed and mixed, or the two may be mixed and dispersed. When the coloring composition of the present invention contains the dye (A3), it may be dispersed together with the pigment (A1) and/or the pigment (A2). Examples of the dispersing machine include a paint shaker, a sand mill, a bead mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like.

In the case of dispersion treatment using a paint shaker, it is preferred to use glass beads or zirconia beads having a diameter of 0.1 to 2 mm. The temperature at which the dispersion treatment is carried out is preferably 0 to 100 ° C or higher, more preferably 20 to 80 ° C or higher. In addition, the time for performing the dispersion treatment is usually 1 to 20 hours, preferably about 1 to 10 hours, and can be appropriately adjusted depending on the composition of the pigment dispersion liquid and the size of the apparatus of the paint shaker.

The pigment dispersion thus obtained and the residue of the resin (B), the solvent (E) The other components contained in the residual and coloring composition are mixed in a specific amount, whereby the intended coloring composition can be obtained. The coloring composition is preferably filtered by a filter having a pore diameter of about 0.5 to 10 μm, as needed.

Examples of the method of forming a pattern using the coloring composition of the present invention include a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred.

The photolithography method is a method in which the above-mentioned colored composition is applied onto a substrate, dried, exposed to light through a photomask, and developed to obtain a pattern.

Examples of the substrate include glass, metal, plastic, and the like, and may be in the form of a plate or a film. Further, a structure such as a color filter, various insulating or conductive films, and a driver circuit can be formed on the substrates.

For the coating on the substrate, for example, a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a slit press coater, a curtain coater) It is carried out by a coating device such as a curtain flow coater or a non-rotating coater.

Examples of the drying method of the film applied to the substrate include heat drying, natural drying, air drying, and reduced pressure drying. It can also be combined with a plurality of methods. The drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C. Further, as the heating time, it is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. The drying under reduced pressure is preferably carried out at a temperature of from 20 to 25 ° C under a pressure of from 50 to 150 Pa. By drying, volatile components such as a solvent contained in the coloring composition can be removed.

The film thickness of the coating film after drying is not particularly limited, and can be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, 0.1 to 20 μm, preferably. It is 1~6 μm.

The dried coating film is exposed through a photomask for forming a target pattern. The shape of the pattern on the photomask at this time is not particularly limited, and a pattern shape suitable for the intended use can be used.

As the light source used for the exposure, a light source that generates light of a wavelength of 250 to 450 nm is preferable. For example, a light that is less than 350 nm can be cut off by a filter that cuts off the band, or a light band near the 436 nm, near 408 nm, and around 365 nm can be selectively extracted by extracting the band pass filters of the bands. Specifically, a mercury lamp, a light-emitting diode, a halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to uniformly illuminate the entire surface of the exposure surface, or to accurately position the reticle and the substrate. Therefore, it is preferable to use a reticle alignment machine or a stepper.

After the exposure, it is brought into contact with the developer to dissolve a specific portion, for example, an unexposed portion, and development is performed, whereby a pattern can be obtained. An organic solvent may be used as the developer. However, since it is difficult to dissolve or swell the exposed portion of the coating film by the developer, a pattern having a good shape is obtained. Therefore, an aqueous solution of a basic compound is preferred.

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

It is preferred to carry out water washing after development.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, and potassium citrate. Sodium carbon number, carbon number potassium, hydrogen carbonate Inorganic basic compound such as sodium, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, etc.; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, single An organic basic compound such as ethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine or ethanolamine. Among them, potassium hydroxide, sodium hydrogencarbonate and tetramethylammonium hydroxide are preferred.

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

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

Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, ethylene oxide/propylene oxide copolymer, and sorbitan. a nonionic surfactant such as a fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a glycerin fatty acid ester, a polyoxyethylene fatty acid ester, or a polyoxyethylene alkylamine; An anionic surfactant such as sodium lauryl sulfate, sodium oleyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate or sodium dodecyl naphthalenesulfonate; A cationic surfactant such as stearylamine hydrochloride or lauryl trimethylammonium chloride.

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

Further, post-baking can be performed as needed. The post-baking is preferably carried out, for example, at 150 to 250 ° C for 1 to 240 minutes.

The pattern obtained as described above is useful as a color filter by the coloring composition of the present invention. The color filter can be used in a machine related to various color images such as a display device (for example, a liquid crystal display device or an organic EL device), a solid-state imaging device, and an electronic paper.

Example

Next, the embodiments will be further described, and the present invention will be further specifically described. In the examples, "%" and "parts" mean % by mass and parts by mass unless otherwise stated.

Synthesis Example 1

174 g of the third pentanol was reacted with 22.2 g of metallic sodium in a nitrogen atmosphere at 130 ° C to synthesize sodium tridecanate. This was heated to 60 ° C, and 91.0 g of 4-bromobenzonitrile, 71.05 g of dip-amyl succinate, and 108.9 g of a third pentanol were added, and the mixture was stirred for 2 hours until the liquid temperature became 85 ° C or lower. The suspension was further stirred for 18 hours or more, and thereafter, it was added to a mixture of 200 g of methanol cooled to -10 ° C and 1000 g of water and 49.21 g of sulfuric acid. After the addition of the suspension was completed, the mixture was kept at 0 ° C and stirred for 5 hours to complete the reaction, after which the solid content was filtered. The solid component was washed alternately with methanol and water until the color of the filtrate disappeared and the salt no longer precipitated. Thereafter, the solid content was dried in a vacuum dryer at 80 ° C for 18 hours to obtain a target red pigment 1. The amount obtained was 107 g.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (A1-1a) and a compound represented by the formula (A1-1b) is introduced. Manufactured, trade name: Chugai Aminol Fast Pink R), 15 parts, 150 parts of chloroform, and 8.9 parts of N,N-dimethylformamide, while maintaining a temperature of 20 ° C or less with stirring, 10.9 parts of sulfite chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the mixture was allowed to react at the same temperature for 5 hours, and then cooled to 20 ° C. The cooled reaction solution was added dropwise to a mixed liquid of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine while maintaining the temperature at 20 ° C or lower under stirring. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Then, the obtained reaction mixture was distilled off by a rotary evaporator to remove the solvent, and a small amount of methanol was added and stirred vigorously. The mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, carefully washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a dye 1 (a mixture of the compounds of the formula (A1-1-1) to the formula (A1-1-8)) 11.3 Share.

Ra=2-ethylhexyl

Synthesis Example 3

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by a little addition of 19.4 parts of 35% hydrochloric acid to dissolve it, and stirred for 2 hours to obtain a suspension containing a diazonium salt. liquid. Then, an aqueous solution in which 5.6 parts of an aminosulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added, and excess sodium nitrite was quenched.

Then, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. One of the above suspensions containing a diazonium salt was added thereto for 15 minutes, and a 10% sodium hydroxide solution was appropriately added to control the pH in the range of 7 to 7.5. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, whereby a yellow suspension was obtained. Stir for 1 hour. The yellow solid obtained by dry filtration under reduced pressure at 60 ° C gave 11.7 parts (yield 87%) of the compound of formula (p-1).

10 parts of the compound of the formula (p-1) was added to 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) to be dissolved, and chromium (III) ammonium sulfate decahydrate was added (Wako Pure Chemical Industries, Ltd.) (manufacturing) 3.1 parts, 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), and heated under reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline solution, and filtered to obtain a red-orange solid. The solid was dried at 60 ° C to obtain 13.6 parts of the compound of formula (z-1). %).

The structure of the compound represented by the formula (z-1) was identified using a mass spectrometer JMS-700 (manufactured by JEOL Ltd.).

Identification of compounds represented by formula (z-1)

(mass analysis) ionization mode = ESI-: m/z = 882.1 [M-Na ⁺ ] ^- Exact Mass: 905.1

In 18 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.), 170 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 1.0 part, 4-(N, N-) were added. Dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.4 parts, triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 18 parts, and stirred for about 30 minutes. Thereafter, slowly added to 10.5 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.), and added anhydrous chloroform (47 parts). After pre-dissolving the solution, it was stirred at room temperature for about 2 hours. The liquid separation operation was carried out twice by 150 parts of a 1 N aqueous hydrochloric acid solution, and then the organic layer was washed twice with 150 parts of 10% saline. Then, 43 parts of anhydrous magnesium sulfate was added, and after stirring for about 30 minutes, the desiccant was filtered, and the solvent was distilled off, whereby 20.6 parts of the compound of the formula (g-1) (yield 90%) was obtained.

The structure of the compound represented by the formula (g-1) was identified using a mass spectrometer JMS-700 (manufactured by JEOL Ltd.).

Identification of compounds represented by formula (g-1)

(mass analysis) ionization mode = ESI +: m / z = 575.3 [M - Cl ^- ] ⁺ Exact Mass: 610.3

A solution (s3) was prepared by adding 4030 parts of methanol to 253 parts of the compound represented by the formula (z-1). Further, 1080 parts of methanol was added to 153 parts of the compound represented by the formula (g-1) to prepare a solution (t3). Thereafter, the solution (s3) and the solution (t3) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 ° C, washed with water 3500 parts, filtered, and dried under reduced pressure at 60 ° C to obtain 263 parts of the compound (dye 2) of formula (A2b-7). (Yield 65%).

The structure of the compound represented by the formula (3a-23) is determined by elemental analysis. The analysis machine was an ICP luminescence analyzer (ICPS-8100; manufactured by Shimadzu Corporation).

C 55.6 H5.1 N 11.9 Cr 3.71

Synthesis Example 4

After adding 100 parts of water to 10 parts of 2,2'-benzidine disulfonic acid (containing 30% of water) represented by formula (a-1), it was cooled in an ice bath to obtain a 30% aqueous sodium hydroxide solution. Adjust the pH to 7~8. The following operations were carried out under ice bath cooling. 5.6 parts of sodium nitrite was added and stirred for 30 minutes. A little bit of 14.8 parts of 35% hydrochloric acid was added to make a brown solution, and the mixture was stirred for 2 hours. An aqueous solution in which 3.8 parts of an aminosulfonic acid was dissolved in 38.3 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

After adding 47.9 parts of water to 9.6 parts of 1-ethyl-3-aminemethane-4-yl-6-hydroxypyridin-2-one represented by formula (c-1), it was cooled in an ice bath. The pH was adjusted to 8-9 with a 30% aqueous sodium hydroxide solution.

The following operations were carried out under ice bath cooling. After the above aqueous solution of the pyridone was stirred to obtain a colorless solution, the suspension was adjusted to a pH of 8 to 9 with a 30% aqueous sodium hydroxide solution, and a suspension containing a diazonium salt was added dropwise by a pump. After completion of the dropwise addition, the mixture was further stirred for 3 hours, whereby a yellow suspension was obtained. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 15.7 parts of the azo compound of the formula (A3c-I-1).

The structure of the azo compound (A3c-I-1) was determined by ¹ H-NMR and ¹³ C-NMR analysis. The analysis machine used ECA-500 (manufactured by JEOL Ltd.).

¹ H-NMR (500 MHz, δ (ppm, TMS basis), DMSO): 1.15 (6H, t, J = 6.9 Hz), 2.25 (6H, s), 3.91 (4H, q, J = 6.9 Hz) , 7.37 (2H, d, J = 8.5 Hz), 7.46 (2H, dd, J = 8.5, 2.3 Hz), 7.51 (2H, br.d, J = 1.9 Hz), 7.71 (2H, br.d, J =1.9 Hz), 8.03 (2H, d, J = 2.3 Hz), 14.44 (2H, s)

¹³ C-NMR (125 MHz, δ (ppm, TMS basis), DMSO): 12.9, 14.1, 33.8, 114.9, 115.1, 123.1, 125.4, 133.9, 135.0, 139.6, 143.8, 146.2, 160.6, 160.7, 166.4

5 parts of azo compound (A3c-I-1), 50 parts of chloroform and 2.1 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, and maintained at 20 ° C while stirring. Hereinafter, 6 parts of sulfite chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the mixture was allowed to react at the same temperature for 5 hours, and then cooled to 20 ° C. The reaction solution after cooling was maintained at 20 ° C or lower while stirring, and a mixture of 4 parts of 1,5-dimethylhexylamine and 14 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred overnight at the same temperature to cause a reaction. Then, the obtained reaction mixture was distilled off by a rotary evaporator, and then a small amount of methanol was added and stirred vigorously. The mixture was added to a mixed liquid of 29 parts of acetic acid and 300 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed carefully with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.6 parts (yield 56%) of the azo compound (dye 3) of the formula (A3c-II-1).

Synthesis Example 5

After adding 300 parts of water to 30 parts of 2,2'-benzidine disulfonic acid (containing 30% of water) represented by formula (a-1), the pH was adjusted with a 30% aqueous sodium hydroxide solution under ice cooling. The value is adjusted to 7~8. The following operations were carried out under ice bath cooling. 12.6 parts of sodium nitrite was added and stirred for 30 minutes. 38.1 parts of 35% hydrochloric acid was added in a little while, and after making a brown solution, it was stirred for 2 hours. An aqueous solution in which 5.3 parts of an aminosulfonic acid was dissolved in 57.4 parts of water was added to the reaction solution, and the mixture was stirred to obtain a suspension containing a diazonium salt.

After adding 372 parts of water to 18.6 parts of N,N'-dimethylbarbituric acid represented by formula (c-2), the pH was adjusted to 8~ with a 30% aqueous sodium hydroxide solution under ice cooling. 9.

The following operations were carried out under ice bath cooling. After the above aqueous solution of barbituric acid was stirred to obtain a colorless solution, the pH was adjusted to 8 to 9 with a 30% aqueous sodium hydroxide solution, and a suspension containing a diazonium salt was added dropwise by a pump. After completion of the dropwise addition, the mixture was further stirred for 3 hours, whereby a yellow suspension was obtained. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 14.6 parts of the azo compound of the formula (A3d-I-1).

The structure of the azo compound (A3d-I-1) was determined by ¹ H-NMR and ¹³ C-NMR analysis. The analysis machine used ECA-500 (manufactured by JEOL Ltd.).

¹ H-NMR (500 MHz, δ (ppm, TMS basis), DMSO, room temperature): 3.22 (6H, s), 3.40 (6H, s), 7.33 (4H, d, J = 8.4 Hz), 7.48 (4H, dd, J=8.4, 2.3 Hz), 8.13 (2H, d, J = 2.3 Hz), 14.31 (2H, s)

¹³ C-NMR (125 MHz, δ value (ppm, TMS basis), DMSO, room temperature): 27.3, 28.2, 115.3, 116.2, 117.3, 133.8, 135.8, 139.5, 146.1, 150.6, 158.8, 160.5

The azo compound represented by the formula (A3d-II-1) is produced in the following manner. 10 parts of azo compound (A3d-I-1), 100 parts of chloroform and 4.2 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, and maintained at 20 ° C while stirring. Hereinafter, 7 parts of sulfite chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the mixture was allowed to react at the same temperature for 5 hours, and then cooled to 20 ° C. While maintaining the cooled reaction solution at 20 ° C or lower with stirring, a mixed liquid of 5 parts of 1,5-dimethylhexylamine and 15 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Then, the obtained reaction mixture was distilled off by a rotary evaporator to remove the solvent, and a small amount of methanol was added and stirred vigorously. The mixture was added to a mixed liquid of 58 parts of acetic acid and 600 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed carefully with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 10.9 parts of azo compound (A3d-II-1; dye 4) (yield 82%).

Synthesis Example 6

133 g of propylene glycol monomethyl ether acetate was placed in a 1 L flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere inside the flask was replaced with nitrogen. Thereafter, the solution in the flask was heated to 100 ° C, and 22.0 g (0.10 mol) containing dicyclopentanyl methacrylate (FA-513M; manufactured by Hitachi Chemical Co., Ltd.) was added dropwise using a dropping funnel over 2 hours. a mixture of benzyl methacrylate 82.8 g (0.47 mol), methacrylic acid 37.0 g (0.43 mol), 2,2'-azobisisobutyronitrile 3.6 g and propylene glycol monomethyl ether acetate 164 g After the completion of the dropwise addition to the flask, the mixture was further stirred at 100 ° C for 5 hours.

After the completion of the stirring, air was introduced into the flask through a gas introduction tube, and the atmosphere inside the flask was replaced with air. Then, 21.5 g (0.15 mol) of glycidyl methacrylate and tris(dimethylaminomethyl) were added to the flask. The phenol 0.9 g and the hydroquinone 0.145 g were reacted at 110 ° C for 6 hours to obtain a weight average molecular weight Mw of 9000, a molecular weight distribution of 1.7, a solid content of 37.8% by mass, and a solid content of 97. A solution of resin 1 of mgKOH/g.

Synthesis Example 7

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a gas introduction tube, nitrogen was passed at 0.02 L/min to make it into a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added thereto, and heated while stirring. Up to 70 ° C. Then 36 parts of acrylic acid; and 4,5-epoxytricyclo[5.2.1.0 ^2,6 ]癸-8-yl acrylate (ie monomer (I-1)} and 3,4-epoxy tricycloacrylate [5.2.1.0 ^2,6 ]癸-8-yl ester {ie a mixture of monomers (II-1)} {monomer (I-1) in the mixture: molar ratio of monomer (II-1) = 50:50} 264 parts were dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a monomer solution. The monomer solution was added dropwise to the flask maintained at 70 ° C for 4 hours using a dropping funnel. On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl ether acetate by using another dropping funnel over 4 hours. A solution of the polymerization initiator in 225 parts was placed in the flask. After completion of the dropwise addition of the polymerization initiator solution, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 9000, a molecular weight distribution of 2.0, a solid content of 33%, and a solid component acid. A resin 2 solution having a value of 90 mg-KOH/g.

The measurement of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the above synthesis example was carried out by the following conditions using a GPC method.

Device: HLC-8120GPC (manufactured by Tosoh)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0 mL/min

Solid concentration of the tested liquid: 0.001~0.01% by mass

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh)

Example 1 [Preparation of coloring composition]

Mixing to obtain a coloring composition.

[Production of pattern]

The coloring composition was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning) of 2 inches square, and then prebaked at 100 ° C for 3 minutes. After cooling, the interval between the substrate coated with the colored composition and the patterned quartz glass mask was set to 100 μm, and an exposure machine (TME-150RSK; TOPCON) was used in an atmosphere. Light exposure was performed at an exposure of 150 mJ/cm ² (365 nm reference). Further, as the photomask, a photomask capable of forming a line pattern of 100 μm lines and gaps was used. After the light irradiation, the coating film was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds, washed with water, and then dried in an oven at 220 ° C. Bake after 20 minutes to obtain a pattern.

[Impurity evaluation]

The obtained pattern was observed by a surface shape optical microscope (magnification: 100 times; VF-7510; manufactured by KEYENCE). When it was confirmed that there was no impurity in the observation field, it was ○, and when it was confirmed that there was an impurity, it was set to ×. The results are shown in Table 1.

[Measurement of film thickness]

The film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 1.

[Color Evaluation]

The obtained pattern was subjected to spectroscopic measurement using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) in the XYZ color system of CIE were measured using the characteristic function of the C light source. Brightness Y. The results are shown in Table 1.

[Contrast evaluation]

A coating film was obtained by performing the same operation as the patterning except that the mask was not used for the exposure. The obtained coating film was subjected to a contrast meter (CT-1; manufactured by Kesaka Electric Co., Ltd., color difference meter BM-5A; manufactured by TOPCON Co., Ltd., light source; F-10, polarizing film; manufactured by Kesaka Electromechanical Co., Ltd.), and the blank value was set. The contrast was measured for 30,000. It can be considered that if the contrast of the coating film is high, the contrast of the pattern is also high. The results are shown in Table 1.

Example 2 [Preparation of coloring composition]

Mixing to obtain a coloring composition. The colored composition was subjected to the same operation as in Example 1 to obtain a high-contrast color filter.

Example 3 [Preparation of coloring composition]

Mixing to obtain a coloring composition. Carrying out and implementing the coloring composition In the same operation as in Example 1, a high-contrast color filter was obtained.

Example 4 [Preparation of coloring composition]

Mixing to obtain a coloring composition. The colored composition was subjected to the same operation as in Example 1 to obtain a high-contrast color filter.

Example 5 [Preparation of coloring composition]

Mixing to obtain a coloring composition. The colored composition was subjected to the same operation as in Example 1 to obtain a high-contrast color filter.

Example 6 [Preparation of coloring composition]

Mixing to obtain a coloring composition. The colored composition was subjected to the same operation as in Example 1 to obtain a high-contrast color filter.

Example 7 [Preparation of coloring composition]

Mixing to obtain a coloring composition. The colored composition was subjected to the same operation as in Example 1 to obtain a high-contrast color filter.

Comparative example 1 [Preparation of coloring composition]

Mixing to obtain a coloring composition. The coloring composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

According to the present invention, a coloring composition which can produce a high contrast color filter can be provided.

Claims (5)

A coloring composition containing a pigment and a resin, and the pigment contains a compound represented by the formula (P) [wherein, R ^a1 , R ^a2 , R ^a3 and R ^a4 each independently represent a hydrogen atom, a bromine atom or a monovalent substituent, and at least one represents a bromine atom]. The colored composition of claim 1, which further contains a dye. A colored composition according to claim 2, wherein the dye is a dibenzopyran dye, an azo dye or a metal fault salt dye. A color filter formed by the coloring composition according to any one of claims 1 to 3. A display device comprising a color filter as in claim 4.