JP6259884B2 - Colored curable resin composition - Google Patents

Description

  The present invention relates to a colored 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. Examples of the red pigment used in such a coloring composition include C.I. which is a diketopyrrolopyrrole pigment. I. Pigment Red 254 (a pigment containing a compound represented by the following formula) is widely known (Non-Patent Document 1).

“Latest Color Filter Technology Trends-Construction Materials, Manufacturing, Evaluation, Overseas Trends” p. 25, 26 (Yasuo Kubota et al .; Information Organization Co., Ltd. issued on May 31, 2005)

  In order to achieve high contrast of the color filter, development of a new colored photosensitive composition is desired.

［式（Ｐ）中、Ｒ^a1、Ｒ^a2、Ｒ^a3及びＲ^a4は、互いに独立に、水素原子、臭素原子又は１価の置換基を表し、少なくとも１つは臭素原子を表す。］
で表される化合物を含む着色組成物。
［２］ さらに染料を含む［１］記載の着色組成物。
［３］ 染料が、キサンテン染料、アゾ染料または金属錯塩染料である［２］記載の着色組成物。
［４］ ［１］〜［３］のいずれかに記載の着色組成物により形成されたカラーフィルタ。
［５］ ［４］記載のカラーフィルタを含む表示装置。 The present invention provides the following [1] to [5].
[1] containing a pigment and a resin, wherein the pigment has the formula (P)

[In the formula (P), 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 coloring composition containing the compound represented by these.
[2] The coloring composition according to [1], further comprising a dye.
[3] The coloring composition according to [2], wherein the dye is a xanthene dye, an azo dye, or a metal complex dye.
[4] A color filter formed from the colored composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the coloring composition which can manufacture a high contrast color filter.

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

［式（Ｐ）中、Ｒ^a1、Ｒ^a2、Ｒ^a3及びＲ^a4は、互いに独立に、水素原子、臭素原子又は１価の置換基を表し、少なくとも１つは臭素原子を表す。］ The pigment (A1) contains a compound represented by the formula (P).

[In the formula (P), 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 in R ^a1 , R ^a2 , R ^a3 and R ^a4 include a halogen atom (excluding 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 can be mentioned.
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 is —NR ^a7 —, —O—, —S—, —SO— or It may be replaced by —SO ₂ —.
R ^a6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and —CH ₂ — contained in the alkyl group is —NR ^a7 —, —O—, —S—, —SO— or —SO _2. It may be replaced with-.
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 is —NR ^a7 —, —O—, — S—, —SO— or —SO ₂ — may be substituted.
R ^a7 represents a hydrogen atom or 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, an n-propyl group, an n-butyl group, an n-pentyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and an isopentyl group.

  Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, and butane-1,3-diyl group. , Pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like.

  Examples of the halogen atom (excluding the bromine atom) include a fluorine atom, a chlorine atom, and an iodine atom, preferably a chlorine atom.

Examples of —OR ^a5 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.
Examples of —SR ^a5 include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and a pentylsulfanyl group.
Examples of —SOR ^a5 include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, a butylsulfinyl group, and a pentylsulfinyl group.
The -SO ₂ R ^a5, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, and the like.

Examples of —NR ^a6 COR ^a5 include an N-acetylamino group, an N-propionylamino group, an N-benzoylamino group, and an N-methyl-N-acetylamino group.
Examples of the group in which R ^a5 and R ^a6 form a ring in —NR ^a6 COR ^a5 include groups represented by the following formulae.

-CONR ^a5 R ^a6 includes N-methylaminocarbonyl group, N-methylaminocarbonyl group, N, N-dimethylaminocarbonyl group, N, N-dimethylaminocarbonyl group, N, N-ethylmethylaminocarbonyl group, N, N-ethylmethylcarbonyl group etc. are mentioned.
In -CONR ^a5 R ^a6 , examples of the group in which R ^a5 and R ^a6 form a ring include groups represented by the following formulae.

Preferably, at least one of R ^a1 , R ^a2 , R ^a3 and R ^a4 is a bromine atom, at least one of R ^a1 and R ^a2 is a bromine atom, R ^a1 is a bromine atom, and R ^a2 is more preferably a bromine atom or a chlorine atom.
R ^a3 and R ^a4 are preferably both hydrogen atoms.

As a compound represented by Formula (P), the compound represented by a following formula is mentioned, for example.

The pigment (A1) may be a pigment containing only the compound represented by the formula (P), or may be a pigment in which a solid solution is formed together with other dyes and derivatives thereof as necessary.
In the pigment (A1), the content of the compound represented by the formula (P) is preferably 1 to 100% by mass, more preferably 20 to 100% by mass.

The pigment (A1) is optionally treated with rosin, surface treatment using a pigment derivative having an acidic group or basic group introduced, grafting onto the pigment surface with a polymer compound, sulfuric acid atomization method, etc. May be subjected to the atomization treatment by, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like. The pigment (A1) preferably has a uniform particle size.
The pigment (A1) can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment (A1). When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

  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 as pigments by the color index (published by The Society of Dyers and Colorists). Specifically, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

Among these, yellow pigments, orange pigments, red pigments, and violet color pigments are preferable, yellow pigments, orange pigments, and red pigments are more preferable. I. Pigment yellow 138, 139, 150, C.I. I. Pigment orange 38, 71 and C.I. I. Pigment Red 177, 242, and 254 are more preferable. These pigments may be used alone or in combination of two or more.
The pigment (A2) is preferably subjected to the above-described dispersion treatment in the same manner as the pigment (A1).

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. Examples thereof include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. The dye (A3) is preferably an organic solvent-soluble dye.
Examples of the dye (A3) include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color Dyeing).

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 162;
C. I. Solvent red 45, 49, 125, 130;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 35, 37, 59, 67;
C. I. Solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 etc. are mentioned.

In addition, C.I. I. As an acid dye, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 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;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 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;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid 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;
C. I. Acid Violet 6B, 7, 9, 17, 19;
C. I. And dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109.

In addition, C.I. I. As a direct dye, C.I. I. 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;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. 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;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Examples include direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82.

Furthermore, C.I. I. As a modern dye, C.I. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern 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;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern 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;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern dyes 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like can be mentioned.

  As the dye (A3), azo dyes, metal complex dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes , A coumarin dye, a quinoline dye, a nitro dye, a phthalocyanine dye, and the like, and an azo dye, a metal complex dye, and a xanthene dye are preferable.

  Among these, as the dye (A3), a xanthene dye (A3a), a metal complex dye (A3b), an azo dye (A3c), and an azo dye (A3d) are more preferable.

  The xanthene dye (A3a) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (A3a) include C.I. I. Acid Red 51, 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 8, C.I. I. Basic Red 10 (Rhodamine B), C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like.

  Among these, as the xanthene dye (A3a), a dye containing a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”) is preferable. When using the compound (1), the content of the compound (1) in the xanthene dye (A3a) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1) as the xanthene dye (A3a).

［式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、−Ｒ⁸又は炭素数６〜１０の１価の芳香族炭化水素基を表す。
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上の整数である場合、複数のＲ⁵は同一であるか相異なる。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、それぞれ独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］

In Expression (1), R ¹ to R ⁴ each independently represents a monovalent aromatic hydrocarbon radical of hydrogen, -R ⁸ or 6 to 10 carbon atoms.
R ^{5 _{is, -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 represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ are the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R 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 are bonded to each other to contain a nitrogen atom and a 3 to 10 member A heterocyclic ring may be formed.
R ¹¹ each 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 R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. It is done.

In the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{1 to} R ⁴ , the hydrogen atom contained in the aromatic hydrocarbon group is 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 may be substituted. . Among these _{^{substituents, -SO 3 -, -SO 3 H}} , -SO 3 - is preferably at least one selected from Z ⁺ and the group consisting of _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and More preferred is at least one selected from the group consisting of —SO ₂ NR ⁹ R ¹⁰ . -SO ₃ in this case ^- Z ^{+ _{The, -SO 3 - + N (R}} 11) 4 are preferred. When R ^{1 to} R ⁴ are these groups, the colored composition containing the compound (1) can form a color filter with less generation of foreign matters and excellent 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 nonyl group. Group, decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched chain alkyl groups; cyclopropyl group, cyclopentyl And a cycloalkyl group having 3 to 20 carbon atoms such as a group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

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

The alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ^7, among the alkyl groups listed above, include those 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 ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When R ¹¹ is these groups, the colored composition containing the compound (1) can form a color filter with few foreign matters.

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

  As the xanthene dye (A3a), a dye containing a compound represented by the formula (2) (hereinafter sometimes referred to as “compound (2)”) is more preferable. In the case of using the compound (2), the content of the compound (2) in the xanthene dye (A3a) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (2) as the xanthene dye (A3a).

［式（２）中、Ｒ²¹〜Ｒ²⁴は、それぞれ独立に、水素原子、−Ｒ²⁶又は炭素数６〜１０の１価の芳香族炭化水素基を表す。
Ｒ²⁵は、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ１⁺又は−ＳＯ₂ＮＨＲ²⁶を表す。
ｍ１は、０〜５の整数を表す。ｍ１が２以上の整数である場合、複数のＲ²⁵は同一であるか相異なる。
ａ１は、０又は１の整数を表す。
Ｘ１は、ハロゲン原子を表す。
Ｒ²⁶は、炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｚ１⁺は、⁺Ｎ（Ｒ²⁷）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ²⁷は、それぞれ独立に、炭素数１〜２０の１価の飽和炭化水素基又はベンジル基を表す。］

Wherein (2), R ²¹ ~R ²⁴ each independently represent a hydrogen atom, a monovalent aromatic hydrocarbon group -R ²⁶ or 6 to 10 carbon atoms.
R ²⁵ is, -SO ₃ ^- represents a Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents the integer of 0-5. When m1 is an integer of 2 or more, the plurality of R ²⁵ are 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 1 to 20 carbon atoms.
Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. ]

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 in R ^{1 to} R ⁴ . Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, may be substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26.
As a combination of R ^{21 to} R ²⁴ , R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbons hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, those substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ preferred. A more preferred combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and hydrogen contained in the aromatic hydrocarbon group atom, -SO ₃ ^- in which are substituted with Z1 ⁺ or -SO ₂ NHR ^26. When R ^{21 to} R ²⁴ are these groups, the colored composition containing the compound (2) can form a color filter having excellent 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 in R ^{8 to} R ¹¹ .
-R ²⁶ in R ²¹ to R ²⁴ each independently represent a hydrogen atom, a methyl group or an ethyl group. As the R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, A 2-ethylhexyl group is more preferred. When R ²⁶ is such a group, the colored composition containing the compound (2) can form a color filter with less generation of foreign matters.

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
As the ⁺ N (R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ²⁷ is preferably 20 to 80, 20 to 60 is more preferable. A colored composition containing the compound (2) in which R ²⁷ is any of these groups can form a color filter with less generation of foreign matters.

  m1 is preferably 1 to 4, and more preferably 1 or 2.

Examples of the compound (2) include compounds represented by the formula (1-1) to the formula (1-22). 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 a 2-ethylhexyl group. Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. The quaternary ammonium salt of 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 xanthene dye (A3a), a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) may be used. it can. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

  The metal complex dye (A3b) is a dye molecule containing a group capable of complexing with a metal atom in the molecule, and a dye complexing a metal atom.

  Examples of the metal complex dye (A3b) include C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161, C.I. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, C.I. I. 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, C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61, C.I. I. Solvent Blue 137, C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63, C.I. I. Acid Yellow 59, 121, C.I. I. Acid Orange 74, 162, C.I. I. Acid red 211, and metal complex dyes described in JP2010-170117A and JP2011-59673A. These metal complex dyes (A3b) may be used alone or in combination of two or more.

Examples of the dye molecule (ligand) include azo dyes and methine dyes, with azo dyes being preferred.
Examples of the metal atom include chromium, cobalt, nickel and the like, and chromium and cobalt are preferable.
The metal complex dye (A3b) includes a 1: 1 type metal complex dye having a bond ratio of metal atoms to dye molecules of 1: 1, and a 1: 2 type metal complex dye having a ratio of 1: 2. And a 1: 2 metal complex dye is preferred.

  As said metal complex salt dye (A3b), the compound represented by Formula (3) and the compound represented by Formula (4) are preferable.

［式（３）中、Ｒ³¹〜Ｒ⁴⁸は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜８の１価の飽和炭化水素基、ニトロ基、フェニル基、−ＳＯ₂ＮＨＲ⁵¹、−ＳＯ₃ ^-、−ＣＯＯＲ⁵¹又は−ＳＯ₂Ｒ⁵¹を表す。
Ｒ⁴⁹及びＲ⁵⁰は、それぞれ独立に、水素原子、メチル基、エチル基又はアミノ基を表す。
Ｒ⁵¹は、それぞれ独立に、水素原子、炭素数１〜１０の１価の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ａ¹〜Ａ⁴は、それぞれ独立に、＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−を表す。＊はＭとの結合手を表す。
Ｍは、Ｃｒ又はＣｏを表す。
ｎは、２〜５の整数を表す。
Ｄ⁺は、ヒドロン、１価の金属カチオン又はキサンテン骨格を有する化合物に由来する１価のカチオンを表す。］

[In the formula (3), R ^{31 to} R ⁴⁸ are each independently 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 , It represents a, -COOR ⁵¹ or -SO ₂ R ^{51 -} -SO _3.
R ⁴⁹ and R ⁵⁰ each independently represents a hydrogen atom, a methyl group, an ethyl group or an amino group.
R ⁵¹ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is replaced by —O— or —CO—. Also good.
A ^{1 to} A ⁴ each independently represent * —O—, * —O—CO—, or * —CO—O—. * Represents a bond with M.
M represents Cr or Co.
n represents an integer of 2 to 5.
D ⁺ represents a monovalent cation derived from hydrone, a monovalent metal cation or a compound having a xanthene skeleton. ]

［式（４）中、Ｒ⁵²〜Ｒ⁶⁰は、それぞれ独立に、水素原子、炭素数１〜８の１価の脂肪族炭化水素基、ニトロ基、−ＳＯ₂ＮＨＲ⁶²、−ＳＯ₃Ｈ又は−ＳＯ₂ＣＨ₃を表す。
Ｒ⁶¹は、それぞれ独立に、水素原子、メチル基又はエチル基を表す。
Ｒ⁶²は、それぞれ独立に、水素原子、炭素数１〜８の１価の脂肪族炭化水素基、炭素数２〜１５のアルコキシアルキル基を表す。
Ａ⁵及びＡ⁶は、それぞれ独立に、＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−を表す。＊はＭ１との結合手を表す。
Ｍ１は、Ｃｒ又はＣｏを表す。
ｎ１は、０〜２の整数を表す。
Ｄ１⁺は、ヒドロン、１価の金属カチオン又はキサンテン骨格を有する化合物に由来する１価のカチオンを表す。］

[In the formula (4), R ^{52 to} R ⁶⁰ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ NHR ⁶² , —SO ₃ H or It represents a -SO ₂ CH _3.
R ⁶¹ each independently represents a hydrogen atom, a methyl group or an ethyl group.
R ⁶² each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.
A ⁵ and A ⁶ each independently represent * —O—, * —O—CO— or * —CO—O—. * Represents a bond with M1.
M1 represents Cr or Co.
n1 represents the integer of 0-2.
D1 ⁺ represents a monovalent cation derived from hydrone, a monovalent metal cation or a compound having a xanthene skeleton. ]

Examples of the monovalent 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 hexyl. Group, heptyl group, octyl group and other linear alkyl groups; isopropyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5- Examples thereof include branched alkyl groups such as dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, and 1,1,5,5-tetramethylhexyl group.
Of R ^{31 to} R ⁴⁸ , at least one is preferably a nitro group. It is preferable that at least one of R ^{52 to} R ⁶⁰ is a nitro group. Having a nitro group is preferable because the spectral concentration of the compound tends to increase.
R ⁴⁹ and R ⁵⁰ are preferably methyl groups.

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms representing R ⁵¹ include a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, Examples thereof include monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms and groups having 4 to 10 carbon atoms in combination of these. Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include straight chain such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. A branched alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

Examples of the hydrocarbon group in which —CH ₂ — is replaced by —O— or —CO— include —R ⁷¹ —O—R ⁷² , —R ⁷¹ —CO—O—R ⁷² , —R ⁷¹ —O—CO -R ⁷² and the like. 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.
Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms representing R ⁷¹ include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a butane-1,4. -Diyl group, butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. Can be mentioned.

—R ⁷¹ —O—R ⁷² includes methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, 2-oxo Examples include -4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group, and the like.

—R ⁷¹ —CO—O—R ⁷² includes methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxycarbonylmethyl group, propoxycarbonylethyl group, butoxycarbonylmethyl group, butoxycarbonyl An ethyl group etc. are mentioned.

—R ⁷¹ —O—CO—R ⁷² includes acetyloxymethyl group, acetyloxyethyl group, ethylcarbonyloxymethyl group, ethylcarbonyloxyethyl group, propylcarbonyloxymethyl group, propylcarbonyloxyethyl group, butylcarbonyloxy Examples thereof include a methyl group and a butylcarbonyloxyethyl group.

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, a methoxypentyl group, a 1-ethoxypropyl group, a 2-ethoxypropyl group, 1-ethoxy-1-methylethyl group, 2-ethoxy-1-methylethyl group, 1-isopropoxypropyl group, 2-isopropoxypropyl group, 1-isopropoxy-1-methylethyl group, 2-isopropoxy- Examples include 1-methylethyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group 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 xanthene skeleton represented by D ⁺ and D1 ⁺ include a cation represented by the formula (5). Since the brightness of the color filter formed from the colored composition can be improved, the D ⁺ and D 1 ⁺ are preferably monovalent cations derived from a compound having a xanthene skeleton.

［式（５）中、Ｒ⁶³〜Ｒ⁶⁷は、それぞれ独立に、水素原子、炭素数１〜６の１価の飽和炭化水素基又は炭素数６〜１０の１価の芳香族炭化水素基を表す。］

[In Formula (5), each of R ^{63 to} R ⁶⁷ independently represents 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. Represent. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 6 carbon atoms represented by R ^{63 to} R ⁶⁷ include those having 1 to 6 carbon atoms among those exemplified as the saturated hydrocarbon group in R ^{31 to} R ^48. Can be mentioned.
Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{63 to} R ⁶⁷ include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group, and butylphenyl group. It is done.
R ^{63 to} R ⁶⁷ are each independently preferably a hydrogen atom or an ethyl group.

［式（６）中、Ｒ^a41〜Ｒ^a58は、互いに独立に、水素原子、ハロゲン原子、炭素数１〜８の１価の脂肪族炭化水素基、ニトロ基、スルホ基、−ＳＯ₂Ｒ⁷²又は−ＳＯ₂ＮＨＲ^a34を表す。
Ｒ^a34は、水素原子、炭素数１〜８の１価の脂肪族炭化水素基、炭素数１〜４のアルキル基で置換されていてもよいシクロヘキシル基、−Ｒ⁷¹−Ｏ−Ｒ⁷²、−Ｒ⁷¹−ＣＯ−Ｏ−Ｒ⁷²、−Ｒ⁷¹−Ｏ−ＣＯ−Ｒ⁷²又は炭素数７〜１０のアラルキル基を表す。
Ｒ⁷¹は、炭素数１〜８の２価の脂肪族炭化水素基を表す。
Ｒ⁷²は、炭素数１〜８の１価の脂肪族炭化水素基を表す。
Ｒ^a59及びＲ^a60は、互いに独立に、水素原子、メチル基、エチル基又はアミノ基を表す。
Ｍ²は、Ｃｒ又はＣｏを表す。
Ｒ^a21〜Ｒ^a24は、互いに独立に、水素原子、炭素数１〜８の１価の脂肪族炭化水素基又は炭素数６〜１０の１価の芳香族炭化水素基を表し、該脂肪族炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、ヒドロキシ基、−ＯＲ⁷²、スルホ基、−ＳＯ₃Ｎａ、−ＳＯ₃Ｋ又はハロゲン原子で置換されていてもよい。
Ｒ^a25及びＲ^a26は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a27は、エチレン基、プロパン−１，３−ジイル基又はプロパン−１，２−ジイル基を表す。
Ｒ^a28は、水素原子又は炭素数１〜４のアルキル基を表す。
ｎは、１〜４の整数を表す。ｎが２以上である場合、複数のＲ^a27は互いに同一でも異なってもよい。］ As the metal complex dye (A3b), a compound represented by the formula (6) is more preferable.

[In the formula (6), R ^{a41 to} R ^a58 are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a sulfo group, or —SO ₂ R ^72. or it represents a -SO ₂ NHR ^a34.
R ^a34 is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ⁷¹ -O-R ⁷² ,- R ⁷¹ —CO—O—R ⁷² , —R ⁷¹ —O—CO—R ⁷² or an aralkyl group having 7 to 10 carbon atoms is represented.
R ⁷¹ represents a C 1-8 divalent aliphatic hydrocarbon group.
R ⁷² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ^a59 and R ^a60 each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.
M ² represents Cr or Co.
R ^{a21 to} R ^a24 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a hydroxy group, —OR ⁷² , a sulfo group, —SO ₃ Na, —SO ₃ K, or a halogen atom.
R ^a25 and R ^a26 each independently represents a hydrogen atom or a methyl group.
R ^a27 represents an ethylene group, a propane-1,3-diyl group, or a propane-1,2-diyl group.
R ^a28 represents 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, the plurality of R ^a27 may be the same as or different from each other. ]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those described above for R ^{31 to} R ⁴⁸ .
R ⁷¹ and R ⁷² represent the same meaning as described above.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms include phenyl groups, methylphenyl groups, dimethylphenyl groups, trimethylphenyl groups, ethylphenyl groups, propylphenyl groups, butylphenyl groups, and naphthyl groups. 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, 2-butylcyclohexyl group, Examples include 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-isopropylcyclohexyl group, 4-butylcyclohexyl group and the like.

Since heat resistance tends to be high, at least one of R ^{a41 to} R ^a58 is preferably a nitro group.
Further, at least one of the at least one and R ^a46 to R ^a50 of R ^a41 to R ^a45, preferably a sulfo group, a -SO ₂ NHR ^a34 or -SO ₂ R ^72, is -SO ₂ R ⁷² It is more preferable that it is —SO ₂ CH ₃ .

R ^{a21 to} R ^a24 are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, since the color density increases. Or it is more preferable that it is an ethyl group.

R ^a27 is preferably an ethylene group or a propane-1,2-diyl group, and more preferably an ethylene group.
R ^a28 is preferably a hydrogen atom.
n is an integer of 1 to 4, an integer of 2 to 4 is preferable, 3 or 4 is more preferable, and 3 is more preferable.
-(R ^a27 -O) n-R ^a28 is a 2- (2-hydroxyethoxy) ethyl group or a 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group in terms of solubility in an organic solvent. Is preferable, and a 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group is more preferable.

  Examples of the metal complex dye (A3b) include compounds represented by formulas (A3b-1) to (A3b-7). The compound represented by formula (A3b-1) to formula (A3b-5) corresponds to the compound represented by formula (3), and the compound represented by formula (A3b-6) is represented by formula (4). The compound represented by the formula (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 with respect to the total amount of the pigment (A1), the pigment (A2), and the dye (A3).
The total amount of the pigment (A1), the pigment (A2) and the dye (A3) is preferably 10 to 60% by mass, more preferably 20 to 45% by mass, based on the solid content of the coloring composition. . Here, solid content means the quantity remove | excluding the solvent (E) from the coloring composition. Solid content can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

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

[In formula (A3c-I), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a C _1-10 saturated aliphatic hydrocarbon group or a carboxyl group.
R ^{5 to} R ¹² are each independently a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxyl group, or a carboxyl group. , A sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group.
R ¹³ and R ¹⁴ each independently represents a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group. ]

Moreover, this invention is the said colored photosensitive resin composition whose at least one of R < ⁵ > -R < ¹² > is an N-substituted sulfamoyl group.

Moreover, this invention is the said colored photosensitive resin composition whose at least 1 of R < ⁵ > -R < ⁸ > and at least 1 of R < ⁹ > -R < ¹² > are N-substituted sulfamoyl groups.

The present invention also provides the above colored photosensitive resin composition, wherein at least one of R ⁶ and R ⁷ and at least one of R ¹⁰ and R ¹¹ is an N-substituted sulfamoyl group.

In the present invention, the N-substituted sulfamoyl group is a —SO ₃ NHR ¹⁵ group, and R ¹⁵ is a C _1-10 substituted aliphatic hydrocarbon group or a C _1-8 alkoxyl group substituted C _{1. The} above-mentioned colored photosensitive resin composition, which represents a _-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxyl group, a C _6-20 aryl group, a C _7-20 aralkyl group, or a C _2-10 acyl group.

In the present invention, at least one of R ¹³ and R ¹⁴ is a —CON (R ¹⁶ ) R ¹⁷ group, and each of R ¹⁶ and R ¹⁷ independently represents a hydrogen atom or a C _1-10 saturated aliphatic hydrocarbon. The above-mentioned colored photosensitive group, which represents a C _1-10 saturated aliphatic hydrocarbon group, a C _6-20 aryl group, a C _7-20 aralkyl group, or a C _2-10 acyl group substituted with a C _1-8 alkoxyl group It is an adhesive resin composition.

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

さらに式（Ａ３ｃ−Ｉ）の好ましい例には、式（Ａ３ｃ−ＩＩ）で表されるような、Ｒ⁵〜Ｒ⁸の少なくとも１つ、並びにＲ⁹〜Ｒ¹²の少なくとも１つが、−ＳＯ₂ＮＨＲ¹⁵基であり、残りの６つが水素原子である化合物も含まれる。

Furthermore, preferred examples of the formula (A3c-I) include, as represented by 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 Also included are compounds that are NHR ¹⁵ groups, the remaining six being hydrogen atoms.

式（Ａ３ｃ−ＩＩ）の好ましい例は、式（Ａ３ｃ−ＩＩ−１）〜（Ａ３ｃ−ＩＩ−８）である。

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

化合物（Ａ３ｃ−Ｉ）の塩としては、Ｒ⁵〜Ｒ¹²がスルホ基の場合のスルホン酸塩、Ｒ⁵〜Ｒ¹²がカルボキシル基の場合のカルボン酸塩が挙げられる。またこれら塩を形成するカチオンは特に限定されないが、溶媒に対する溶解性を考慮すると、リチウム塩、ナトリウム塩、カリウム塩のようなアルカリ金属塩；アンモニウム塩；及びエタノールアミン塩、アルキルアミン塩のような有機アミン塩などが好ましい。特にアルカリ金属塩（好ましくはナトリウム塩）は、偏光膜基材に含有させる場合に有用である。また有機アミン塩は、樹脂硬化性化合物に含有させる場合に有用であり、さらには非金属塩であるため、絶縁性が重要視される分野でも有用である。

Examples of the salt of compound (A3c-I) include a sulfonate when R ^{5 to} R ¹² are sulfo groups, and a carboxylate when R ^{5 to} R ¹² are carboxyl groups. The cations forming these salts are not particularly limited, but considering solubility in solvents, alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamine salts. Organic amine salts and the like are preferred. In particular, an alkali metal salt (preferably a sodium salt) is useful when contained in a polarizing film substrate. In addition, the organic amine salt is useful when it is contained in a resin curable compound. Furthermore, since it is a non-metallic salt, it is also useful in fields where insulation is important.

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

[In the formula (A3d-I), Z represents an oxygen atom or a sulfur atom.
R ¹ to R ⁴ are each independently a hydrogen atom, C _1-10 saturated aliphatic hydrocarbon group, C _1-10 saturated aliphatic hydrocarbon radical hydroxyl group is substituted, C _1-8 alkoxyl group There C _1-10 saturated aliphatic hydrocarbon radical which is substituted, C _1-8 thioalkoxyalkyl C _1-10 saturated aliphatic cyclohexyl group is substituted hydrocarbon group, C _6-20 aryl group, C _7-20 Represents an aralkyl group or a C _2-10 acyl group.
R ^{5 to} R ¹² are each independently a hydrogen atom, halogen atom, C _1-10 saturated aliphatic hydrocarbon group, halogenated C _1-10 saturated aliphatic hydrocarbon group, C _1-8 alkoxyl group, carboxyl Represents a group, a sulfo group, a sulfamoyl group or an N-substituted sulfamoyl group. ]

Moreover, this invention is the said colored photosensitive resin composition whose at least 1 of R < ⁵ > -R < ¹² > is an N-substituted sulfamoyl group.

Moreover, this invention is the said colored photosensitive resin composition whose at least 1 of R < ⁵ > -R < ⁸ > and at least 1 of R < ⁹ > -R < ¹² > are N-substituted sulfamoyl groups.

The present invention also provides the above colored photosensitive resin composition, wherein at least one of R ⁵ and R ⁸ and at least one of R ⁹ and R ¹² is an N-substituted sulfamoyl group.

In the present invention, the N-substituted sulfamoyl group is a —SO ₂ NHR ¹³ group, and R ¹³ is a C _1-10 substituted aliphatic hydrocarbon group or a C _1-8 alkoxyl group substituted C _{1. The} above-mentioned colored photosensitive resin composition representing a _-10 saturated aliphatic hydrocarbon group, a C _6-20 aryl group, a C _7-20 aralkyl group, or a C _2-10 acyl group.

  As the compound (A3d-I), one type may be used alone, or two or more types may be used in combination.

When two or more compounds (A3d-I) are used in combination, the amount of the compound (A-soluble) in the organic solvent is greater than when one of them is used alone. Therefore, from the viewpoint of oil solubility, it is also a preferred embodiment to use a combination of two or more kinds of the compound (A3d-I) as the pigment of the liquid crystal display device. As an example of a combination that improves oil solubility, a compound having two N-substituted sulfamoyl groups (A3d-I) (disulfonamide) and a compound having one N-substituted sulfamoyl group and one sulfo group (A3d-I) ) (Monosulfonamide). Among such combinations, one of R ^{5 to} R ⁸ and one of R ^{9 to} R ¹² is an N-substituted sulfamoyl group, and the remainder is a hydrogen atom, and R ^{5 to} R A combination with a monosulfonamide in which one of ⁸ is an N-substituted sulfamoyl group, one of R ^{9 to} R ¹² is a sulfo group, and the remainder is a hydrogen atom is preferred.

Among the compounds having an N-substituted sulfamoyl group (A3d-I), at least one of R ^{5 to} R ⁸ and at least one of R ^{9 to} R ¹² as represented by the formula (A3d-II) are: A compound having a —SO ₂ NHR ¹³ group and the remainder being a hydrogen atom is preferred.

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

  Preferred examples of formula (A3d-II) are formulas (A3d-II-1) to (A3d-II-7).

Examples of the salt of the compound (A3d-I) include a sulfonate when R ^{5 to} R ¹² are sulfo groups, and a carboxylate when R ^{5 to} R ¹² are carboxyl groups. The cations forming these salts are not particularly limited, but considering solubility in solvents, alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamine salts. Organic amine salts and the like are preferred. In particular, an alkali metal salt (preferably a sodium salt) is useful when contained in a polarizing film substrate. In addition, the organic amine salt is useful when it is contained in a resin curable compound. Furthermore, since it is a non-metallic salt, it is also useful in fields where insulation is important.

The coloring composition of this invention contains resin (B). Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin. As the resin (B), the following resin [K1]
-[K6] etc. are mentioned.
Resin [K1] At least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a monomer (b) (hereinafter sometimes referred to as “(b)”) having an ethylenically unsaturated bond.
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) Copolymer with Resin [K3] (a) and (c) Resin [K4] Obtained by reacting (b) with copolymer of (a) and (c) Resin.
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

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

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

(B) has, for example, a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. It refers to a polymerizable compound. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

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

  (B1) is, for example, a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as “(b1-1)”), an unsaturated alicyclic hydrocarbon And a monomer (b1-2) (hereinafter sometimes referred to as “(b1-2)”) having an epoxidized structure.

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

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I), and Formula (II) The compound etc. which are represented by these are mentioned.

[In Formula (I) and Formula (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ¹ and X ² each independently represent a single bond, * —R ^c —, * —R ^c —O—, * —R ^c —S—, * —R ^c —NH—.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ¹ and R ² are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

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

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

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

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

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

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

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

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

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

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

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%)
Structural unit derived from (b); 50 to 98 mol% (more preferably 55 to 90 mol%)
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.

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

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

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

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

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

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
(A) 2 to 55 mol%, more preferably 10 to 50 mol%
(C) 45-98 mol%, more preferably 50-90 mol%
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
(A) 5 to 50 mol%, more preferably 10 to 45 mol%
(C) 50 to 95 mol%, more preferably 55 to 90 mol%

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

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

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

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl. Resin such as acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic Acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyl Resin such as oxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) Resin such as acrylic acid copolymer, styrene / (meth) acrylic acid copolymer [K3]; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, tri Resin with glycidyl (meth) acrylate added to cyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin [K4], such as a resin obtained by adding glycidyl (meth) acrylate to the coalescence; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclo Copolymerization of decyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin such as a resin obtained by reacting (meth) acrylic acid with [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, and tetrahydrophthal Examples thereof include a resin [K6] such as a resin reacted with an acid anhydride.
These resins may be used alone or in combination of two or more.

  Especially, as resin (B), resin [K1], resin [K2], and 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 further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the solubility of the unexposed portion in the developer tends to be high, and the remaining film ratio and hardness of the resulting pattern tend to be high.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
The acid value of the resin (B) is preferably 50 to 180 mg-KOH / g, more preferably 60 to 150 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

  The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the solid content of the colored composition. . When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

  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 not particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) by being irradiated with light, for example, polymerizable ethylenically unsaturated Examples thereof include a compound having a bond.

Among these, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meta ) Acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) 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, caprolactone modified pentaerythritol tetra (meth) acrylate And caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among these, 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 with respect to 100 parts by mass of the resin (B) in the colored composition.

  It is preferable that the coloring composition of this invention contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound that generates an active radical or an acid by the action of light and / or heat and initiates the polymerization of the polymerizable compound (C). An agent can be used. Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds. These polymerization initiators may be used alone or in combination of two or more.

Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュアＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9 Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may 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.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc. Is mentioned. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) Thenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  Further, as the polymerization initiator (D), an acid generator that generates an acid by the action of light and / or heat may be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluenesulfonate, 4-acetoxyphenylmethylbenzyl. Onium salts such as sulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples include benzoin tosylate. The triazine compound can also be used as an acid generator.

  Content of a polymerization initiator (D) becomes like this. Preferably it is 1-30 mass% with respect to solid content of a coloring composition, More preferably, it is 5-20 mass%.

The coloring composition of the present invention may contain a polymerization initiation assistant (D1). When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D). The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D).
Examples of the polymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. These polymerization initiation assistants may be used alone or in combination of two or more.
Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

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

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

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When using the polymerization initiation assistant (D1), the content thereof is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, relative to 1 mol of the polymerization initiator (D).
Moreover, the total content of the polymerization initiator (D) and the polymerization initiation assistant (D1) is preferably 1 to 35% by mass, more preferably 5 to 25% by mass, based on the solid content of the colored composition. More preferably, it is 10-20 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.

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

  Compounds having two or more —SH in the molecule include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl). Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), tri Methylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyl Echirutorisu (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane and 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 with respect to 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within this range, the sensitivity tends to be high and the developability tends to be good.

［式（Ｓ）中、Ｒ^s1〜Ｒ^s3は、互いに独立に、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基又は炭素数２〜４のアルコキシアルコキシ基を表し、少なくとも２つは炭素数１〜４のアルコキシ基又は炭素数２〜４のアルコキシアルコキシ基を表す。］
炭素数１〜４のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられる。
炭素数１〜４のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられ、好ましくはメトキシ基及びエトキシ基である。
炭素数２〜４のアルコキシアルコキシ基としては、メトキシメトキシ基、エトキシメトキシ基、プロポキシメトキシ基、メトキシエトキシ基、エトキシエトキシ基等が挙げられ、好ましくはメトキシエトキシ基である。
Ｒ^s1〜Ｒ^s3のうち２つが炭素数１〜４のアルコキシ基であり、好ましくはＲ^s1〜Ｒ^s3のいずれもが炭素数１〜４のアルコキシ基である。 The coloring composition of the present invention may contain a silane compound (S). The silane compound (S) is a compound having a group represented by the formula (S).

[In the formula (S), R ^{s1 to} R ^s3 each independently represent a C 1-4 alkyl group, a C 1-4 alkoxy group or a C 2-4 alkoxy alkoxy group, and at least 2 One represents an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy 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.
As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, Preferably they are a methoxy group and an ethoxy group.
Examples of the alkoxyalkoxy group having 2 to 4 carbon atoms include a methoxymethoxy group, an ethoxymethoxy group, a propoxymethoxy group, a methoxyethoxy group, and an ethoxyethoxy group, and a methoxyethoxy group is preferable.
Two of R ^{s1 to} R ^s3 are alkoxy groups having 1 to 4 carbon atoms, and preferably all of R ^{s1 to} R ^s3 are alkoxy groups having 1 to 4 carbon atoms.

  Examples of the silane compound (S) include methyltrimethoxysilane, methyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, (3-chloropropyl) trimethoxysilane, (3- Chloropropyl) methyldimethoxysilane, (3-chloropropyl) methyldiethoxysilane, (3-glycidyloxypropyl) trimethoxysilane, (3-glycidyloxypropyl) triethoxysilane, (3-glycidyloxypropyl) methyldimethoxysilane , (3-sulfanylpropyl) trimethoxysilane, (3-methacryloyloxypropyl) trimethoxysilane, (3-methacryloyloxypropyl) methyldimethoxysilane, [2- (3,4-epoxy Chlohexyl) ethyl] trimethoxysilane, [N-2- (N-vinylbenzylaminoethyl) -3-aminopropyl] trimethoxysilane hydrochloride, (triaminopropyl) trimethoxysilane, (3-aminopropyl) trimethoxy Silane, (3-aminopropyl) triethoxysilane, (3-aminopropyl) methyldiethoxysilane, (3-aminopropyl) tris (2-methoxyethoxy) silane, [3- (2-aminoethyl) -3- Aminopropyl] trimethoxysilane, [3- (2-aminoethyl) -3-aminopropyl] methyldimethoxysilane, (3-ureidopropyl) trimethoxysilane, (3-ureidopropyl) triethoxysilane, (N-amino) Ethyl-3-aminopropyl) trimethoxysilane, (N-amino) Ethyl-3-amino propyl) dimethoxysilane, (N- methyl-3-aminopropyl) trimethoxysilane, include (N- phenyl-3-aminopropyl) trimethoxysilane.

  The content of the silane compound (S) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to the solid content of the coloring composition. When the content of the silane compound (S) is within this range, there is a tendency that pattern peeling during development is small.

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

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

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

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

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.
Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, cyclohexanone and the like are preferable, 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 is more preferable.

  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. At this time, the content of the solvent having a boiling point at 1 atm of 170 ° C. or more and 250 ° C. or less 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 colored composition tends to be excellent in coatability.

  Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to a coloring composition, More preferably, it is 75-92 mass%. In other words, the solid content of the coloring composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and 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 silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

  Examples of the silicone-based surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan GK), etc. are mentioned.

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

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

These surfactants may be used alone or in combination of two or more.
The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, based on the colored composition. More preferably, it is 0.01 mass% or more and 0.05 mass% or less. However, the content of the pigment dispersant is not included in the content of the surfactant (F). 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, an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, and a chain transfer agent, if necessary.

The coloring composition of the present invention can be prepared, for example, as follows.
First, it is preferable that the pigment (A1) is mixed with the solvent (E) and dispersed using a disperser until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) 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 then mixed, or both may be mixed and then dispersed together. When the coloring composition of this invention contains dye (A3), you may make it disperse | distribute with a pigment (A1) and / or a pigment (A2). Examples of the disperser include a paint shaker, a sand grinder, a bead mill, a ball mill, a roll mill, a stone mill, a jet mill, and a homogenizer.

  When the dispersion treatment is performed using a paint shaker, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to 2 mm. The temperature at which the dispersion treatment is performed is preferably 0 to 100 ° C or higher, and more preferably 20 to 80 ° C or higher. The time for performing the dispersion treatment is usually 1 to 20 hours, preferably about 1 to 10 hours, but may be appropriately adjusted depending on the composition of the pigment dispersion and the size of the paint shaker device. .

  By mixing a predetermined amount of the pigment dispersion thus obtained, the remainder of the resin (B), the remainder of the solvent (E), and other components contained in the coloring composition, the target coloring composition is obtained. Can be obtained. The colored composition is preferably filtered with a filter having a pore size of about 0.5 to 10 μm as necessary.

Examples of a method for forming a pattern using the colored composition of the present invention include a photolithographic method, an inkjet method, a printing method, and the like. Of these, the photolithographic method is preferable.
The photolithographic method is a method of obtaining a pattern by applying the colored composition to a substrate, drying, exposing through a photomask, and developing.

Examples of the substrate include glass, metal, plastic, and the like, and may be plate-shaped or film-shaped. In addition, structures such as a color filter, various insulating or conductive films, and a driving circuit may be formed on these substrates.
Application to the substrate can be performed using a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater, a curtain flow coater, or a spinless coater) or an inkjet.

Examples of the method for drying the film applied to the substrate include methods such as heat drying, natural drying, ventilation drying, and vacuum drying. A plurality of methods may be combined. As drying temperature, 10-120 degreeC is preferable and 25-100 degreeC is more preferable. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. The vacuum drying is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa. By drying, volatile components such as a solvent contained in the colored composition are removed.
The film thickness of the coating film after drying is not particularly limited and can be appropriately adjusted depending on the material used, application, and the like, and is, for example, 0.1 to 20 μm, preferably 1 to 6 μm.

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

After exposure, a pattern can be obtained by contacting a developing solution to dissolve a predetermined portion, for example, an unexposed portion, and developing. As the developer, an organic solvent can be used, but an aqueous solution of a basic compound is preferable because the developer does not easily dissolve or swell the exposed portion of the coating film, and a pattern having a good shape is obtained.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

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 silicate, potassium silicate, and sodium carbonate. Inorganic basic compounds such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine Organic basic compounds such as monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Of these, potassium hydroxide, sodium hydrogen carbonate and tetramethylammonium hydroxide are preferable.
The density | concentration in the aqueous solution of these inorganic and organic basic compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The aqueous solution of the basic compound may contain a surfactant.
Surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters , Nonionic surfactants such as polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine;
Anionic surfactants such as sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate;
And cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium 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, and particularly preferably 0.1 to 5% by mass.

  Furthermore, you may post-bake as needed. Post baking is preferably performed, for example, in the range of 150 to 250 ° C. for 1 to 240 minutes.

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

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

Synthesis example 1
Sodium tert-amyl alcoholate was synthesized by reacting 174 g of tert-amyl alcohol with 22.2 g of metallic sodium under a nitrogen atmosphere at 130 ° C. This was heated to 60 ° C., 91.0 g of 4-bromobenzonitrile, 71.05 g of di-tert-amyl oxalate, and 108.9 g of tert-amyl alcohol were added, and the solution temperature was adjusted to 85 ° C. or lower. Stir for hours. This suspension was further stirred for 18 hours or more and then added to a mixed solution of 200 g of methanol, 1000 g of water and 49.21 g of sulfuric acid cooled to −10 ° C. After the addition of the suspension was completed, the reaction was completed by stirring for 5 hours while maintaining the temperature at 0 ° C., and then the solid content was filtered. The solid content was washed repeatedly with methanol and water alternately until the filtrate was no longer colored and no salt precipitation occurred. Thereafter, the solid content was dried with a vacuum dryer at 80 ° C. for 18 hours to obtain the intended red pigment 1. The yield was 107 g.

Synthesis example 2
In a flask equipped with a condenser and a stirrer, a mixture of a compound represented by the formula (A1-1a) and a compound represented by the formula (A1-1b) (manufactured by Chugai Kasei Co., Ltd., trade name: Chugai Aminol Fast Pink R) Part, 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added dropwise and 10.9 parts of thionyl chloride was added dropwise while maintaining at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and dye 1 (compounds represented by formula (A1-1-1) to formula (A1-1-8)). 11.3 parts of a mixture were obtained.

Synthesis example 3
After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-4-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of a 35% aqueous sodium nitrite solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little to dissolve, followed by stirring for 2 hours. A suspension containing was obtained. Subsequently, an aqueous solution in which 5.6 parts of amidosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added to quench excess sodium nitrite.
Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) is suspended in 70 parts of water, and the pH is adjusted to 8.0 using sodium hydroxide. did. The suspension containing the diazonium salt was added dropwise over 15 minutes while adding a 10% sodium hydroxide solution appropriately so that the pH was in the range of 7 to 7.5. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 11.7 parts (yield 87%) of the compound represented by the formula (p-1).

  10 parts of the compound of formula (p-1) are dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved in ammonium sulfate chromium (III) 12 water (manufactured by Wako Pure Chemical Industries, Ltd.) 3.1. After adding 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated to reflux for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% brine, the reddish orange solid obtained after filtration was dried at 60 ° C., and 13.6 parts of the compound represented by the formula (z-1) ( 63%).

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 compound represented by formula (z-1) (mass spectrometry) ionization mode = ESI−: m / z = 882.1 [M−Na ⁺ ] ⁻
Exact Mass: 905.1

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

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 compound represented by formula (g-1) (mass spectrometry) 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 at 60 ° C. under reduced pressure, washed with 3500 parts of water, filtered, and dried under reduced pressure at 60 ° C. to obtain 263 parts (yield) of the compound (dye 2) represented by the formula (A2b-7). 65%) was obtained.
The structure of the compound represented by the formula (3a-23) was determined by elemental analysis. As an analytical instrument, an ICP emission analyzer (ICPS-8100; manufactured by Shimadzu Corporation) was used.
C55.6 H5.1 N11.9 Cr3.71

Synthesis example 4
100 parts of water was added to 10 parts of 2,2′-benzidinedisulfonic acid (containing 30% water) represented by the formula (a-1), and then adjusted to pH 7-8 with 30% aqueous sodium hydroxide solution under ice cooling. did. The following operations were performed under ice cooling. 5.6 parts of sodium nitrite was added and stirred for 30 minutes. After adding 14.8 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution in which 3.8 parts of amidosulfuric 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-carbamoyl-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-1), The pH was adjusted to 8-9 with a 30% aqueous sodium hydroxide solution.

  The following operations were performed under ice cooling. The aqueous alkaline solution of pyridones was stirred to give a colorless solution, and then a suspension containing a diazonium salt was added dropwise with a pump while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 15.7 parts of an azo compound represented by 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. As an analytical instrument, ECA-500 (manufactured by JEOL Ltd.) was used.
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), 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 value (ppm, TMS standard), 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

  A flask equipped with a condenser and a stirrer is charged with 5 parts of an azo compound (A3c-I-1), 50 parts of chloroform and 2.1 parts of N, N-dimethylformamide, and maintained at 20 ° C. or lower with stirring. While, 6 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 4 parts of 1,5-dimethylhexylamine and 14 parts of triethylamine was added dropwise. Thereafter, the reaction was carried out by stirring overnight at the same temperature. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and 3.6 parts of an azo compound (dye 3) represented by the formula (A3c-II-1) (yield 56 %).

Synthesis example 5
After adding 300 parts of water to 30 parts of 2,2′-benzidinedisulfonic acid (containing 30% water) represented by the formula (a-1), the mixture was adjusted to pH 7-8 with 30% aqueous sodium hydroxide solution under ice cooling. Adjusted. The following operations were performed under ice cooling. 12.6 parts of sodium nitrite was added and stirred for 30 minutes. After adding 38.1 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution in which 5.3 parts of amidosulfuric acid was dissolved in 57.4 parts of water was added to the reaction solution and 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 the formula (c-2), the pH was adjusted to 8-9 with a 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The aqueous barbituric acid aqueous solution was stirred to give a colorless solution, and a suspension containing a diazonium salt was added dropwise with a pump while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 14.6 parts of an azo compound represented by 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. As an analytical instrument, ECA-500 (manufactured by JEOL Ltd.) was used.
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), 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 standard), 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) was produced as follows. A flask equipped with a condenser and a stirrer is charged with 10 parts of an azo compound (A3d-I-1), 100 parts of chloroform, and 4.2 parts of N, N-dimethylformamide, while maintaining the temperature at 20 ° C. or lower with stirring. 7 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 5 parts of 1,5-dimethylhexylamine and 15 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed solution of 58 parts of acetic acid and 600 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 10.9 parts (yield 82%) of an azo compound (A3d-II-1; dye 4).

Synthesis Example 6
133 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 ° C., and 22.0 g (0.10 mol) of dicyclopentanyl methacrylate (FA-513M; manufactured by Hitachi Chemical Co., Ltd.), 82.8 g (0 mol) of benzyl methacrylate. .47 mol), 37.0 g (0.43 mol) of methacrylic acid, 3.6 g of 2,2′-azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate were added using a dropping funnel for 2 hours. The mixture was added dropwise to the flask, and after completion of the addition, the mixture was further stirred at 100 ° C. for 5 hours.
After completion of the stirring, air was introduced into the flask through a gas introduction tube, and the atmosphere in the flask was replaced with air. Then, 21.5 g (0.15 mol) of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and hydroquinone 0 .145 g was charged into the flask, and the reaction was continued at 110 ° C. for 6 hours. Resin 1 having 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 acid value of 97 mgKOH / g A solution was obtained.

Synthesis example 7
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and gas introduction tube, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added while stirring. Heated to ° C. Then 36 parts of acrylic acid; and 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate {ie monomer (I-1)} and 3,4-epoxytri Cyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate {ie, monomer (II-1)} mixture {monomer (I-1) in mixture: monomer (II -1) molar ratio = 50: 50} 264 parts; was dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a monomer solution. The monomer solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel. On the other hand, a polymerization initiator solution in which 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts of propylene glycol monomethyl ether acetate was added for 4 hours using another dropping funnel. And dropped into the flask. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature, weight average molecular weight Mw: 9000, molecular weight distribution: 2.0, solid content 33%, solid content acid value 90 mg. A resin 2 solution of -KOH / g was obtained.

About the measurement of polystyrene conversion weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by said synthesis example, it carried out on condition of the following using GPC method.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)

Example 1
(Preparation of coloring composition)
Pigment: 70 parts of pigment 1
A pigment dispersion in which 28 parts of a pigment dispersant and 462 parts of propylene glycol monomethyl ether acetate are mixed and the pigment is sufficiently dispersed using a bead mill,
Resin: Resin 1 (solid content conversion) 65 parts,
Polymerizable compound: 35 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound) 10 parts,
Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; manufactured by BASF; alkylphenone compound)
6 parts Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound) 2 parts Polymerization initiation assistant: 4,4 '-Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts, and Solvent: 267 parts of propylene glycol monomethyl ether acetate,
Were mixed to obtain a colored composition.

[Preparation of pattern]
A colored composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored composition and the quartz glass photomask having a pattern is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) is used in an air atmosphere at 150 mJ / Light was irradiated with an exposure amount of cm ² (reference to 365 nm). As a photomask, a mask on which a 100 μm line and space pattern was formed was used. After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and 220 ° C. in an oven. Was post-baked for 20 minutes to obtain a pattern.

[Foreign matter evaluation]
About the obtained pattern, it observed with the surface shape optical microscope (100-times multiplication factor; VF-7510; product made by Keyence Corporation). In the case where no foreign matter was observed in the observation visual field, the mark was “◯”, and in the case where a foreign matter was found, the mark was ×. The results are shown in Table 1.

[Film thickness measurement]
About the obtained pattern, film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.)
) Was used to measure the film thickness. The results are shown in Table 1.

[Chromaticity evaluation]
About the obtained pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinates in the XYZ color system of CIE (Characteristic function of C light source) x, y) and brightness Y were measured. The results are shown in Table 1.

[Contrast evaluation]
A coating film was obtained in the same manner as the pattern production except that no photomask was used during exposure. About the obtained coating film, a contrast meter (CT-1; manufactured by Aisaka Electric Co., Ltd., color / color difference meter BM-5A; manufactured by Topcon Corporation, light source: F-10, polarizing film; manufactured by Aisaka Electric Co., Ltd.) The contrast was measured using a blank value of 30000. If the contrast in the coating film is high, it can be said that the pattern is similarly high in contrast. The results are shown in Table 1.

Example 2
(Preparation of coloring composition)
Pigment: 36 parts of pigment 1
14 parts of a pigment dispersant and 238 parts of propylene glycol monomethyl ether acetate are mixed, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
Pigment: C.I. I. 36 parts of Pigment Red 242,
A pigment dispersion in which 18 parts of a pigment dispersant and 194 parts of propylene glycol monomethyl ether acetate are mixed and the pigment is sufficiently dispersed using a bead mill,
Resin: Resin 1 (solid content conversion) 65 parts,
Polymerizable compound: 35 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound) 10 parts,
Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; manufactured by BASF; alkylphenone compound)
6 parts Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound) 2 parts Polymerization initiation assistant: 4,4 '-Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts, and Solvent: 319 parts propylene glycol monomethyl ether acetate
Are mixed to obtain a colored composition. About this coloring composition, operation similar to Example 1 was performed and the high contrast color filter was obtained.

Example 3
(Preparation of coloring composition)
Pigment: 35 parts of Pigment 1
14 parts of a pigment dispersant and 234 parts of propylene glycol monomethyl ether acetate are mixed, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
Pigment: C.I. I. 35 parts of Pigment Red 177,
A pigment dispersion in which 16 parts of a pigment dispersant and 191 parts of propylene glycol monomethyl ether acetate are mixed and the pigment is sufficiently dispersed using a bead mill,
Resin: Resin 1 (solid content conversion) 65 parts,
Polymerizable compound: 35 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound) 10 parts,
Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; manufactured by BASF; alkylphenone compound)
6 parts Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound) 2 parts Polymerization initiation assistant: 4,4 '-Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts, and Solvent: 314 parts propylene glycol monomethyl ether acetate
Are mixed to obtain a colored composition. About this coloring composition, operation similar to Example 1 was performed and the high contrast color filter was obtained.

Example 4
(Preparation of coloring composition)
Pigment: 53 parts of Pigment 1
A pigment dispersion in which 21 parts of a pigment dispersant and 353 parts of propylene glycol monomethyl ether acetate are mixed and the pigment is sufficiently dispersed using a bead mill,
Dye: Dye 1 13 parts Resin: Resin 1 (solid content conversion) 16 parts Resin: Resin 2 (solid content conversion) 49 parts Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 35 Part,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound) 10 parts,
Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; manufactured by BASF; alkylphenone compound)
6 parts Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound) 2 parts Polymerization initiation assistant: 4,4 '-Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts, and Solvent: 343 parts of propylene glycol monomethyl ether acetate,
Are mixed to obtain a colored composition. About this coloring composition, operation similar to Example 1 was performed and the high contrast color filter was obtained.

Example 5
(Preparation of coloring composition)
Pigment: 53 parts of Pigment 1
A pigment dispersion in which 21 parts of a pigment dispersant and 353 parts of propylene glycol monomethyl ether acetate are mixed and the pigment is sufficiently dispersed using a bead mill,
Dye: Dye 2 13 parts Resin: Resin 1 (solid content conversion) 16 parts Resin: Resin 2 (solid content conversion) 49 parts Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 35 Part,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound) 10 parts,
Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; manufactured by BASF; alkylphenone compound)
6 parts Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound) 2 parts Polymerization initiation assistant: 4,4 '-Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts Surfactant: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts,
Solvent: 252 parts of ethyl lactate and Solvent: 91 parts of propylene glycol monomethyl ether acetate
Are mixed to obtain a colored composition. About this coloring composition, operation similar to Example 1 was performed and the high contrast color filter was obtained.

Example 6
(Preparation of coloring composition)
Pigment: 53 parts of Pigment 1
A pigment dispersion in which 21 parts of a pigment dispersant and 353 parts of propylene glycol monomethyl ether acetate are mixed and the pigment is sufficiently dispersed using a bead mill,
Dye: Dye 3 13 parts Resin: Resin 1 (solid content conversion) 16 parts Resin: Resin 2 (solid content conversion) 49 parts Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 35 Part,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound) 10 parts,
Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; manufactured by BASF; alkylphenone compound)
6 parts Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound) 2 parts Polymerization initiation assistant: 4,4 '-Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts,
Solvent: 252 parts of ethyl lactate and Solvent: 91 parts of propylene glycol monomethyl ether acetate
Are mixed to obtain a colored composition. About this coloring composition, operation similar to Example 1 was performed and the high contrast color filter was obtained.

Example 7
(Preparation of coloring composition)
Pigment: 53 parts of Pigment 1
A pigment dispersion in which 21 parts of a pigment dispersant and 353 parts of propylene glycol monomethyl ether acetate are mixed and the pigment is sufficiently dispersed using a bead mill,
Dye: Dye 4 13 parts Resin: Resin 1 (solid content conversion) 16 parts Resin: Resin 2 (solid content conversion) 49 parts Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 35 Part,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound) 10 parts,
Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; manufactured by BASF; alkylphenone compound)
6 parts Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound) 2 parts Polymerization initiation assistant: 4,4 '-Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts Surfactant: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts,
Solvent: 252 parts of ethyl lactate and Solvent: 91 parts of propylene glycol monomethyl ether acetate
Are mixed to obtain a colored composition. About this coloring composition, operation similar to Example 1 was performed and the high contrast color filter was obtained.

Comparative Example 1
(Preparation of coloring composition)
Pigment: C.I. I. 72 parts of Pigment Red 254,
A pigment dispersion in which 33 parts of a pigment dispersant and 391 parts of propylene glycol monomethyl ether acetate are mixed and the pigment is sufficiently dispersed using a bead mill,
Resin: Resin 1 (solid content conversion) 65 parts,
Polymerizable compound: 35 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound) 10 parts,
Polymerization initiator: 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; manufactured by BASF; alkylphenone compound)
6 parts Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; manufactured by DKSH Japan; triazine compound) 2 parts Polymerization initiation assistant: 4,4 '-Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts, and Solvent: 368 parts of propylene glycol monomethyl ether acetate,
Were mixed to obtain a colored composition. The coloring composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the coloring composition which can manufacture a high contrast color filter.

Claims (4)

A pigment, a metal complex dye and a resin, wherein the pigment has the formula (P)

[In the formula (P), 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. ]
In comprises a compound represented by the metal complex dye, the colored composition is a compound represented by the formula (3).

[In the formula (3), R ^{31 to} R ⁴⁸ are each independently 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 ^-, -CO
OR ⁵¹ or —SO ₂ R ⁵¹ is represented.
R ⁴⁹ and R ⁵⁰ each independently represents a hydrogen atom, a methyl group, an ethyl group or an amino group.
R ⁵¹ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is replaced by —O— or —CO—. Also good.
A ^{1 to} A ⁴ each independently represent * —O—, * —O—CO—, or * —CO—O—. * Represents a bond with M.
M represents Cr or Co.
n represents an integer of 2 to 5.
D ⁺ represents a monovalent cation derived from hydrone, a monovalent metal cation or a compound having a xanthene skeleton. ] The coloring composition according to claim 1, wherein the resin is at least one selected from the group consisting of the following resins [K1] to [K6].
Resin [K1]: Monomer having at least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond Copolymer with body (b)
Resin [K2]: (a), (b), monomer (c) copolymerizable with (a) ((c) is different from (a) and (b)) Copolymer with
Resin [K3]: Copolymer of (a) and (c)
Resin [K4]: Resin obtained by reacting (b) with the copolymer of (a) and (c)
Resin [K5]: Resin obtained by reacting (a) with the copolymer of (b) and (c)
Resin [K6]: a resin obtained by reacting the copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride A color filter formed by the coloring composition according to claim 1 or 2. A display device comprising the color filter according to claim 3 .