JP2012214719A - Salt for dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a salt showing a good spectral density, a dye and a colored composition using the same.SOLUTION: The salt is represented by formula (0), wherein Xand Xrepresent -CO-O- or the like; Land Lrepresent alkanediyl; Rrepresents methyl or the like; Rrepresents -CN or the like; Rrepresents alkyl; Rto Rrepresent sulfonyl amide or amino; ring Zand ring Zrepresent an aromatic ring; Rto Rrepresent an aliphatic hydrocarbon group or the like; and Xrepresents H or Cl.

Description

  The present invention relates to salts useful as dyes.

  Conventionally, a dye of a metal complex salt compound has been used for color display using reflected light or transmitted light in various fields (for example, fiber materials, liquid crystal display devices, etc.). Examples of such a dye include C.I. represented by the following formula, which is a chromium complex dye having an azo compound as a ligand. I. Solvent Yellow 21 is widely known.

Industrial Dies Chemistry, Properties, Applications, WILEY-VCH, 2003.

  However, the above-mentioned C.I. I. In Solvent Yellow 21, the spectral density was not always fully satisfactory.

［式（０）中、Ｘ^１及びＸ^２は、互いに独立に、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−を表す。
Ｌ^１及びＬ^２は、互いに独立に、炭素数１〜８のアルカンジイル基を表す。
Ｒ¹は、水素原子、メチル基またはエチル基を表す。
Ｒ^２は、水素原子、−ＣＮ、又は−ＣＯＮＨ_２を表す。
Ｒ^３は、ハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基を表す。
Ｒ^４〜Ｒ^７は互いに独立に、−Ｒ^８、−ＯＲ^８、−ＣＯＯＲ^８、−ＣＯＲ^８、−ＯＣＯＯＲ^８、−ＯＣＯＲ^８、−ＣＮ、−ＮＯ_２、ハロゲン原子、−ＳＯ_３Ｈ、−ＳＯ_３Ｎａ、−ＳＯ_３Ｋ、−ＳＯ_２ＮＲ^８Ｒ^９又は−ＮＲ^１１Ｒ^１２を表すか、Ｒ^４及びＲ^５、Ｒ^５及びＲ^６並びにＲ^６及びＲ^７は、互いに結合してベンゼン環の炭素を含んだ６〜７員環を形成する。
Ｒ^８及びＲ^９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、炭素数７〜１２のアラルキル基、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、該アラルキル基及び該芳香族炭化水素基に含まれる水素原子は、−ＯＲ^１０で置換されていてもよい。
Ｒ^１０は、水素原子、炭素数１〜８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。
Ｒ^１１及びＲ^１２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、炭素数２〜８のアシル基又はテトラヒドロフルフリル基を表すか、Ｒ^１１及びＲ^１２は、互いに結合して窒素原子を含んだ環を形成する。
環Ｚ^１及び環Ｚ^２は、互いに独立に、置換基を有していてもよい芳香環を表し、Ｒ^２１及びＲ^２２は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表し、Ｒ^２３及びＲ^２４は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表すか、Ｒ^２３とＲ^２４が一緒になってアルカンジイル基を形成する。Ｒ^２５及びＲ^２６は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表すか、Ｒ^２５とＲ^２６が一緒になってアルカンジイル基を形成する。Ｒ^２７及びＲ^２８は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表すか、Ｒ^２７とＲ^２８が一緒になってアルカンジイル基を形成する。Y^１は、水素原子又は塩素原子を表す。]
［２］Ｒ^４〜Ｒ^７が、互いに独立に、−Ｒ^８、−ＯＲ^８、−ＣＯＯＲ^８、−ＣＮ、−ＮＯ_２、ハロゲン原子、−ＳＯ_３Ｈ、−ＳＯ_３Ｎａ、−ＳＯ_３Ｋ、−ＳＯ_２ＮＲ^８Ｒ^９又は−ＮＲ^１１Ｒ^１２である［１］記載の塩。
［３］Ｘ^１が、＊−Ｏ−ＣＯ−（＊は、Ｌ^１との結合位置を表す。）である上記［１］又は［２］記載の塩。
［４］Ｒ^２が、−ＣＮである上記［１］〜［３］のいずれか記載の塩。
［５］Ｒ^２３〜Ｒ^２６が、互いに独立に、炭素数１〜８の１価の脂肪族炭化水素基である上記［１］〜［４］のいずれか記載の塩。
［６］Ｒ^２１及びＲ^２２が、互いに独立に、炭素数１〜１２の脂肪族炭化水素基である［１］〜［５］のいずれか記載の塩。
［７］Ｚ^１およびＺ^２が、メチル基で置換されてもよいベンゼン環である［１］〜［６］のいずれか記載の塩。
［８］上記［１］〜［７］のいずれか記載の塩を有効成分とする染料。
［９］上記［８］記載の染料、樹脂及び溶剤を含む着色樹脂組成物。 The present invention provides the following [1] to [9].
[1] A salt represented by the formula (0).

[In Formula (0), X ¹ and X ² each independently represent —CO—O— or —O—CO—.
L ¹ and L ² each independently represent an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a hydrogen atom, a methyl group or an ethyl group.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4 to} R ⁷ are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —COR ⁸ , —OCOOR ⁸ , —OCOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, — _{SO 3 Na, -SO 3 K,} -SO 2 NR 8 R 9 or ^-NR 11 or represents ^{R 12, R 4} and ^R 5, ^{R 5} and ^{R 6} and ^{R 6} and ^{R 7,} benzene combined with each other A 6-7 membered ring containing the ring carbon is formed.
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -OR ¹⁰ .
R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ¹¹ and R ¹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group, or R ¹¹ and R 12 ¹² combine with each other to form a ring containing a nitrogen atom.
Ring Z ¹ and Ring Z ² each independently represent an optionally substituted aromatic ring, and R ²¹ and R ²² each independently represent a substituent having 1 to 1 carbon atoms. 12 represents an aliphatic hydrocarbon group or a hydrogen atom having 12 carbon atoms, and R ²³ and R ²⁴ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ²³ and R ²⁴ together form an alkanediyl group. R ²⁵ and R ²⁶ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, or R ²⁵ and R ²⁶ together represent an alkanediyl group. Form. R ²⁷ and R ²⁸ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, or R ²⁷ and R ²⁸ together form an alkanediyl group. Form. Y ¹ represents a hydrogen atom or a chlorine atom. ]
[2] R ^{4 to} R ⁷ are independently of each other —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K. a _-SO 2 ^NR 8 ^{R 9} or ^-NR 11 ^{R 12} [1] salt according.
[3] The salt according to the above [1] or [2], wherein X ¹ is * —O—CO— (* represents a bonding position with L ¹ ).
[4] The salt according to any one of the above [1] to [3], wherein R ² is —CN.
[5] The salt according to any one of [1] to [4], wherein R ^{23 to} R ²⁶ are each independently a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
[6] The salt according to any one of [1] to [5], wherein R ²¹ and R ²² are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
[7] The salt according to any one of [1] to [6], wherein Z ¹ and Z ² are benzene rings optionally substituted with a methyl group.
[8] A dye comprising the salt according to any one of [1] to [7] as an active ingredient.
[9] A colored resin composition comprising the dye, resin and solvent according to [8] above.

  The salts of the present invention exhibit good spectral density.

The salt of the present invention comprises an anion represented by the following formula (A1) (hereinafter sometimes referred to as “anion (A1)”) and a cation represented by the following formula (A2) (hereinafter referred to as “cation (A2)”). A salt (hereinafter sometimes referred to as “salt (0)”).
In addition, tautomers of the salts of the present invention are also included in the present invention.

  The anion (A1) can be selected according to the color of the target color filter. It is preferable that the salt containing an anion (A1) is sufficiently dissolved in a solvent. Furthermore, the anion (A1) is preferably dissolved in a developer used for pattern formation to such an extent that the pattern can be formed.

In the anion (A1), X ¹ and X ² are —CO—O— or —O—CO—, and the bond orientations may be the same or different from each other.
Among these, X ¹ is preferably * —O—CO— (* represents a bond with L ¹ ).
It is preferable that X ¹ is * —O—CO— because the salt of the present invention can be easily produced.

In the anion (A1), L ¹ and L ² are alkanediyl groups having 1 to 8 carbon atoms.
Examples of the alkanediyl group having 1 to 8 carbon atoms include methylene group, 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.

In the anion (A1), R ¹ is a hydrogen atom, a methyl group or an ethyl group.

In the anion ^{(A1), -L 1 -X 1} -L 2 -X 2 -R 1 is a group having two groups having an ester bond or one ester bond and one carboxyl group. Having such a group is preferable because the solubility of the salt in an organic solvent tends to be improved.
The ^{-L 1 -X 1 -L 2 -X 2} -R 1, for example, groups represented respectively by formula (f-1) ~ formula (f-18) are mentioned.

  Among these, groups represented by formula (f-4) and formula (f-5) are preferable because the raw materials are easily available.

In the anion (A1), R ² is a hydrogen atom, —CN or —CONH ₂ . Especially, -CN is preferable at the point which is easy to acquire a raw material.

In the anion (A1), R ³ is an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a halogen atom.
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 halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As a C1-C4 alkyl group substituted by the halogen atom, a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned, for example.
R ³ is preferably a methyl group or a trifluoromethyl group, and more preferably a methyl group.

In the anion (A1), R ^{4 to} R ⁷ are, independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —COR ⁸ , —OCOOR ⁸ , —OCOR ⁸ , —CN, —NO ₂ , a halogen atom _{, -SO 3 H, -SO 3 Na} , -SO 3 K, a -SO 2 ^NR 8 ^{R 9} or ^-NR 11 ^{R 12.} R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may be bonded to each other to form a 6 to 7 membered ring containing carbon of a benzene ring.
R ^{4 to} R ⁷ are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K, —SO it is preferably ₂ NR ⁸ R ⁹ or ^-NR 11 ^{R 12.}

In the anion (A1), R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or 6 to 10 carbon atoms. The hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group, and the aromatic hydrocarbon group may be substituted with —OR ¹⁰ .
R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.

In the anion (A1), examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ⁸ and R ⁹ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. A linear aliphatic hydrocarbon group such as a group, n-hexyl group, n-heptyl group, n-octyl group;
Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl Group, 1- (1-methylethyl) butyl group, 1- (1-methylethyl) -2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group Group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1- (1-methylethyl) pentyl group, 1-butylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl-3 -Methylbutyl group, 1- (1,1-dimethylethyl) butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3- Dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4- Dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethyl Rupentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1, 1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3- Dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl Group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1 -Propyl-3-methylbutyl group, 1- (1-methylethyl) -1-methylbutyl group, 1- (1-methylethyl) -2-methylbutyl group, 1- (1-methylethyl) -3-methylbutyl group, And branched aliphatic hydrocarbon groups such as 1,1-diethylbutyl group and 1,2-diethylbutyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms in R ⁸ and R ⁹ include a benzyl group, a diphenylmethyl group, a phenylethyl group, and a 3-phenylpropyl group.
Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ⁸ and R ⁹ include aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, and an anthryl group.

In the anion (A1), examples of —OR ⁸ in R ^{4 to} R ⁷ include a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. , 2-ethylhexyloxy group, phenoxy group, benzyloxy group, benzoyloxy group and the like.
Examples of —OR ⁸ substituted with —OR ¹⁰ include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, 1-ethoxypropyl group, 2-ethoxypropyl group, 1- Ethoxy-1-methylethyl group, 1-methyl-2-ethoxyethyl group, 1- (1-methylethoxy) propyl group, 2- (1-methylethoxy) propyl group, 1- (1-methylethoxy) -1 -Methylethyl group, 2- (1-methylethoxy) -1-methylethyl group, 3-ethoxypropyl group and the like can be mentioned.

In the anion (A1), examples of —COOR ⁸ in R ^{4 to} R ⁷ include a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group.

In the anion (A1), examples of —COR ⁸ in R ^{4 to} R ⁷ include an acetyl group, a propionyl group, an isobutyryl group, a valeryl group, and an isovaleryl group.
In the anion (A1), examples of —OCOOR ⁸ in R ^{4 to} R ⁷ include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, an n-butoxycarbonyloxy group, Examples include isobutoxycarbonyloxy group, sec-butoxycarbonyloxy group, n-pentyloxycarbonyloxy group, phenoxycarbonyloxy group and the like.
Examples of —OCOR ⁸ in R ^{4 to} R ⁷ include an acetyloxy group and a pivaloyloxy group.

In the anion (A1), examples of —NR ¹¹ R ¹² in R ^{4 to} R ⁷ include N-methylamino group, N, N-dimethylamino group, N-ethylamino group, N, N-diethylamino group, N -Propylamino group, N, N-dipropylamino group, N-butylamino group, N, N-dibutylamino group, N-pentylamino group, N-acetylamino group and the like can be mentioned.
Examples of —NR ¹¹ R ¹² in which R ¹¹ and R ¹² are bonded to each other to form a ring containing a nitrogen atom include a 1-pyrazolyl group, a pyrrolidino group, a piperidino group, and a morpholino group.
Among these, an N-acetylamino group is preferable from the viewpoint of solubility in an organic solvent.

In the anion (A1), examples of —SO ₂ NR ⁸ R ⁹ in R ^{4 to} R ⁷ include an unsubstituted sulfamoyl group, an N-1 substituted sulfamoyl group, and an N, N-2 substituted sulfamoyl group.

Examples of the N-1-substituted sulfamoyl group include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, and N-butylsulfamoyl group. N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- ( 2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentyl Rufamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1- Methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group An N-1 substituted sulfamoyl group substituted with an aliphatic hydrocarbon group such as a group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N-allylsulfamoyl group;
N- (2-hydroxyethyl) sulfamoyl group, N- (3-hydroxypropyl) sulfamoyl group, N- (2-hydroxypropyl) sulfamoyl group, N- (2,3-dihydroxypropyl) sulfamoyl group, N- (2 -Hydroxybutyl) sulfamoyl group, N- (4-hydroxybutyl) sulfamoyl group, N-substituted sulfamoyl group substituted with an aliphatic hydrocarbon group having a hydroxy group such as N- (1-hydroxymethylethyl) sulfamoyl group ;
N- (2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N-methoxypropylsulfamoyl group, N-ethoxypropylsulfamoyl group N-propoxypropylsulfamoyl group, N-isopropoxypropylsulfamoyl group, N-hexyloxypropylsulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (3-tert- Butoxypropyl) sulfamoyl group, N- (4,4-dimethoxybutyl) sulfamoyl group, N-substituted sulfamoyl group substituted with an alkyl group or cycloalkyl group having an alkoxy group such as N-methoxyhexylsulfamoyl group;
An N-1 substituted sulfamoyl group substituted with an aliphatic hydrocarbon group having an alkoxyalkyl group such as an N- [1- (2-ethoxyethoxy) propyl] sulfamoyl group;
An N-1-substituted sulfamoyl group substituted with an aryl group such as an N-phenylsulfamoyl group and an N- (1-naphthyl) sulfamoyl group;
N-benzylsulfamoyl group, N- (1-phenylethyl) sulfamoyl group, N- (2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl Group, N- [2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) ethyl] sulfamoyl group, N- (3-phenyl-1-propyl) sulfamoyl group, N- ( N-1-substituted sulfamoyl group substituted with an aralkyl group such as 3-phenyl-1-methylpropyl) sulfamoyl group;
N- (3,4,5-trimethoxybenzyl) sulfamoyl group, N- [2- (3,4-dimethoxyphenyl) ethyl] sulfamoyl group, N- [2- (2-ethoxyphenyl) ethyl] sulfamoyl group, etc. N-1 substituted sulfamoyl group substituted with an aralkyl group having the following substituents;

Examples of the N, N-2 substituted sulfamoyl group include N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, and N, N-propylmethyl. Sulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) ) N, N-substituted sulfamoyl group substituted by two aliphatic hydrocarbon groups such as sulfamoyl group, N, N-heptylmethylsulfamoyl group;
N, N-bis (2-hydroxyethyl) sulfamoyl group, N, N-bis (2-methoxyethyl) sulfamoyl group, aliphatic hydrocarbon having substitution such as N, N-bis (2-ethoxyethyl) sulfamoyl group And N, N-2 substituted sulfamoyl group substituted with a group.

In the anion (A1), R ⁸ and R ⁹ contained in —SO ₂ NR ⁸ R ⁹ include a branched alkyl group having 6 to 8 carbon atoms, an allyl group, a phenyl group, and an aralkyl having 8 to 10 carbon atoms. Group, a C2-C8 hydroxy group-containing alkyl group or aryl group, or a C2-C8 alkoxy group-containing alkyl group or aryl group is preferable, and a 2-ethylhexyl group is more preferable.

Next, the cation (A2) will be described.
It is preferable that the salt containing a cation (A2) is sufficiently dissolved in a solvent. Furthermore, it is preferable that the salt containing a cation (A2) is dissolved in a developer used for pattern formation described later to such an extent that the pattern can be formed.

  In addition, since the cation (A2) has a resonance structure, a cation in which the charge of the cation described in the formula (A2) is transferred is also included in the present invention.

In the cation (C), the ring Z ¹ and the ring Z ² each independently represent an aromatic ring which may have a substituent. The aromatic ring is preferably a benzene ring or a naphthalene ring.

Examples of the substituent on the benzene ring and the naphthalene ring include
Aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl;
Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group;
Aryloxy groups such as phenoxy groups;
An aralkyloxy group such as a benzyloxy group;
Acyloxy groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group;
Methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group Alkylsulfamoyl groups such as a famoyl group, n-butylsulfamoyl group, di-n-butylsulfamoyl group;
Alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Examples thereof include a nitro group and a cyano group.
When the substituent has a hydrogen atom, the hydrogen atom is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group. , Isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; aryloxy group such as phenoxy group, benzyloxy group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group An aromatic hydrocarbon group such as a group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group; carboxy group; cyano group; nitro group;

From the viewpoint of solubility, the ring Z ¹ and the ring Z ² are each preferably a benzene ring that may be substituted, and more preferably an unsubstituted benzene ring.

In the cation (A2), Y ¹ is preferably a hydrogen atom.

In the cation (A2), when R ²¹ and R ²² are an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, the aliphatic hydrocarbon group includes, for example, a methyl group, Ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group, hexyl group, Examples include isohexyl group, 5-methylhexyl group, heptyl group, and octyl group.
Examples of the substituent in the aliphatic hydrocarbon group include:
Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Examples thereof include alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and benzyloxy group.
Halogen groups such as fluoro, chloro, bromo and iodo groups;
Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.

In the cation (A2), R ²¹ and R ²² are each independently an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and preferably has a substituent. An aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms having no substituent, and further preferably an n-butyl group. R ²¹ and R ²² are preferably the same group. When R ²¹ and R ²² are the same group, the molar extinction coefficient tends to be better.

In the cation (A2), when R ^{23 to} R ²⁸ are an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, examples of the aliphatic hydrocarbon group include: Methyl, ethyl, vinyl, ethynyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, 2-propynyl, butyl, isobutyl, sec-butyl, tert- Butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-penten-4-ynyl group, Examples include hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, and octyl group.
Examples of the substituent in the aliphatic hydrocarbon group include:
Examples thereof include alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and benzyloxy group.
Halogen groups such as fluoro, chloro, bromo and iodo groups;
Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.
Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, A hexane-1,6-diyl group is mentioned.

In the cation (A2), when R ^{23 to} R ²⁸ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, preferably has a substituent. An alkyl group having 1 to 3 carbon atoms, more preferably a methyl group which may have a substituent, and still more preferably a methyl group having no substituent. R ²³ and R ²⁴ , R ²⁵ and R ²⁶ , R ²⁷ and R ²⁸ are preferably the same group.

In the cation (A2), when R ²³ and R ²⁴ together form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms. More preferably a pentane-1,5-diyl group.

In the cation (A2), when R ²⁵ and R ²⁶ together form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms. More preferably a pentane-1,5-diyl group.

  Examples of the hydrocarbon ring formed from the alkanediyl group include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. The hydrocarbon ring may have a substituent, and specific examples of the substituent include an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. be able to.

In the cation (A2), when R ²⁷ and R ²⁸ together form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 3 to 5 carbon atoms. More preferably a propane-1,5-diyl group.

  Examples of the hydrocarbon ring formed from the alkanediyl group include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, and a cycloheptene ring. The hydrocarbon ring may have a substituent, and specific examples of the substituent include an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. be able to.

In the salt (0), the cation (A2) is preferably a cation represented by the formulas (II-1) to (II-36).

Examples of the salt (0) include a salt (I-1) to a salt (I-148). Y ¹ represents -L ¹ -X ¹ -L ² -X ² -R ¹ , and A ⁺ represents a cation (A2). In Table 1, the columns Y ¹ and A ⁺ indicate the numbers of the groups or cation formulas exemplified above.

［式中、
Ｒ^１−Ａ−Ｘ^２−Ａ−Ｌ^２−Ａ−Ｘ^１−Ａ−Ｌ^１−Ａ−は全体として、CH₃COOCH₂COOCH₂CH₂−又はCH₃OCOCH₂CH₂COOCH₂CH₂-を表し、
Ｒ^５−Ａは、水素原子、−ＯＲ^８−B (ここでＲ^８−Bは炭素数１〜８の１価の脂肪族炭化水素基を表す。)、又は−ＮＨＲ^１１−Ａ(ここでＲ^１１−Aは炭素数１〜８の１価の脂肪族炭化水素基を表す。)を表し、
Ｒ^６−Ａは、水素原子、又は−ＯＲ^８−B (ここでＲ^８−Bは炭素数１〜８の１価の脂肪族炭化水素基を表す。)を表し、
Ｒ^２１−Ａは、炭素数１〜４の１価の飽和炭化水素基を表し、
Ｒ^２２−Ａは、炭素数１〜４の１価の飽和炭化水素基を表し、
Ｒ^{１００−Ａ}は、水素原子、又はメチル基を表す。］
塩（Ｉ−１）〜塩（Ｉ−３）及び塩（Ｉ−１４７）が、分光濃度が特に高く、好ましい。 As an aspect of the salt of this invention, the following are mentioned, for example.
A compound represented by formula (0-A).

[Where:
R ^{1 -A} -X ^{2 -A} -L ^{2 -A} -X ^{1 -A} -L ^{1 -A} -is, as a whole, CH ₃ COOCH ₂ COOCH ₂ CH ₂ -or CH ₃ OCOCH ₂ CH ₂ COOCH ₂ CH _2-. Represents
R5 ^-A is a hydrogen atom, -OR8 ^-B (wherein R8 ^-B represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms), or -NHR11 ^-A (wherein R ^11-A represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms).
R6 ^-A represents a hydrogen atom or -OR8 ^-B (wherein R8 ^-B represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms);
R ^21-A represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms,
R ^22-A represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms,
R ^100-A represents a hydrogen atom or a methyl group. ]
The salt (I-1) to the salt (I-3) and the salt (I-147) are preferable because they have a particularly high spectral density.

  A method for producing the salt (0) of the present invention will be described.

  The salt (0) is formed by using a compound represented by the formula (d) (hereinafter sometimes referred to as “compound (d)”) and a chromium compound to form a salt containing the anion (A1), It can manufacture by carrying out the salt exchange reaction of the salt containing A1) and the salt containing a cation (A2).

[In formula (d), R ^{1 to} R ⁷ , L ¹ , L ² , X ¹ and X ² represent the same meaning as in formula (0). ]

First, a method for producing the compound (d) will be described.
The azo compound can be produced, for example, by the method described in JP-B-7-88633, that is, by diazo coupling a diazonium salt and a pyridone compound.
The diazonium salt represented by the formula (a2) can be obtained, for example, by diazotizing the amine represented by the formula (a1) with nitrous acid, nitrite or nitrite.

[In formula (a1) and formula (a2), R ^{4 to} R ⁷ represent the same meaning as in formula (0). A ¹ represents an inorganic or organic anion. ]

Examples of the inorganic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, and the like.
Examples of the organic anion, for ^{_{example, CH 3 COO -, C 6}} H 5 COO - , and the like.
Preferably, chloride ion, bromide _ion, CH 3 COO ^-, and the like.

Compound (d) wherein X ¹ is * —O—CO— (* represents a bond to L ¹ ), that is, a compound represented by formula (d1) (hereinafter referred to as “compound (d1)”) Will be described.

[In formula (d1), R ^{1 to} R ⁷ , L ¹ , L ² and X ² represent the same meaning as in formula (0). ]

  The diazonium salt represented by the formula (a2) and the compound represented by the formula (b1) are subjected to diazo coupling in an aqueous solvent, whereby the compound represented by the formula (c1) (hereinafter referred to as “compound (c1) ) ”May be manufactured. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

[In formula (b1) and formula (c1), R ^{2 to} R ⁷ and L ¹ represent the same meaning as in formula (0). ]

［式（ｅ１）中、Ｒ^１、Ｌ^２、及びＸ^２は、式（０）におけるものと同じ意味を表す。Ｚ^１は塩素原子又は臭素原子を表す。］ Next, compound (d1) is obtained by reacting compound (c1) with a compound represented by formula (e1) (hereinafter sometimes referred to as “compound (e1)”) in the presence of an organic solvent. Can do. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

[In formula (e1), R ¹ , L ² and X ² represent the same meaning as in formula (0). Z ¹ represents a chlorine atom or a bromine atom. ]

  Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform, alcohol solvents such as methanol, ethanol and butanol, and nitrated hydrocarbon solvents such as nitrobenzene, Examples include ketone solvents such as methyl isobutyl ketone and amide solvents such as 1-methyl-2-pyrrolidone.

  The amount of compound (b2) to be used is preferably 1 mol or more and 8 mol or less, more preferably 1 mol or more and 4 mol or less, per 1 mol of compound (c1).

Next, compound (d) in which X ¹ is * —CO—O— (* represents a bond to L ¹ ), that is, a compound represented by formula (d2) (hereinafter “compound (d2)”) Will be described.

[In formula (d2), R ^{1 to} R ⁷ , L ¹ , L ² and X ² represent the same meaning as in formula (0). ]

  In the same manner as described above, a diazonium salt represented by the formula (a2) and a pyridone compound represented by the formula (b2) are mixed in an aqueous solvent with a compound represented by the formula (c2) (hereinafter “compound (c2)”. Can be manufactured). The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include the same solvents as mentioned above.

[In Formula (b2) and Formula (c2), R ^{2 to} R ⁷ and L ¹ represent the same meaning as in Formula (0). ]

Next, the compound (d2) is obtained by reacting the compound (c2) with the compound represented by the formula (e2) (hereinafter sometimes referred to as “compound (b4)”) in the presence of an organic solvent. Can do. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.
R ¹ —X ² —L ² —OH (e2)
[In formula (b4), R ¹ , X ² and L ² represent the same meaning as in formula (0). ]
Examples of the organic solvent used here include the same solvents as those used in the reaction between the compound (c1) and the compound (e1).

  The amount of compound (e2) to be used is preferably 1 to 8 mol, more preferably 1 to 4 mol, per 1 mol of compound (c2).

In the reaction, it is more preferable to add an acidic catalyst so that the reaction proceeds smoothly.
Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.

The amount of these catalysts to be used is arbitrary, but relative to 1 mol of compound (e2)
Preferably it is 0.01 mol or more and 4 mol or less, More preferably, it is 0.8-2 mol.

  The method for obtaining the target compound (d) (that is, the compound (d1) or the compound (d2)) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, the reaction mixture can be mixed with an acid (such as acetic acid) and water, and the precipitated crystals can be collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 50 ° C. or lower, and further preferably 20 ° C. or higher and 30 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The chromium complex salt comprises compound (d) and a chromium compound in an aqueous solvent (for example, N, N-dimethylformamide, N-methylpyrrolidone, etc.), preferably at 70 to 150 ° C. (more preferably 70 to 130 ° C.). It can manufacture by making it react for 3 to 10 hours.

Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, chromium fluoride, ammonium sulfate chromium, and preferably chromium formate, ammonium sulfate, and the like.
It is preferable that the usage-amount of a chromium compound is 0.5-1 mol with respect to 1 mol of compounds (d).

  In order to promote the reaction, an inorganic base can be present together.

  Examples of the inorganic base include sodium hydroxide, calcium hydroxide, sodium carbonate, calcium carbonate, sodium acetate, calcium acetate and the like, preferably sodium carbonate and sodium acetate.

  The salt represented by the formula (0) can be produced by subjecting a chromium complex salt of an anion portion and a rhodamine compound of a cation portion to a salt exchange reaction in a solvent. It is preferable to react the chromium complex salt of the anion portion and the rhodamine compound of the cation portion in a molar ratio of 1: 1 to 1: 4.

  The method for obtaining the target compound salt (0) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with an inorganic salt (eg, sodium chloride) and water, and the precipitated crystals can be collected by filtration. The inorganic salt is preferably prepared by preparing an aqueous solution of an inorganic salt in advance and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 10 ° C. or higher and 40 ° C. or lower, and further preferably 10 ° C. or higher and 25 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an inorganic salt, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The salt of the present invention thus obtained is useful as a dye. In particular, since the salt of the present invention has a high spectral density, it is useful as a dye used for color filters, fiber materials, and the like of display devices such as liquid crystal display devices that perform color display using reflected light or transmitted light.

  The dye of the present invention is a dye containing the salt of the present invention as an active ingredient. The content of the salt of the present invention contained in the dye is preferably 3 to 100% by mass, more preferably 10 to 100% by mass.

  The colored resin composition of the present invention contains the dye of the present invention as a colorant (hereinafter sometimes referred to as “colorant (A)”), and further contains a resin (B) and a solvent (E). The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).

In addition to the dye of the present invention, the colorant (A) may further contain a pigment and / or a dye different from the dye of the present invention.
As dyes different from the dyes of the present invention, the Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, reactive, direct And dyes classified as (Direct), Disperse, or Vat. More specifically, dyes having the following color index (CI) numbers can be mentioned, but the dye is not limited thereto.
C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54,76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Green 1,5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

Examples of the pigment include organic pigments and inorganic pigments usually used for pigment dispersion resists. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and other metal compounds. Oxides or mixed metal oxides may be mentioned.
Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment under the Color Index (published by The Society of Dyers and Colorists). More specifically, the following color index (C.I.
) Numbered pigments, but are not limited thereto.

C. I. Pigment yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment Green 7, 10, 15, 25, 36, 47 and 58 etc.

The content of the colorant (A) is preferably 5 to 60% by mass with respect to the solid content in the colored resin composition. Here, solid content means the sum total of the component except a solvent in a colored resin composition.
The content of the dye of the present invention contained in the colorant (A) is preferably 3 to 100% by mass.
Dyes and pigments different from the dye of the present invention may be used alone or in combination of two or more with the dye of the present invention.

The resin (B) is not particularly limited, and any resin may be used.
The resin (B) is preferably an alkali-soluble resin, and more preferably a resin containing a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Specific examples of the resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, and the like.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 5,000 to 35,000, and more preferably 6,000 to 30,000.
The acid value of the resin (B) is preferably 50 to 150 mg-KOH / g, more preferably 60 to 135 mg-KOH / g.
Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a colored resin composition, More preferably, it is 13-60 mass%.

  The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical, an acid, or the like generated from the polymerization initiator (D). For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned.

The polymerizable compound (C) is preferably a photopolymerizable compound having 3 or more polymerizable groups. Examples of the photopolymerizable compound having 3 or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Is mentioned. The photopolymerizable compounds (C) may be used alone or in combination of two or more.
It is preferable that content of a polymeric compound (C) is 5-65 mass% with respect to solid content of a colored resin composition, More preferably, it is 10-60 mass%.

As said polymerization initiator (D), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by the action of heat or light. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.
Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Examples include benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (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) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-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 and the like.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.
The polymerization initiators (D) may be used alone or in combination of two or more.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator is within the above range, it is preferable because the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

  Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and cyclopentanone. And cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Chill, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ -Butyrolactone etc. are mentioned.

Examples of the amides 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.

  Content of the solvent (E) in a colored resin composition becomes like this. Preferably it is 70-95 mass% with respect to a colored resin composition, More preferably, it is 75-90 mass%.

  The colored resin composition of the present invention can be used in various ways such as surfactants, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc. An additive may be included.

The compounds of the present invention are useful as dyes. Since it has a high molar extinction coefficient and a high spectral density, it is particularly useful as a dye used in a color filter of a display device such as a liquid crystal display device.
Further, the colored resin composition of the present invention relates to various colored images such as a display device (for example, a known liquid crystal display device, an organic EL device, etc.) having a color filter as a part of its constituent parts, a solid-state image sensor, and the like. It can be used in a known manner for the device to be used.

Next, the present invention will be described more specifically with reference to examples.
In Examples and Comparative Examples,% and part representing content or amount used are based on mass unless otherwise specified.

  In the following Examples, the structure of the compound is NMR (JMM-ECA-500; manufactured by JEOL Ltd.), mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type) and elemental analysis (VARIO). -EL; (Elemental Co., Ltd.)).

[Example 1]
After adding 80 parts of water to 13.7 parts of anthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 part of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  On the other hand, 26.0 parts of acetoacetic acid ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 24.4 parts of 2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) The parts were mixed and stirred at 95 ° C. for 24 hours. The reaction solution was cooled to room temperature, added to a mixed solution of 304 parts of water and 35 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of a suction filter and dried to obtain 20.4 parts of a compound represented by the formula (b1a).

  Subsequently, 20.4 parts of the compound represented by the formula (b1a) were suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. 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 33.5 parts of a compound represented by the formula (c1a).

Next, 27.28 parts of the acid chloride represented by the formula (e1a) was added to 34.2 parts of the compound represented by (c1a), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 42.35 parts of a compound represented by the formula (d1a). ^The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by the formula (d1a);
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.05 (3H, s), 2.57 (3H, s), 4.13 (2H, t), 4 .31 (2H, t), 4.57 (2H, s), 7.38 (1H, t), 7.76 (1H, t), 8.02 (1H, d), 8.04 (1H, d), 15.7 (1H, s).

  Next, after adding 50 parts of N-methylpyrrolidone to 2.0 parts of the compound represented by the formula (d1a) and heating to 80 ° C. to dissolve, chromium formate n hydrate (manufactured by Nacalai Tesque) 1.2 parts were added and stirred at 120 ° C. for about 7 hours to obtain a dark orange solution. This solution was poured into 300 parts of a 20% saline solution, and the resulting orange solid was filtered and dried under vacuum at 60 ° C. to obtain 1.6 parts of a compound represented by the formula (z-1) (inclusive). 76%).

Identification of the compound represented by the formula (z-1);
(Mass spectrometry) Ionization mode = ESI−: m / z = 932.2 [M−H ⁺ ] ⁻
Exact Mass: 933.1

２，３，３−トリメチル−３H−インドール(和光純薬工業製) ６３部にヨウ化ブチル(和光純薬工業製) ８４部を加えて１４０℃で７時間加熱環流を行った。冷却後、ジエチルエーテル１２０部を加えて生じた沈殿をろ取し、冷アセトンにて洗浄した後、減圧下で乾燥してヨウ化１−ブチル−２，３，３−トリメチル−３H−インドリウム１０５部を得た（８５％）。 続いてピリジン４７０部、トリエチルアミン７０部とともにヨウ化１−ブチル−２，３，３−トリメチル−３H−インドリウム１００部とオルトギ酸エチル (和光純薬工業製)５６部を１２０℃で１時間反応させた。冷却後、ジエチルエーテル８００部を徐々に加えることにより得られる沈殿をろ過により得る。この固体をエタノールを用いて再結晶を行った後、６０℃２４時間減圧乾燥することにより、式（ｇ−１）で表される化合物を１４９部得た（９０％）。

84 parts of butyl iodide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 63 parts of 2,3,3-trimethyl-3H-indole (manufactured by Wako Pure Chemical Industries, Ltd.), and heated to reflux at 140 ° C. for 7 hours. After cooling, 120 parts of diethyl ether was added and the resulting precipitate was collected by filtration, washed with cold acetone, dried under reduced pressure, and 1-butyl-2,3,3-trimethyl-3H-indolium iodide. 105 parts were obtained (85%). Subsequently, 470 parts of pyridine and 70 parts of triethylamine are reacted with 100 parts of 1-butyl-2,3,3-trimethyl-3H-indolium iodide and 56 parts of ethyl orthoformate (manufactured by Wako Pure Chemical Industries) at 120 ° C. for 1 hour. I let you. After cooling, a precipitate obtained by gradually adding 800 parts of diethyl ether is obtained by filtration. The solid was recrystallized from ethanol and then dried under reduced pressure at 60 ° C. for 24 hours to obtain 149 parts of a compound represented by the formula (g-1) (90%).

Identification of compound represented by formula (g-1) (mass spectrometry) ionization mode = ESI +: m / z = 441.3 [M−I ⁻ ] ⁺
Exact Mass: 568.2

A solution (s1) was prepared by adding 200 parts of N-methylpyrrolidone to 10.9 parts of the compound represented by the formula (z-1). Further, 150 parts of methanol was added to 6.5 parts of the compound represented by the formula (g-1) to prepare a solution (t1). Thereafter, the solution (s1) and the solution (t1) were mixed at room temperature, stirred for about 1 hour, and poured into 1320 parts of water. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 11.1 parts (yield 70%) of the salt represented by the formula (I-1).
Identification of a salt represented by formula (I-1);
(Elemental analysis) C62.1 H5.4 N10.0 Cr3.8

[Example 2]
A compound represented by the formula (d1b) was obtained in the same manner as in Example 1 except that the acid chloride represented by the formula (e1a) was replaced with the acid chloride represented by the formula (e1b). ^The structure was confirmed by ¹ H-NMR. ^The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by the formula (d1b);
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.50 (2H, 2H, overlapped) 2.55 (3H, s), 3.51 (3H, s), 4.11 (2H, t), 4.23 (2H, t), 7.37 (1H, t), 7.74 (1H, t), 8.02 (1H, d), 8.03 (1H , D), 15.6 (1H, s).

  Next, 93 parts of N-methylpyrrolidone is added to 3.7 parts of the compound represented by the formula (d1b), heated to 80 ° C. and dissolved, and then 1.8 parts of chromium formate n hydrate is added to 120 parts. Stir at about 7 hours for a dark orange solution. This solution was poured into 210 parts of a 20% saline solution, and the resulting orange solid was filtered and dried under vacuum at 60 ° C., whereby 3.2 parts of the compound represented by the formula (z-2) ( Yield 82%).

Identification of the compound represented by the formula (z-2);
(Mass spectrometry) Ionization mode = ESI−: m / z = 960.0 [M−H ⁺ ] ⁻
Exact Mass: 961.2

  To 5.5 parts of the compound represented by the formula (z-2), 80 parts of N-methylpyrrolidone was added to prepare a solution (s2). Further, 50 parts of methanol was added to 3.2 parts of the compound represented by the formula (g-1) to prepare a solution (t2). Thereafter, the solution (s2) and the solution (t2) were mixed at room temperature, stirred for about 1 hour, and poured into 480 parts of water. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 5.6 parts (yield 72%) of the salt represented by the formula (I-2).

Identification of a salt represented by formula (I-2);
(Elemental analysis) C62.2 H5.3 N10.0 Cr3.9

Example 3
After adding 100 parts of water to 5.5 parts of 2-amino-4,5-dimethoxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.2 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 6.1 parts of sodium nitrite was added, and then 23.1 parts of 35% hydrochloric acid was added little by little. Thereafter, the mixture was stirred for 2.5 hours under ice cooling, and 70 parts of a 9% amidosulfuric acid aqueous solution was slowly added to quench excess nitrous acid, followed by stirring for about 10 minutes to obtain a suspension containing a diazonium salt.

  Next, 5.9 parts of the compound represented by the formula (b1a) was suspended in 53 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. Here, the suspension containing the diazonium salt was dropped with a pump over about 1 hour while maintaining the pH of the suspension at 7.5 to 9.0. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours to obtain a red-orange suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 9.3 parts of the compound represented by the formula (c1c).

Next, 3.1 parts of acid chloride (e1b) was added to 4.2 parts of the compound represented by the formula (c1c), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the mixture was charged in water to obtain 4.9 parts of a pyridone azo compound (d1c) represented by the following structure. ^The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by the formula (d1c);
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.50-2.52 (2H, 2H, overlapped), 2.56 (3H, t), 3.52 ( 3H, s), 3.83 (3H, s), 3.93 (3H, s), 4.11 (2H, t), 4.23 (2H, t), 7.43 (1H, s), 7.48 (1H, s), 15.7 (1H, s).

  Next, 120 parts of N-methylpyrrolidone is added to 11.0 parts of the compound represented by the formula (d1c) and heated to 80 ° C. to dissolve, and then 1.0 part of chromium formate n hydrate is added to 110 parts. Stir at about 0 ° C. for about 1 hour. The temperature was then lowered to 80 ° C., 2.3 parts of sodium carbonate was added, and the mixture was again stirred at 110 ° C. for about 3.5 hours to obtain a dark orange solution. The solution was poured into 530 parts of a 10% saline solution, and the resulting orange solid was filtered and dried in vacuo at 60 ° C. to obtain a compound represented by the formula (z-3) (yield 65%). Of 7.6 parts.

Identification of the compound represented by the formula (z-3);
(Mass Spectrometry) Ionization mode = ESI−: m / z = 1080.2 [M−Na ⁺ ] ⁻
Exact Mass: 1103.2

A solution (s3) was prepared by adding 250 parts of N-methylpyrrolidone to 12.5 parts of the compound represented by formula (z-3). Further, 65 parts of N-methylpyrrolidone was added to 6.5 parts of the cyanine 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, stirred for about 1 hour, and poured into 1650 parts of water. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 14.8 parts (yield 85%) of the salt represented by the formula (I-3).
Identification of a salt represented by formula (I-3);
(Elemental analysis) C60.6 H5.5 N9.1 Cr3.3

Example 4
After adding 80 parts of water to 19.4 parts of 5-acetamidoanthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.
Subsequently, 20.4 parts of the compound represented by the formula (b1a) were suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. 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 39.1 parts of a compound represented by the formula (c1e).

Next, 30.1 parts of acid chloride (Wako Pure Chemical Industries, Ltd.) represented by the formula (e1b) is added to 39.9 parts of the compound represented by the formula (c1e), and in N-methylpyrrolidone, Stir at 70 ° C. for 3 hours. After completion of the reaction, the reaction mixture was charged in water to obtain 50.1 parts of a compound represented by the formula (d1e). The obtained compound was orange and the maximum absorption wavelength (λmax) was measured in an ethyl lactate solvent to show 459 nm. Further, the structure was confirmed by ¹ H-NMR.

Identification of the compound represented by the formula (d1e);
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ): 1.05 (3H, m), 2.06 (3H, s), 2.37 (2H, t), 2.40 (2H, t), 2.48 (3H, m), 3.83 (2H, m), 3.91 (2H, m), 5.08 (2H, m), 7.88 (1H, s), 7.89 (1H, s), 8.29 (1H, m), 10.2 (1H, d)

  Next, 98 parts of N-methylpyrrolidone is added to 7.0 parts of the compound represented by the formula (d1e) and heated to 80 ° C. to dissolve, and then 1.6 parts of chromium formate n hydrate is added to add 110 parts. Stir at about 0 ° C. for about 1 hour. The temperature was then lowered to 80 ° C., 2 parts of sodium carbonate was added, and the mixture was stirred again at 110 ° C. for about 5 hours to obtain a dark orange solution. This solution was poured into 330 parts of a 20% saline solution, and the resulting orange solid was filtered and dried under vacuum at 60 ° C. to obtain 2.7 parts of the salt represented by the formula (z-4) ( Yield 40%).

Identification of the compound represented by formula (z-4);
(Mass Spectrometry) Ionization Mode = ESI−: m / z = 1074.2 [M−Na ⁺ ] ⁻
Exact Mass: 1097.2

  Instead of 2,3,3-trimethyl-3H-indole used for the synthesis of the compound represented by formula (g-1), 2,3,3,5-tetramethylindolenine was used instead of butyl iodide. A compound represented by the following compound formula (g-2) was synthesized in the same manner except that methyl iodide was used.

Identification of compound represented by formula (g-2) (mass spectrometry) ionization mode = ESI +: m / z = 385.3 [M−I ⁻ ] ⁺
Exact Mass: 512.2

A solution (s4) was prepared by adding 220 parts of N-methylpyrrolidone to 21.1 parts of the compound represented by the formula (z-4). Further, 80 parts of N-methylpyrrolidone was added to 10.1 parts of the compound represented by the formula (g-2) to prepare a solution (t4). Thereafter, the solution (s4) and the solution (t4) were mixed at room temperature, stirred for about 1 hour, and poured into 1580 parts of water. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 21.3 parts (yield 75%) of the salt represented by the formula (I-147).
Identification of a salt represented by the formula (I-147);
(Elemental analysis) C60.0 H5.1 N11.5 Cr3.5

<Measurement of absorbance>
A solution having a concentration of 0.028 g / L was prepared by dissolving 0.35 g of the salt in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to 100 cm ³ . The absorbance at the maximum absorption wavelength (λmax) and the maximum absorption wavelength (λmax) of the solution was measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). It was measured. The results are shown in Table 2.

  In Table 2, the salt (R-1) is C.I. I. Solvent Yellow 21 (Oleosol Fast Yellow 2G; manufactured by Taoka Chemical Industry Co., Ltd.).

Example 8
<Preparation of colored resin composition>
(A) Colorant: salt (I-1): salt synthesized in Example 1 20 parts (B-1) resin: methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, Acid value 70 mg-KOH / g) 70 parts (C-1) polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 30 parts (D-1) polymerization initiator: benzyldimethyl ketal (Irgacure (registered trademark) 651; manufactured by BASF Japan Ltd.) 15 parts and (E-1) solvent: 680 parts of ethyl lactate are mixed to obtain a colored resin composition.

<Production of color filter>
On the glass, the colored resin composition obtained above is applied by a spin coating method to volatilize volatile components. After cooling, light irradiation is performed using a quartz glass photomask having a pattern and an exposure machine. After light irradiation, development is performed with an aqueous potassium hydroxide solution, and the color filter is obtained by heating to 200 ° C. in an oven.

Example 9
A colored resin composition and a color filter are obtained in the same manner as in Example 8, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-2) synthesized in Example 2.

Example 10
A colored resin composition and a color filter are obtained in the same manner as in Example 8, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-3) synthesized in Example 3.

Example 11
A colored resin composition and a color filter are obtained in the same manner as in Example 8, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-4) synthesized in Example 4.

Example 12
A colored resin composition and a color filter are obtained in the same manner as in Example 8, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-5) synthesized in Example 5.
Example 13
A colored resin composition and a color filter are obtained in the same manner as in Example 8, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-6) synthesized in Example 6.

Example 14
A colored resin composition and a color filter are obtained in the same manner as in Example 8, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-147) synthesized in Example 7.

上記の樹脂のポリスチレン換算重量平均分子量の測定については、ＧＰＣ法を用いて、以下の条件で行った。
装置 ；ＨＬＣ−８１２０ＧＰＣ（東ソー（株）製）
カラム ；ＴＳＫ−ＧＥＬＧ２０００ＨＸＬ
カラム温度 ；４０℃
溶媒 ；ＴＨＦ
流速 ；１．０ｍＬ／ｍｉｎ
被検液固形分濃度；０．００１〜０．０１％
注入量 ；５０μＬ
検出器 ；ＲＩ
校正用標準物質 ；ＴＳＫ ＳＴＡＮＤＡＲＤ ＰＯＬＹＳＴＹＲＥＮＥ
Ｆ−４０、Ｆ−４、Ｆ−２８８、Ａ−２５００、Ａ−５００
（東ソー（株）製） <Synthesis of Resin B1 Solution>
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the following formula (b-1) and a formula (b-2) The compound to be mixed is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts and 140 parts of ethyl lactate, and the solution is added at 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask kept warm. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After the addition of the solution of the polymerization initiator is completed, 4 hours, kept at 70 ° C., then cooled to room temperature, and the weight average molecular weight Mw, 1.3 × 10 ^4, a solid content 33 wt%, a solution acid value A resin B1 solution of 34 mg-KOH / g was obtained. Calculated from the above solid content and the solution acid value, the solid content acid value of the resin B1 was 100 mg-KOH / g.

About the measurement of the polystyrene conversion weight average molecular weight of said resin, 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 concentration: 0.001 to 0.01%
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 15
<Preparation of colored photosensitive resin composition>
(A) Colorant: Salt (I-1): Salt synthesized in Example 1 30 parts (B-2) Resin: Resin B1 (in terms of solid content) 40 parts (C-2) Polymerizable compound: Dipentaerythritol Mixture of pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 60 parts (D-2) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanyl) Phenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Japan Ltd.) 12 parts (D-3) Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one (Irgacure (registered trademark) 369; manufactured by BASF Japan Ltd.) 6 parts (D2) Polymerization initiation assistant: 4,4′-bis (diethi Amino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts (E-2) Solvent: Propylene glycol monomethyl ether acetate 528 parts (E-3) Solvent: Propylene glycol monomethyl ether 69 parts, and (F) Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.09 part is mixed to obtain a colored photosensitive resin composition.

<Production of color filter>
Using the resulting colored photosensitive resin composition, a color filter is obtained in the same manner as in Example 8.

  From the results of Table 2, it can be seen that the salt of the present invention has a high spectral density because of its high absorbance. In addition, the colored resin composition containing the salt has excellent color performance and can produce a high-quality color filter.

  The salt of the present invention is useful as a dye. Since the salt of the present invention has a high absorbance, the spectral density representing the color density per unit density is high, and is particularly useful as a dye used in a color filter of a display device such as a liquid crystal display device.

Claims (9)

A salt represented by the formula (0).

[In Formula (0), X ¹ and X ² each independently represent —CO—O— or —O—CO—.
L ¹ and L ² each independently represent an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a hydrogen atom, a methyl group or an ethyl group.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4 to} R ⁷ are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —COR ⁸ , —OCOOR ⁸ , —OCOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, — _{SO 3 Na, -SO 3 K,} -SO 2 NR 8 R 9 or ^-NR 11 or represents ^{R 12, R 4} and ^R 5, ^{R 5} and ^{R 6} and ^{R 6} and ^{R 7,} benzene combined with each other A 6-7 membered ring containing the ring carbon is formed.
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -OR ¹⁰ .
R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ¹¹ and R ¹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group, or R ¹¹ and R 12 ¹² combine with each other to form a ring containing a nitrogen atom.
Ring Z ¹ and Ring Z ² each independently represent an optionally substituted aromatic ring, and R ²¹ and R ²² each independently represent a substituent having 1 to 1 carbon atoms. 12 represents an aliphatic hydrocarbon group or a hydrogen atom having 12 carbon atoms, and R ²³ and R ²⁴ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ²³ and R ²⁴ together form an alkanediyl group. R ²⁵ and R ²⁶ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, or R ²⁵ and R ²⁶ together represent an alkanediyl group. Form. R ²⁷ and R ²⁸ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, or R ²⁷ and R ²⁸ together form an alkanediyl group. Form. Y ¹ represents a hydrogen atom or a chlorine atom. ] R ^{4 to} R ⁷ are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K, —SO ₂ NR ⁸ R ⁹ or ^-NR 11 salt according to claim 1 wherein ^{R 12.} The salt according to claim 1 or 2, wherein X ¹ is * -O-CO-.
[* Represents the bonding position to ^{L 1.} ] The salt according to any one of claims 1 to 3, wherein R ² is -CN. R < ²³ > -R < ²⁶ > is a C1-C8 monovalent | monohydric aliphatic hydrocarbon group mutually independently, The salt in any one of Claims 1-4. The salt according to any one of claims 1 to 5, wherein R ²¹ and R ²² are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms. The salt according to any one of claims 1 to 6, wherein Z ¹ and Z ² are benzene rings which may be substituted with a methyl group.   A dye comprising the salt according to any one of claims 1 to 7 as an active ingredient.   The coloring resin composition containing the dye of Claim 8, resin, and a solvent.