JP5758595B2 - Method for producing pigment dispersion and coloring composition, coloring pattern and color filter - Google Patents

Description

  The present invention relates to a method for producing a pigment dispersion and a coloring composition, a coloring pattern, and a color filter.

  Conventionally, pigment dispersions used for color filters and the like have been manufactured by, for example, dispersing a pigment, a dispersant, a resin, a viscosity reducing agent, a solvent, and the like (for example, Patent Document 1). In this dispersion treatment, the viscosity characteristic and its stability are controlled without adversely affecting the color characteristic by controlling the dispersion and mixing order of each component, in which a viscosity reducing agent is adsorbed more by the dispersant and then the pigment is added. I tried to improve the sex.

JP 2003-327864 A

However, the resist coating film containing the pigment dispersion obtained by such a method sometimes generates foreign matters. Further, depending on the additive used at the time of dispersion, there is a problem that the brightness of the color filter is lowered.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a pigment dispersion that can further reduce the generation of foreign matters and obtain a color filter with high brightness.

The present invention provides the following [1] to [9].
[1] A method for producing a pigment dispersion comprising a step of simultaneously dispersing a dye and a pigment in a solvent.
[2] The method for producing a pigment dispersion according to [1], wherein the dye is a dye containing at least one selected from the group consisting of an azo compound, a metal complex having an azo compound as a ligand, and a xanthene compound.

（式（１）中、
Ｒ^１〜Ｒ^４は、それぞれ独立に、水素原子、−Ｒ^６又は炭素数６〜１０の１価の芳香族炭化水素基を表し、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、−Ｒ^６、−ＯＨ、−ＯＲ^６、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３Ｍ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^６、−ＳＯ_３Ｒ^６、−ＳＯ_２ＮＨＲ^８又は−ＳＯ_２Ｎ（Ｒ^８）Ｒ^９で置換されていてもよい。
Ｒ^５は、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３Ｍ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^６、−ＳＯ_３Ｒ^６、−ＳＯ_２ＮＨＲ^８又は−ＳＯ_２Ｎ（Ｒ^８）Ｒ^９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Ｒ^５は、同一であっても異なっていてもよい。
Ｘは、ハロゲン原子を表す。ａは、０又は１の整数を表す。
Ｒ^６は、置換基を有していてもよい炭素数１〜１０の１価の飽和炭化水素基を表し、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^6ａ−で置換されていてもよい。Ｒ^6ａは、水素原子又は炭素数１〜４のアルキル基を表す。
Ｒ^８及びＲ^９は、それぞれ独立に、置換基を有していてもよい炭素数１〜１０のアルキル基、置換基を有していてもよい炭素数３〜３０のシクロアルキル基又は−Ｑを表す。あるいはＲ^８及びＲ^９は、互いに結合して、置換基を有していてもよい炭素数１〜１０の複素環を形成していてもよい。前記アルキル基及び該シクロアルキル基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^６ａ−で置換されていてもよい。
Ｑは、置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基又は置換基を有していてもよい炭素数３〜１０の１価の芳香族複素環基を表す。
Ｍは、ナトリウム原子又はカリウム原子を表す。
ただし、式（１）で表される化合物の＋電荷数と−電荷数とが同一である。）
［４］染料及び顔料は、染料：顔料＝１：９９〜９９：１の質量比で含有されてなる［１］〜［３］のいずれか記載の顔料分散液の製造方法。
［５］顔料が、Ｃ．Ｉ．ピグメントブルー１５：６、Ｃ．Ｉ．ピグメントグリーン３６、Ｃ．Ｉ．ピグメントグリーン５８、Ｃ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１３９、Ｃ．Ｉ．ピグメントイエロー１５０、Ｃ．Ｉ．ピグメントレッド１７７、Ｃ．Ｉ．ピグメントレッド２４２及びＣ．Ｉ．ピグメントレッド２５４からなる群から選ばれる少なくとも１種を含む顔料である［１］〜［４］のいずれか記載の顔料分散液の製造方法。
［６］顔料がＣ．Ｉ．ピグメントブルー１５：６を含む顔料である［１］〜［５］のいずれか記載の顔料分散液の製造方法。 [3] The method for producing a pigment dispersion according to [1] or [2], wherein the dye is a dye containing a compound represented by the formula (1).

(In the formula (1),
R ^{1 to} R ⁴ each independently represent a hydrogen atom, —R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom , —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or it may be substituted by _{^{-SO 2 N (R 8) R}} 9.
R ⁵ is —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ N (R ⁸ ). R ⁹ is represented.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
X represents a halogen atom. a represents an integer of 0 or 1.
R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and —CH ₂ — contained in the saturated hydrocarbon group is —O—, —CO—. Alternatively, it may be substituted with —NR ^6a —. R ^6a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ⁸ and R ⁹ are each independently an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted cycloalkyl group having 3 to 30 carbon atoms, or -Q. Represents. Or R < ⁸ > and R < ⁹ > may couple | bond together and may form the C1-C10 heterocyclic ring which may have a substituent. —CH ₂ — contained in the alkyl group and the cycloalkyl group may be substituted with —O—, —CO—, —NH—, or —NR ^6a —.
Q is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 3 to 10 carbon atoms which may have a substituent. Represents.
M represents a sodium atom or a potassium atom.
However, the number of + charges and the number of −charges of the compound represented by the formula (1) are the same. )
[4] The method for producing a pigment dispersion according to any one of [1] to [3], wherein the dye and the pigment are contained at a mass ratio of dye: pigment = 1: 99 to 99: 1.
[5] The pigment is C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The method for producing a pigment dispersion according to any one of [1] to [4], which is a pigment containing at least one selected from the group consisting of CI Pigment Red 254.
[6] The pigment is C.I. I. The method for producing a pigment dispersion according to any one of [1] to [5], which is a pigment containing CI Pigment Blue 15: 6.

  [7] Selected from the group consisting of a pigment dispersion obtained by the method for producing a pigment dispersion according to any one of [1] to [6], a solvent, a resin, a photopolymerizable compound, and a photopolymerization initiator. The manufacturing method of the coloring composition including the process of mixing at least 1 sort (s).

[8] A colored pattern formed using the colored composition obtained by the method for producing a colored composition according to [7].
[9] A color filter comprising the colored pattern according to [8].
[10] A liquid crystal display device comprising the color filter according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the pigment dispersion liquid and coloring composition which can reduce generation | occurrence | production of a foreign material more can be provided. This makes it possible to manufacture high-performance coloring patterns, color filters, liquid crystal display devices, and the like.

The method for producing a pigment dispersion of the present invention includes a step of simultaneously dispersing a dye and a pigment in a solvent.
The dyes and pigments used in this method are not particularly limited in their types, and any dyes and pigments known in the art can be used.
The dye is preferably an organic solvent-soluble dye, more preferably an azo compound, a dye containing at least one selected from the group consisting of a metal complex having an azo compound as a ligand, and a xanthene compound. It is more preferable that it is a dye containing at least 1 sort (s) chosen from the group which consists of a compound represented by 1)-Formula (3), and it is most preferable that it is a dye containing the compound represented by Formula (1). Here, the organic solvent-soluble dye refers to a dye that dissolves in any of the solvents used in the present invention described later.

  In the present specification, unless otherwise specified, specific chemical substituents described later can be applied to any chemical structural formula having the same substituents while appropriately selecting the number of carbon atoms. Those which can take any of linear, branched or cyclic are included unless otherwise specified, and in the same group, linear, branched and / or cyclic partial structures are mixed. It may be. When stereoisomers exist, all of those stereoisomers are included.

（式（１）中、
Ｒ^１〜Ｒ^４は、それぞれ独立に、水素原子、−Ｒ^６又は炭素数６〜１０の１価の芳香族炭化水素基を表し、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、−Ｒ^６、−ＯＨ、−ＯＲ^６、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３Ｍ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^６、−ＳＯ_３Ｒ^６、−ＳＯ_２ＮＨＲ^８又は−ＳＯ_２Ｎ（Ｒ^８）Ｒ^９で置換されていてもよい。
Ｒ^５は、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３Ｍ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^６、−ＳＯ_３Ｒ^６、−ＳＯ_２ＮＨＲ^８又は−ＳＯ_２Ｎ（Ｒ^８）Ｒ^９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Ｒ^５は、同一であっても異なっていてもよい。
Ｘは、ハロゲン原子を表す。ａは、０又は１の整数を表す。
Ｒ^６は、置換基を有していてもよい炭素数１〜１０の１価の飽和炭化水素基を表し、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^6ａ−で置換されていてもよい。Ｒ^6ａは、水素原子又は炭素数１〜４のアルキル基を表す。
Ｒ^８及びＲ^９は、それぞれ独立に、置換基を有していてもよい炭素数１〜１０のアルキル基、置換基を有していてもよい炭素数３〜３０のシクロアルキル基又は−Ｑを表す。あるいはＲ^８及びＲ^９は、互いに結合して、置換基を有していてもよい炭素数１〜１０の複素環を形成していてもよい。前記アルキル基及び該シクロアルキル基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^6ａ−で置換されていてもよい。
Ｑは、置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基又は置換基を有していてもよい炭素数３〜１０の１価の複素環基を表す。
Ｍは、ナトリウム原子又はカリウム原子を表す。
ただし、式（１）で表される化合物の＋電荷数と−電荷数とが同一である。） The dye is preferably a dye containing a xanthene compound, and more preferably a dye containing a compound represented by the formula (1).

(In the formula (1),
R ^{1 to} R ⁴ each independently represent a hydrogen atom, —R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom , —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or it may be substituted by _{^{-SO 2 N (R 8) R}} 9.
R ⁵ is —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ N (R ⁸ ). R ⁹ is represented.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
X represents a halogen atom. a represents an integer of 0 or 1.
R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and —CH ₂ — contained in the saturated hydrocarbon group is —O—, —CO—. Alternatively, it may be substituted with —NR ^6a —. R ^6a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ⁸ and R ⁹ are each independently an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted cycloalkyl group having 3 to 30 carbon atoms, or -Q. Represents. Or R < ⁸ > and R < ⁹ > may couple | bond together and may form the C1-C10 heterocyclic ring which may have a substituent. —CH ₂ — contained in the alkyl group and the cycloalkyl group may be substituted with —O—, —CO—, —NH— or —NR ^6a —.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 10 carbon atoms which may have a substituent. .
M represents a sodium atom or a potassium atom.
However, the number of + charges and the number of −charges of the compound represented by the formula (1) are the same. )

Here, examples of the monovalent aromatic hydrocarbon group include an aryl group and an aralkyl group.
Examples of the aryl group include phenyl, biphenyl, naphthyl, anthryl, phenanthryl, tolyl, xylyl, cumenyl, and mesityl groups.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group and the like.
Examples of the halogen atom include fluorine, chlorine, bromine and the like.

The monovalent saturated hydrocarbon group may be an alkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, or an alkyl group substituted with a cycloalkyl group.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 1-methylpropyl group, and 2-methyl. Propyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, 1-dimethyl-n-propyl group, 1,2-dimethylpropyl group, 2,2- A dimethylpropyl group etc. are mentioned.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecanyl group.

等が挙げられる。なお、複素環基の結合手は上に記載した位置の他、任意の位置とすることができる。 The heterocyclic ring may be aromatic or may not have aromaticity.
As the aromatic group, that is, the monovalent aromatic heterocyclic group,

Etc. In addition, the bond of the heterocyclic group can be at any position other than the positions described above.

等が挙げられる。 As a heterocyclic group having no aromaticity,

Etc.

Examples of —OR ⁶ include alkoxy groups such as methoxy, ethoxypropoxy, butoxy, hexyloxy and 2-ethylhexyloxy.
The -CO ₂ R ^6, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, pentyloxy group, isopentyloxy group, neopentyloxy group , Cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, cycloheptyloxycarbonyl group, octyloxycarbonyl, 2-ethylhexyloxycarbonyl group, cyclooctyloxycarbonyl group, nonyloxycarbonyl group, decyl Oxycarbonyl group, tricyclodecyloxycarbonyl group, methoxypropoxycarbonyl group, ethoxypropyloxycarboni Group, hexyloxy propoxycarbonyl group, 2-ethylhexyloxy propoxycarbonyl group, such as methoxy hexyloxycarbonyl group.

Examples of —SO ₃ R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a hexyloxysulfonyl group, and a decyloxysulfonyl group.

As —SO ₂ NHR ⁸ , sulfamoyl group, N- (methyl) sulfamoyl group, N- (ethyl) sulfamoyl group, N- (propyl) sulfamoyl group, N- (isopropyl) sulfamoyl group, N- (butyl) sulfamoyl group N- (isobutyl) sulfamoyl group, N- (pentyl) sulfamoyl group, N- (isopentyl) sulfamoyl group, N- (neopentyl) sulfamoyl group, N- (cyclopentyl) sulfamoyl group, N- (hexyl) sulfamoyl group, N -(Cyclohexyl) sulfamoyl group, N- (heptyl) sulfamoyl group, N- (cycloheptyl) sulfamoyl group, N- (octyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) (Hexyl) sulfa Yl group, N- (cyclooctyl) sulfamoyl group, N- (nonanesulfamoyl group, N- (decyl) sulfamoyl group, N- (tricyclodecyl) sulfamoyl group, N- (methoxypropyl) sulfamoyl group, N- (Ethoxypropyl) sulfamoyl group, N- (propoxypropyl) sulfamoyl group, N- (isopropoxypropyl) sulfamoyl group, N- (hexyloxypropyl) sulfamoyl, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (Methoxyhexyl) sulfamoyl group, N- (3-phenyl-1-methylpropyl) sulfamoyl group and the like can be mentioned.

_Further, as the -SO 2 NHR ^8, or may be a group represented by the following formula. However, in the following formulas, X ¹ represents a halogen atom. X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom. X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom. .
Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include a trifluoromethyl group in addition to the above-described alkyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include the above-described alkyl groups, particularly a methoxy group, an ethoxy group, and a propoxy group.

Examples of —SO ₂ N (R ⁸ ) R ⁹ include the following groups.

Examples of the heterocyclic ring formed by combining R ⁸ and R ⁹ with each other include groups represented by the following formulae.

The alkyl group in ^{R 8} and ^{R 9,} as the substituent of the cycloalkyl group can be suitably selected from the above structure, for example, a halogen atom, hydroxy _{group, -Q, -CH = CH 2,} - CH = CHR ⁶ etc. are illustrated.
Especially, as R < ⁸ > and R < ⁹ >, a C1-C10 alkyl group, a C5-C7 cycloalkyl group, an allyl group, a phenyl group, a C8-C10 aralkyl group, C2-C2 8 alkyl group-containing alkyl groups and aryl groups, C2-C8 alkoxy group-containing alkyl groups and aryl groups are preferred, C6-C8 branched alkyl groups are more preferred, and 2-ethylhexyl groups. Is particularly preferred.

As a substituent of a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in Q, an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, —SO ₃ R ⁶ or —SO ₂ NHR ⁸ is preferable. _Here, the ^{R 8} in -SO 2 NHR ^8, especially preferably a cycloalkyl group of the alkyl group and 3 to 30 carbon atoms having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, more A branched alkyl group having 6 to 8 carbon atoms is more preferable, and a 2-ethylhexyl group is particularly preferable.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent in Q include a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a hexylphenyl group. Group, decanylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, hydroxyphenyl group, methoxyphenyl group, dimethoxyphenyl group, ethoxyphenyl group, hexyloxyphenyl group, decanyloxyphenyl group, trifluoromethylphenyl group , A biphenyl group, a dimethylphenylphenyl group and the like, and a group in which —SO ₂ NHR ⁸ is further substituted for these groups.

Examples of the substituent of the monovalent aromatic heterocyclic group having 3 to 10 carbon atoms in Q include an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, —SO ₃ R ⁶ or —SO ₂ NHR ⁸ . _Here, the ^{R 8} in -SO 2 NHR ^8, especially preferably a cycloalkyl group of the alkyl group and 3 to 30 carbon atoms having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, more A branched alkyl group having 6 to 8 carbon atoms is more preferable, and a 2-ethylhexyl group is particularly preferable.

Further, examples of the substituent of the monovalent saturated hydrocarbon group representing R ^6, for example, a halogen atom, and the like alkoxy groups having 1 to 10 carbon atoms.
Here, as the alkoxy group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, pentoxy group, isopentyloxy group, neopentyloxy group, hexyloxy group, heptyloxy group, octyloxy Group, 1-methylpropoxy group, 2-methylpropoxy group, 1-methylbutoxy group, 2-methylbutoxy group, 3-methylbutoxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 2,2-dimethylpropoxy group and the like can be mentioned.

In the compound represented by the formula (1), at least one of R ¹ and R ² or at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or a substituent. It is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.
At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or an optionally substituted monovalent group having 6 to 10 carbon atoms. An aromatic hydrocarbon group is preferred.
At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an optionally substituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Further preferred.

R ⁵ represents a carboxy group, an ethoxycarbonyl group, a sulfo group, an N- (2-ethylhexyloxypropyl) sulfamoyl group, an N- (1,5-dimethylhexyl) sulfamoyl group, or N- (3-phenyl-1-methyl). Propyl) sulfamoyl group and N- (isopropoxypropyl) sulfamoyl group are preferable.

  The compound represented by Formula (1) is preferably at least one compound selected from the group consisting of compounds represented by Formula (1-1) to Formula (1-4), for example.

(In the formulas (1-1) to (1-4),
R ¹¹ , R ¹² , R ^13, and R ¹⁴ each independently represent a hydrogen atom, —R ^6, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and are included in the aromatic hydrocarbon group. The hydrogen atom is a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ Na, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , It may be substituted with —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ¹⁵ represents a hydrogen atom, —SO ₃ ^— , —SO ₃ H, —SO ₂ NHR ⁸ or —SO ₂ N (R ⁸ ) R ⁹ .
R ¹⁶ represents —SO ₃ ^— , —SO ₃ H, —SO ₂ NHR ⁸ or —SO ₂ N (R ⁸ ) R ⁹ .
R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and are included in the aromatic hydrocarbon group. The hydrogen atom is a halogen atom, —R ²⁶ , —OH, —OR ²⁶ , —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ²⁶ , —SO ₃ H, —SO ₃ R ²⁶ or It may be substituted with —SO ₂ NHR ²⁸ .
R ²⁵ represents —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ²⁶ , —SO ₃ H or SO ₂ NHR ²⁸ .
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an alkoxy group having 1 to 10 carbon atoms or a halogen atom. .
R ²⁸ is a hydrogen ^atom, -R _26, represents a monovalent aromatic hydrocarbon radical of -CO ^{2 R 26} or a C 6-10, hydrogen atom contained in the aromatic hydrocarbon group, ^{-R 26} or it may be substituted with ^{-OR 26.}
R ³¹ and R ³² each independently represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably a phenyl group, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, It may be substituted with —R ²⁶ , —OR ²⁶ , —CO ₂ R ²⁶ , —SO ₃ R ²⁶ or —SO ₂ NHR ²⁸ .
R ³³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ³⁴ represents a hydrogen atom, —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ⁴¹ and R ⁴² each independently represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably a phenyl group, and the hydrogen atom contained in the aromatic hydrocarbon group is represented by —R ²⁶ or it may be substituted with _-SO 2 ^{NHR 28.}
R ⁴³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meaning as described above. )
In the compounds represented by Formula (1-1) to Formula (1-4), the number of + charges and the number of −charges in the compounds are the same.
Of these, formula (1-4) is preferred.

（式中、Ｒ^ｂ及びＲ^ｃは、それぞれ独立に、水素原子、−ＳＯ_３ ⁻、−ＣＯ_２Ｈ又は−ＳＯ_２ＮＨＲ^ａを表す。
Ｒ^ｄ、Ｒ^ｅ及びＲ^ｆは、それぞれ独立に、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ又は−ＳＯ_２ＮＨＲ^ａを表す。
Ｒ^ｇ、Ｒ^ｈ及びＲ^ｉは、それぞれ独立に、水素原子、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ又は−ＳＯ_２ＮＨＲ^ａを表す。
Ｒ^ａは、１〜１０のアルキル基、好ましくは、２−エチルヘキシル基を表す。
Ｘ及びａは、上記と同じ意味を表す。）
式（１ｂ）で表される化合物は、式（１ｂ−１）で表される化合物の互変異性体である。
なかでも、式（１ｅ）で表される化合物及び式（１ｆ）で表される化合物が好ましい。 As a compound represented by Formula (1), the compound represented by Formula (1a)-Formula (1f) is mentioned, for example. However, the compounds represented by formula (1a) to formula (1f) have the same number of + charges and −charges in the compounds.

(In the formula, R ^b and R ^c each independently represent a hydrogen atom, —SO ₃ ^— , —CO ₂ H, or —SO ₂ NHR ^a .
R ^d , R ^e and R ^f each independently represent —SO ₃ ^— , —SO ₃ Na or —SO ₂ NHR ^a .
R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, —SO ₃ ^— , —SO ₃ H or —SO ₂ NHR ^a .
^Ra represents a 1 to 10 alkyl group, preferably a 2-ethylhexyl group.
X and a represent the same meaning as described above. )
The compound represented by the formula (1b) is a tautomer of the compound represented by the formula (1b-1).
Of these, the compound represented by the formula (1e) and the compound represented by the formula (1f) are preferable.

The compound represented by formula (1) is obtained by, for example, chlorinating a dye or dye intermediate having —SO ₃ H by a conventional method, and converting the obtained dye or dye intermediate having —SO ₂ Cl into R ⁸ —NH. It can manufacture by making it react with the amine represented by ₂ . Moreover, it can manufacture by making the pigment | dye manufactured by the method of Unexamined-Japanese-Patent No. 3-78702 page 3 right upper column-lower left column react with an amine after chlorination like the above.

［式（２）中、Ａ^０は、置換基を有していてもよい炭素数６〜１４の２価の芳香族炭化水素基を表す。
Ｂ^０は、置換基を有していてもよい炭素数６〜１４の１価の芳香族炭化水素基又は置換基を有していてもよい炭素数３〜１４の１価の芳香族複素環基を表す。
Ｒ^５１は、水素原子、置換基を有していてもよい炭素数１〜１６の１価の脂肪族炭化水素基又は置換基を有していてもよい炭素数２〜１８のアシル基を表す。
ｐは、１又は２を表す。ｐが２である場合、複数のＡ^０、Ｂ^０、Ｒ^５１及びＲ^５２は、互いに同一であっても異なっていてもよい。
ｐが１である場合、Ｒ^５２は、水素原子又は置換基を有していてもよい炭素数１〜１６の１価の脂肪族炭化水素基を表し、ｐが２である場合、Ｒ^５２は、置換基を有していてもよい炭素数１〜３５の２価の脂肪族炭化水素基を表し、該１価の脂肪族炭化水素基及び該２価の脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−及び−ＮＲ’−で置き換わっていてもよい。
Ｒ’は、水素原子又は炭素数１〜６の１価の脂肪族炭化水素基を表す。］ The dye is preferably a dye containing an azo compound, and more preferably a dye containing a compound represented by the formula (2).

Wherein (2), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.
B ⁰ is a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms that may have a substituent or a monovalent aromatic heterocyclic ring having 3 to 14 carbon atoms that may have a substituent. Represents a group.
R ⁵¹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or an acyl group having 2 to 18 carbon atoms which may have a substituent. .
p represents 1 or 2. When p is 2, the plurality of A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same as or different from each other.
When p is 1, R ⁵² represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, and when p is 2, R ⁵² is Represents a C1-C35 divalent aliphatic hydrocarbon group which may have a substituent, and is contained in the monovalent aliphatic hydrocarbon group and the divalent aliphatic hydrocarbon group- CH ₂ — may be replaced by —O—, —S—, —CO— and —NR′—.
R ′ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. ]

［式（２−１）中、Ｚ^１、Ｚ^２及びＺ^３は、それぞれ独立に、置換基を有していてもよい炭素数１〜１６の２価の脂肪族炭化水素基を表し、Ｚ^１、Ｚ^２及びＺ^３に含まれる−ＣＨ_２−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
Ｒ^５３及びＲ^５４は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜１６の１価の脂肪族炭化水素基又は置換基を有していてもよい炭素数２〜１８のアシル基を表す。
Ａ^１及びＡ^２は、それぞれ独立に、置換基を有していてもよい炭素数６〜１４の２価の芳香族炭化水素基を表す。
Ｂ^１及びＢ^２は、それぞれ独立に、置換基を有していてもよい炭素数６〜１４の１価の芳香族炭化水素基又は置換基を有していてもよい炭素数３〜１４の１価の芳香族複素環基を表す。］ The compound represented by the formula (2) is preferably a compound represented by the formula (2-1).

[In Formula (2-1), Z ¹ , Z ² and Z ³ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent, and Z ¹ , —CH ₂ — contained in Z ² and Z ³ may be replaced by —CO— or —O—.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon number which may have 2 substituents. Represents an acyl group of ˜18.
A ¹ and A ² each independently represent a C 6-14 divalent aromatic hydrocarbon group which may have a substituent.
B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a C ^{3 to} 14 carbon group which may have a substituent. Represents a monovalent aromatic heterocyclic group. ]

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms that may have a substituent representing R ⁵² include an alkanediyl group having 1 to 35 carbon atoms, such as a methylene group, an ethylene group, and propane. Examples thereof include a diyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group, and a hexadecanediyl group.
—CH ₂ — contained in the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms may be replaced by —O—, —S—, —CO— or —NR′—. The hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 35 carbon atoms may be substituted with a halogen atom such as a fluorine atom.
Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms representing R ′ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.

Z ¹ , Z ² and Z ³ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent. Carbon number of a substituent is not contained in carbon number of a C1-C16 bivalent aliphatic hydrocarbon group, The number becomes like this. Preferably it is 2-10, More preferably, it is 2-8.
Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include alkanediyl groups having 1 to 16 carbon atoms, such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, Examples include a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group, and a hexadecanediyl group.
—CH ₂ — contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be replaced by —CO— or —O—. The hydrogen atom contained in the C1-C16 divalent aliphatic hydrocarbon group may be substituted with a halogen atom such as a fluorine atom.

Z ¹ and Z ² are preferably an alkanediyl group having 1 to 8 carbon atoms which may contain —O—, and an alkanediyl group having 5 to 7 carbon atoms which may contain —O—. More preferably. Preferable groups include, for example, — (CH ₂ ) ₃ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —O— (CH _{2) 2} - or _-CH 2 -CH (CH ₃₎ - and the like.
Z ³ is preferably a C 1-8 divalent aliphatic hydrocarbon group which may contain —C (═C) —, and is an unsubstituted alkanediyl group having 1 to 8 carbon atoms. More preferably, it is an unsubstituted alkanediyl group having 4 to 8 carbon atoms. Preferable groups include, for example, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, or —CH ₂ —C (═CH ₂ ) —.

The monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms representing R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is preferably 6 to 10, more preferably 1 to 4.
Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , Methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), methylhexyl group (such as 1,5-dimethylhexyl group), ethylhexyl group (such as 2-ethylhexyl group), cyclopentyl group, cyclohexyl group, methyl Examples thereof include a cyclohexyl group (such as 2-methylcyclohexyl group) and a cyclohexylalkyl group.
The hydrogen atom contained in the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxy group. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group (such as 3- (isopropoxy) propyl group) and an alkoxypropyl group (3- (2-ethylhexyloxy) propyl group, etc.). As a C1-C16 aliphatic hydrocarbon group substituted by the carboxy group, 2- (carboxy) ethyl group, 3- (carboxy) propyl group, 4- (carboxy) butyl group, etc. are mentioned.

A hydrogen atom contained in an acyl group having 2 to 18 carbon atoms representing R ⁵¹ , R ⁵³ and R ⁵⁴ may be substituted with an alkoxy group having 1 to 8 carbon atoms. The carbon number of the acyl group having 2 to 18 carbon atoms which may have a substituent is counted including the carbon number of the substituent, and the number is preferably 6 to 10. Examples of the acyl group that may have a substituent include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

R ⁵³ and R ⁵⁴ are preferably a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Preferable groups include, for example, a hydrogen atom, an acetyl group, or a propionyl group.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms representing A ⁰ , A ¹ and A ² include a phenylene group and a naphthalenediyl group, and among them, a phenylene group is preferable.

Examples of the substituent for the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, a sulfamoyl group, and N-substituted sulfamoyl groups and the like can be mentioned.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom, a chlorine atom, or a bromine atom is preferable.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is particularly preferable.

  Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. An alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

Examples of the N-substituted sulfamoyl group include SO ₂ NHR ⁵⁵ and —SO ₂ N (R ⁵⁵ ) R ⁵⁶ , and specifically, —SO ₂ NHR ⁸ and —SO in the compound represented by the formula (1). ₂ N (R ⁸ ) R ^{9 includes the} same groups as mentioned above. Among them, R ⁵⁵ and R ⁵⁶ are each independently an optionally substituted aliphatic hydrocarbon group having 1 to 16 carbon atoms or an optionally substituted acyl having 2 to 18 carbon atoms. The group N-substituted sulfamoyl group is preferred.

［Ｒは、水素原子又はメチル基を表す。］ B ⁰ , B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or 3 carbon atoms which may have a substituent. Represents a monovalent aromatic heterocyclic group of -14.
Examples of the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.
Examples of the monovalent aromatic heterocyclic group having 3 to 14 carbon atoms include the groups shown below.

[R represents a hydrogen atom or a methyl group. ]

The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and the monovalent aromatic heterocyclic group having 3 to 14 carbon atoms is a hydroxy group, an oxo group, or a monovalent group having 1 to 16 carbon atoms. May be substituted with an aliphatic hydrocarbon group, a cyano group, an amino group or an N-substituted amino group.
As the N-substituted amino group, —NHR ⁵⁷ group or —NR ⁵⁷ R ⁵⁸ group is preferable. However, each of R ⁵⁷ and R ⁵⁸ independently represents an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms or optionally substituted 3 to 3 carbon atoms. 14 monovalent aromatic heterocyclic groups. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms and the monovalent aromatic heterocyclic group having 3 to 14 carbon atoms include the same groups as described above.

［式（２−１ａ）中、Ｒ^５９は水素原子又は置換基を有していてもよい炭素数１〜１６の１価の脂肪族炭化水素基を表す。Ｒ^６０は、置換基を有していてもよい炭素数１〜１６の１価の脂肪族炭化水素基を表す。］
式（２−１ａ）で表される基のピリドン環は、ケト型であってもエノール型であってもよい。 B ⁰ , B ¹ and B ² are preferably each independently a group represented by the formula (2-1a).

[In Formula (2-1a), R ⁵⁹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. R ⁶⁰ represents a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. ]
The pyridone ring of the group represented by the formula (2-1a) may be keto type or enol type.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms of R ⁵⁹ and R ⁶⁰ include those described above, and R ⁵⁹ represents a methylbutyl group (1,1,3,3-tetramethylbutyl group). Methylhexyl group (such as 1,5-dimethylhexyl group), ethylhexyl group (such as 2-ethylhexyl group), methylcyclohexyl group (such as 2-methylcyclohexyl group) and alkoxypropyl group (3- A branched chain aliphatic hydrocarbon group such as (2-ethylhexyloxy) propyl group) is preferable.
Examples of the substituent in R ⁵⁹ and R ⁶⁰ include a hydroxy group, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, and an acyloxy group having 1 to 8 carbon atoms.
Here, examples of the alkoxy group having 1 to 8 carbon atoms include a toxi group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. Etc.
Examples of the acyloxy group having 1 to 8 carbon atoms include acetyloxy group, propionyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, benzoyloxy group and the like.
R ⁶⁰ is preferably a methyl group.

Examples of the compound represented by formula (2) include compounds represented by formula (I-1) to formula (I-18). A ¹ , A ² , Z ^1, and Z ² in the table represent a bond in which the right bond is closer to Z ³ .

B ¹ and B ² are preferably the same type of group, and more preferably A ¹ and A ² , R ⁵³ and R ⁵⁴ , and Z ¹ and Z ² are the same type of group, respectively. When these groups are used, the compound represented by the formula (2-1) can be easily produced.

  The compound represented by the formula (2-1) is a compound represented by the formula (IA) and a compound represented by the formula (IA ′) and a compound represented by the formula (IB) in a solvent. It can manufacture by making the represented compound react at 0-150 degreeC.

［式（Ｉ−Ａ）、式（Ｉ−Ａ’）及び式（Ｉ−Ｂ）中、Ｚ^１、Ｚ^２、Ｚ^３、Ｒ^５３、Ｒ^５４、Ａ^１、Ａ^２、Ｂ^１及びＢ^２は上記と同じ意味を表す。
Ｒ^６７及びＲ^６８は、それぞれ独立に、−ＯＲ^６９又はハロゲン原子を表す。Ｒ^６９は、１価の炭素数１〜１６の脂肪族炭化水素基を表す。］

[In formula (IA), formula (IA ′) and formula (IB), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² Represents the same meaning as above.
R ⁶⁷ and R ⁶⁸ each independently represents —OR ⁶⁹ or a halogen atom. R ⁶⁹ represents a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms. ]

Examples of the compound represented by the formula (IB) include dimethyl malonate, isobutyl succinate, dimethyl adipate, and diethyl suberate, malonic acid chloride, succinic acid chloride, adipic acid chloride, and suberic acid chloride. .
The amount of the compound represented by the formula (IB) is 1 mol relative to the total amount of the compound represented by the formula (IA) and the compound represented by the formula (IA ′). For example, it is preferably 0.5 to 3 mol. In addition, when water is contained in the solvent, it is preferable to use the compound represented by the formula (IB) in excess of the above amount.
When R ³¹ and R ³² of the compound represented by the formula (IB) are —OR ³³ , it is preferable to add a known acid catalyst. Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid. The usage-amount of an acid catalyst is 0.01-2 mol with respect to 1 mol of total amounts with the compound represented by the compound represented by a formula (IA), and a formula (IA '), for example. Preferably there is.

The reaction of the compound represented by the formula (IA) and the compound represented by the formula (IA ′) with the compound represented by the formula (IB) is performed in a solvent. Examples of the solvent include water; ethers such as 1,4-dioxane (particularly cyclic ethers); chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, Halogenated hydrocarbons such as amyl chloride and 1,2-dibromoethane; Ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Carbon-based aromatics such as benzene, toluene and xylene; N, N-dimethylformamide, N , N-dibutylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and other alkylamides are preferred, and two or more solvents may be used in combination. The amount of the solvent used is preferably, for example, 1 to 20 parts by mass with respect to 1 part by mass of the total amount of the compound represented by the formula (IA) and the compound represented by the formula (IA ′). More preferably, it is 2-10 mass parts.
The reaction between the compound represented by the formula (IA) and the compound represented by the formula (IA ′) and the compound represented by the formula (IB) is performed under a nitrogen atmosphere or an argon atmosphere. The reaction may be carried out in air dried with calcium chloride or the like.
The reaction temperature is, for example, preferably 0 to 150 ° C, more preferably 10 to 130 ° C. For example, the reaction time is preferably 1 to 25 hours, more preferably 3 to 15 hours.

The order of addition of the compound represented by the formula (IA), the compound represented by the formula (IA ′), the compound represented by the formula (IB), and the solvent is not particularly limited. The compound represented by the formula (IB) is preferably added (dropped) to a solution comprising the compound represented by -A), the compound represented by the formula (IA ′) and a solvent. When an acid catalyst is used, the compound represented by the formula (IB) is added to a solution comprising the compound represented by the formula (IA), the compound represented by the formula (IA ′), the acid catalyst and a solvent. The compound to be added is preferably added (dropped).
The method for obtaining the compound represented by the formula (2-1), which is the target compound, from the reaction mixture obtained as described above is not particularly limited, and various known techniques can be employed. It can be purified by extraction with an organic solvent. Moreover, you may refine | purify as needed by well-known methods, such as washing | cleaning by alkaline aqueous solution or acidic aqueous solution, and recrystallization.

  In addition, the compound represented by the formula (2-1) is represented by the compound represented by the formula (IC), the compound represented by the formula (ID), and the formula (ID ′). The compound can be produced by a coupling reaction. The salt of the compound represented by the formula (IC), the compound represented by the formula (ID) and the compound represented by the formula (ID ′) are, for example, 20 to 60 ° C. in an aqueous solvent. By making it react by, the compound represented by Formula (2-1) can be manufactured.

（式（Ｉ−Ｃ）及び式（Ｉ−Ｄ）中、Ｚ^１、Ｚ^２、Ｚ^３、Ｒ^５３、Ｒ^５４、Ａ^１、Ａ^２、Ｂ^１及びＢ^２は上記と同じ意味を表す。
Ｘ⁻は、無機又は有機アニオンを表す。）

(In Formula (IC) and Formula (ID), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² represent the same meaning as described above.
X ⁻ represents an inorganic or organic anion. )

Examples of the inorganic or organic anion of the compound represented by the formula (IC) include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ —COO ^−. , Ph-COO ^- is like, preferably chloride, _bromide, CH 3 -COO ^- and the like.

  The dye is preferably a dye containing a metal complex having an azo compound as a ligand, and more preferably a dye containing a compound represented by the formula (3). The compound represented by the formula (3) is a salt of a chromium complex anion or a cobalt complex anion and a cation.

［式（３）中、Ｒ^ａ１〜Ｒ^ａ１８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価の脂肪族炭化水素基、ニトロ基、フェニル基、−ＳＯ_２ＮＨＲ^ａ３０、−ＳＯ_３ ^-又はＣＯＯＲ^ａ３１を表す。
Ｒ^ａ１９及びＲ^ａ２０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。
Ｒ^ａ３０及びＲ^ａ３１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−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｍ^１は、Ｃｒ又はＣｏを表す。
ｎ^１は、１〜５の整数を表す。
Ｄ^１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 ^{a1 to} R ^a18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a phenyl group, or —SO ₂ NHR ^a30. , -SO ₃ ^- or COOR ^a31 .
R ^a19 and R ^a20 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group.
R ^a30 and R ^a31 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or —CO—. It may be replaced.
M ¹ represents Cr or Co.
n ¹ represents an integer of 1 to 5.
D ¹ represents a monovalent cation derived from a compound having hydrone, a monovalent metal cation or a xanthene skeleton. ]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms representing R ^{a1 to} R ^a18 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, dexyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl Group, 1,6-dimethylheptyl group, 2-ethylhexyl group, 1,1,5,5-tetramethylhexyl group and the like.

^Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms representing R ^a30 and R ^a31 include a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and a monovalent alicyclic carbon group having 3 to 10 carbon atoms. Examples thereof include a hydrogen group, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a group having 4 to 10 carbon atoms in combination thereof. Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include the same groups as described above, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is represented by the formula (1). And the same groups as those represented by Q of the compound. 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 ^a32 —O—R ^a33 , —R ^a32 —CO—O—R ^a33 , —R ^a32 —O—CO -R ^a33 is mentioned. R ^a32 is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ^a33 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 ^a32 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.

As —R ^a32 —O—R ^a33 , 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 ^a32 —CO—O—R ^a33 includes methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxycarbonylmethyl group, propoxycarbonylethyl group, butoxycarbonylmethyl group, butoxycarbonyl An ethyl group etc. are mentioned.

—R ^a32 —O—CO—R ^a33 includes acetyloxymethyl group, acetyloxyethyl group, ethylcarbonyloxymethyl group, ethylcarbonyloxyethyl group, propylcarbonyloxymethyl group, propylcarbonyloxyethyl group, butylcarbonyloxy Examples thereof include a methyl group and a butylcarbonyloxyethyl group.

As —SO ₂ NHR ^a30 , a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, 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-cyclopentylsulfamoyl group, N-hexylsulfamoyl 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, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group, sulfamoyl group substituted with an aliphatic hydrocarbon group such as N-allylsulfamoyl group;

N- (2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-methoxypropylsulfamoyl) group, N- (3- Ethoxypropyl) sulfamoyl group, N- (3-propoxypropyl) sulfamoyl group, N- (3-isopropoxypropyl) sulfamoyl group, N- (3-hexyloxypropylsulf) famoyl group, N- (2-ethylhexyloxypropyl) A sulfamoyl group substituted with —R ³¹ —O—R ³² such as a sulfamoyl group, an N- (3-tert-butoxypropyl) sulfamoyl group, an N- (4-octyloxybutyl) sulfamoyl group;
N- (methoxycarbonylmethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (ethoxycarbonylmethyl) sulfamoyl group, N- (ethoxycarbonylethyl) sulfamoyl group, N- (propoxycarbonylmethyl) sulfamoyl group, A sulfamoyl group substituted with —R ³¹ —CO—O—R ³² such as N- (propoxycarbonylethyl) sulfamoyl group, N- (butoxycarbonylmethyl) sulfamoyl group, N- (butoxycarbonylethyl) sulfamoyl group;
N- (acetyloxymethyl) sulfamoyl group, N- (acetyloxyethyl) sulfamoyl group, N- (ethylcarbonyloxymethyl) sulfamoyl group, N- (ethylcarbonyloxyethyl) sulfamoyl group, N- (propylcarbonyloxymethyl) Substituted with —R ³¹ —O—CO—R ³² such as sulfamoyl group, N- (propylcarbonyloxyethyl) sulfamoyl group, N- (butylcarbonyloxymethyl) sulfamoyl group, N- (butylcarbonyloxyethyl) sulfamoyl group, etc. Sulfamoyl groups;

N-cyclohexylsulfamoyl group, N- (2-methylcyclohexyl) sulfamoyl group, N- (3-methylcyclohexyl) sulfamoyl group, N- (4-methylcyclohexyl) sulfamoyl group, N- (4-butylcyclohexyl) sulfamoyl A sulfamoyl group substituted with a cyclohexyl group having a substituent such as a 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- ( And a sulfamoyl group substituted with an aralkyl group such as a 3-phenyl-1-methylpropyl) sulfamoyl group.

Since heat resistance tends to be high, at least one of R ^{a1 to} R ^a18 is preferably a nitro group.

As R ^a30 and R ^a31 , 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 ^a32 —O—R ^a33 , —R ^a32 —CO—O—R ^a33 and —R ^a32 —O—CO—R ^a33 are preferred.

  In the compound represented by the formula (3), preferred examples of the pyrazole azo compound that serves as a ligand for the complex anion include compounds represented by the formula (1-a1) to the formula (1-a56). .

  In the compound represented by formula (3), preferred examples of the complex anion include anions represented by formula (1-b1) to formula (1-b50).

D ¹ is a monovalent cation derived from a compound having hydron, a monovalent metal cation or a xanthene skeleton. Among these, a monovalent cation derived from a compound having a xanthene skeleton is preferable in that the lightness of the obtained color filter is high. Examples of the compound having a xanthene skeleton include a compound represented by the formula (1).

［式（３−１）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、スルホ基又は−ＳＯ_２ＮＨＲ^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、−Ｒ^ａ３２−Ｏ−Ｒ^ａ３３、−Ｒ^ａ３２−ＣＯ−Ｏ−Ｒ^ａ３３、−Ｒ^ａ３２−Ｏ−ＣＯ−Ｒ^ａ３３又は炭素数７〜１０のアラルキル基を表す。
Ｒ^ａ３２は、炭素数１〜８の２価の脂肪族炭化水素基を表す。
Ｒ^ａ３３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。
Ｍ^２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、−ＯＲ^３２、スルホ基、−ＳＯ_３Ｎａ、−ＳＯ_３Ｋ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以上の整数である場合、複数のＲ^２７は互いに同一であっても異なっていてもよい。］ The compound represented by Formula (3) is preferably a compound represented by Formula (3-1) from the viewpoint of solubility in an organic solvent.

[In Formula (3-1), 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. Represents NHR ^a34 .
R ^a34 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ^a32 -O-R ^a33 ,- R ^a32 —CO—O—R ^a33 , —R ^a32 —O—CO—R ^a33 or an aralkyl group having 7 to 10 carbon atoms is represented.
R ^a32 represents a C 1-8 divalent aliphatic hydrocarbon group.
R ^a33 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 ³² , a sulfo group, —SO ₃ Na, —SO ₃ K, or a halogen atom.
R ^a25 and R ^a26 each independently represent a hydrogen atom or a methyl group.
R ^a27 represents 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 an integer greater than or equal to 2, several R < ²⁷ > may mutually be same or different. ]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those described above for R ^{a1 to} R ^a18 .
Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those described above for R ^a32 .

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 it exists in the tendency for heat resistance to be high, it is preferable that it is at least 1 nitro group among R ^{< a41 >} -R ^{< a58 >} .
^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 or _-SO 2 ^{NHR _a34,} and more preferably -SO ^{2 NHR a34.} Among these, R ^a34 is preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrogen atom or a 2-ethylhexyl group. When a plurality of —SO ₂ NHR ^a34 are ^contained , these may be the same as or different from each other.

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 and 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.

  In the compound represented by the formula (3-1), preferable examples of the cation derived from the xanthene compound include cations represented by the formula (1-c1) to the formula (1-c48).

Specific examples of the compound represented by Formula (3-1) include compounds represented by Formula (1-1) to Formula (1-20).

  Among the specific examples of the compound represented by the formula (3-1), in terms of solubility in an organic solvent, the formula (1-1), the formula (1-3) to the formula (1-5), the formula ( Compounds represented by formula (1-7) to formula (1-9), formula (1-11) to formula (1-16) and formula (1-18) to formula (1-20) are preferred, The compound represented by -1) and the compound represented by Formula (1-3) are more preferable.

In order to produce the compound represented by the formula (3), a chromium complex salt is formed using the compound represented by the formula (3d) and the chromium compound, or the compound represented by the formula (3d) and cobalt. A cobalt complex salt is formed using the compound. Thereafter, the compound represented by the formula (3) can be produced by subjecting the complex salt and the salt having D ¹ to a salt exchange reaction as necessary.

[In formula (3d), R ^{a1 to} R ^a5 , R ^{a11 to} R ^a14 and R ^a19 represent the same meaning as in formula (3). ]
The compound represented by the formula (3d) can be produced by a diazo coupling method of a diazonium salt and a pyrazole compound, which is well known in the dye field.

The compound represented by the formula (3-1) is produced by subjecting the complex salt and the xanthene compound represented by the formula (b) to a salt exchange reaction.

[In formula (b), R ^{a21 to} R ^a28 and n represent the same meaning as in formula (3-1). A ⁻ represents a monovalent anion. ]
Examples of the monovalent anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ^{− and} BF ₄ ⁻ .

［式（ｂ０）及び式（ｂ１）中、Ｒ^ａ２１〜Ｒ^ａ２８及びｎは、式（２−１）におけるものと同じ意味を表す。Ａ⁻は、式（ｂ）におけるものと同じ意味を表す。］
前記反応において、反応温度は１５℃〜６０℃が好ましく、反応時間は１時間〜１２時間が好ましい。また、反応時間短縮や収率向上の点で、酸触媒及び／又は脱水剤を用いることが好ましい。
酸触媒としては、硫酸、ｐ−トルエンスルホン酸などが挙げられる。
脱水剤としては、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、1-エチル-3-（3-ジメチルアミノプロピル）カルボジイミド塩酸塩等のカルボジイミド類；１−アルキル−２−ハロピリジウム塩類；１，１’−カルボニルジイミダゾール；ビス（２−オキソ−3−オキサゾリジニル）ホスフィン酸塩化物；ジ−２−ピリジル炭酸塩などが挙げられる。中でも、脱水剤としては、後処理及び精製が容易であることから、1-エチル-3-（3-ジメチルアミノプロピル）カルボジイミド塩酸塩が好ましい。
前記反応に用いられる有機溶媒としては、ジクロロメタン、クロロホルム、テトラヒドロフラン、トルエン、アセトニトリルなどが挙げられる。 The xanthene compound represented by the formula (b) can be produced by reacting the compound represented by the formula (b0) and the compound represented by the formula (b1) in an organic solvent.

[In formula (b0) and formula (b1), R ^{a21 to} R ^a28 and n represent the same meaning as in formula (2-1). A ⁻ represents the same meaning as in formula (b). ]
In the above reaction, the reaction temperature is preferably 15 ° C. to 60 ° C., and the reaction time is preferably 1 hour to 12 hours. Moreover, it is preferable to use an acid catalyst and / or a dehydrating agent in terms of shortening the reaction time and improving the yield.
Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid.
Examples of the dehydrating agent include carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride; 1-alkyl-2-halopyridinium salts; 1,1′-carbonyldiimidazole; Bis (2-oxo-3-oxazolidinyl) phosphine acid chloride; di-2-pyridyl carbonate and the like can be mentioned. Among these, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride is preferable as the dehydrating agent because of easy post-treatment and purification.
Examples of the organic solvent used in the reaction include dichloromethane, chloroform, tetrahydrofuran, toluene, and acetonitrile.

  The compound represented by the formula (3-1) can be produced by subjecting the complex salt and the xanthene compound represented by the formula (b) to a salt exchange reaction in a solvent. The cobalt complex salt and the xanthene compound (b) are preferably reacted at a molar ratio of 1: 1 to 1: 4.

The pigment may be either an organic pigment or an inorganic pigment, but is preferably an organic pigment.
As the organic pigment, for example, any of those described in JP-A No. 2003-327864 can be used. Especially, C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58; 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; 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. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Is preferred.

When producing a color filter using a coloring composition, the coloring composition is each adjusted as a blue composition, a green composition, and a red composition.
The blue composition is C.I. I. Pigment red violet 23, C.I. I. Preferably at least one pigment selected from CI Pigment Blue 15: 3 and 15: 6; I. More preferably, it contains CI Pigment Blue 15: 6. The green composition is C.I. I. Pigment green 36, 58, C.I. I. It is preferable to contain at least one selected from Pigment Yellow 138 and 150. The red composition is C.I. I. Pigment yellow 138, 139, 150, C.I. I. It is preferable to contain at least one selected from CI Pigment Red 177, 242, and 254. These pigments may be used alone or in combination of two or more.

  For pigments, especially organic pigments, rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, or removal of impurities as necessary. For example, a cleaning process using an organic solvent or water, a removal process using an ion exchange method for ionic impurities, or the like may be performed. The pigment preferably has a uniform particle size.

The pigment used in the method for producing a pigment dispersion of the present invention is preferably a pigment that has been subjected to a refinement treatment. Examples of such refinement treatment include salt milling treatment and sulfuric acid atomization treatment, and salt milling treatment is preferable.
Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid. The pigment is crushed using the high hardness of the inorganic salt during salt milling. Since the crushing of the pigment and the crystal growth on the active surface caused by the crushing occur simultaneously, the primary particle diameter of the pigment to be obtained varies depending on the kneading conditions.

The kneading temperature is preferably 40 to 150 ° C. When the kneading temperature is within the above range, crystal growth during kneading is promoted, and the shape of the resulting pigment particles tends to be uniform. On the other hand, when the heating temperature is less than 40 ° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes undesirably close to amorphous. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds excessively and the primary particle diameter of the pigment increases, which is not preferable as a colorant for the color filter coloring composition. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.
By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution in which the primary particle diameter is very fine and the distribution range is wide. A color filter obtained using a coloring composition containing such a pigment is excellent in color characteristics.

  As the water-soluble inorganic salt used for the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000% by mass, and most preferably 300 to 1,000% by mass, based on the total amount of the pigment, from both the treatment efficiency and the production efficiency.

  The water-soluble organic solvent serves to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. A solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of being hard to evaporate at the temperature during salt milling and from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000% by mass, more preferably 50 to 500% by mass, based on the total amount of the pigment.

  When performing the salt milling treatment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably hardly soluble or insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200% by mass with respect to the total amount of pigment.

In the method for producing a pigment dispersion of the present invention, it is preferable to use a pigment dispersant for improving the dispersibility of the pigment and improving the dispersion stability. Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more.
When a pigment dispersant is used, the amount used is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.05 part by mass or more and 0.5 parts by mass per 1 part by mass of the pigment. Or less. When the amount of the pigment dispersant used is within this range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

  In the method for producing a pigment dispersion of the present invention, a pigment derivative (however, different from a dye) or the like may be used as a dispersion aid for improving the dispersibility of the pigment and improving the dispersion stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Derivatives such as pyrrole and dioxazine pigments may be mentioned. Usually, pigment derivatives are hardly soluble in organic solvents. As substituents of pigment derivatives, sulfo groups, sulfamoyl groups and quaternary salts thereof, phthalimidomethyl groups, N, N-dialkylaminoalkyl groups, hydroxy groups, carboxy groups, carbamoyl groups, etc. are directly in the pigment skeleton or alkyl groups, aryl And a sulfamoyl group, a quaternary salt thereof, and a sulfo group are preferable, and a sulfo group is more preferable. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindoline pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, Examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

  In the method for producing a pigment dispersion of the present invention, part or all of a resin selected from the resin (B) described later may be contained. Specifically, in the dispersion treatment step in the preparation of the pigment dispersion described below, the binder resin contributes to the dispersion stability through a synergistic effect with the dispersant by including the binder resin together with the pigment dispersant described above. Therefore, it is preferable.

In the present invention, the dye and the pigment are preferably contained in a mass ratio of dye: pigment = 1: 99 to 99: 1, more preferably 1:99 to 60:40, and 5:95 to More preferably, it is 40:60. By setting such a ratio, the transmission spectrum can be easily optimized, a colored pattern with high contrast and high brightness can be obtained, and the resulting colored pattern has good heat resistance and chemical resistance.
When the coloring composition is a blue composition, C.I. I. Pigment Blue 15: 6 and the dye have a mass ratio of preferably 99: 1 to 40:60, more preferably 97: 3 to 50:50, and 97: 3 to 70:30. Further preferred. In the case of a green composition, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 138 and C.I. I. The mass ratio of at least one selected from CI Pigment Green 150 and the dye is preferably 99: 1 to 40:60, more preferably 99: 1 to 50:50, and 95: 5 to 55:45. More preferably. In the case of a red composition, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The mass ratio of at least one selected from Pigment Red 254 and the dye is preferably 99: 1 to 40:60, more preferably 99: 1 to 50:50, and 97: 3 to 65:35. More preferably.

  In the method for producing a pigment dispersion of the present invention, the above-described dye and pigment are simultaneously dispersed in a solvent.

The following are mentioned as a solvent used in this invention.
Examples thereof include alcohols such as monoalcohols and polyhydric alcohols.
Examples of such alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.

Moreover, glycol ethers, such as ethylene glycol and propylene glycol, are mentioned.
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether and ethylene glycol monobutyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, di Dipropylene glycol dialkyl ethers such as propylene glycol methyl ethyl ether;
Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether and dipropylene glycol monopropyl ether;
Butyldiol monoalkyl ethers such as 3-methoxybutanol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol;
Examples include diethylene glycol dimethyl ether.

Examples include ethers including ether acetates and ether propionates.
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate;
Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate;
Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate;
Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate;
Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate;
Diethylene glycol monoalkyl ether acetates such as diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate;
Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate;
Propylene glycol monoethyl ether acetate and the like;
And methoxypentyl acetate.

Aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of hydrocarbons include cyclohexane.

  Examples of ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, 4-hydroxy-4-methyl-2-pentanone, 2-butanone, 2-heptanone, 3-heptanone, 4- Examples include heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

  Esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, Ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-methyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxy Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxyvinegar Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2- Ethyl butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propionate 3-methoxypropionate Butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, Examples include propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and ethyl pyruvate.

Examples of cyclic ethers include tetrahydrofuran, pyran, tetrahydropyran and the like.
Examples of cyclic esters include γ-butyrolactone.

Examples of amides include N, N′-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
As the solvent used in the dispersion step, ethers including ether acetates and ether propionates are preferable, ether acetates are more preferable, and propylene glycol monomethyl ether acetate is more preferable. When these solvents are used, there is a tendency that foreign matters are less likely to appear on the surface of the obtained color filter.
These solvents may be used alone or in combination of two or more. There may also be solvents classified into a plurality of classes.

  In the method for producing a pigment dispersion of the present invention, a pigment and a dye are uniformly dispersed simultaneously in a solvent. The term “simultaneous” here does not mean an instantaneous time, but among the above-mentioned solvents, both operations are continuously performed on the same solvent, that is, other operations such as heating, cooling, stirring, and mixing. Means that the materials are added in sequence without any substantial or minimal, and after both are present in the same solvent, they are optionally dispersed by heating, cooling, stirring, mixing, etc. To do. That is, as one step, both are put in the same solvent and dispersed.

  The method for simultaneously dispersing the dye and the pigment is not particularly limited, and can be carried out by using a known apparatus or a known method in this field. A pigment, a dye, a pigment dispersant, a solvent, and if necessary, a dispersion aid and a resin may be mixed and dispersed at the same time, or the dye, the pigment dispersant, and the resin may be dissolved in a solvent in advance and mixed. It may be dispersed. The dispersion is preferably performed using a disperser such as a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, or a homogenizer. Since the pigment is finely divided by dispersing as described above, the coating properties of the colored composition are improved, and the transmittance and contrast of the color filter obtained from the colored composition are improved.

  When dispersion 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. 0-100 degreeC or more is preferable and the temperature which disperse | distributes has more preferable 20-80 degreeC or more. The time for dispersing is 1 to 20 hours, preferably about 1 to 10 hours, and may be appropriately adjusted depending on the composition of the pigment dispersion and the size of the paint shaker device.

The method for producing the colored composition of the present invention comprises the above-described pigment dispersion (A), a solvent (E), a resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D). The method of mixing at least 1 sort is mentioned.
As the solvent, those contained in the pigment dispersion may be used as they are, or the above-mentioned solvents may be appropriately selected and mixed.

In the colored composition to be produced, the total amount of the dye and the pigment is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, based on the solid content in the colored composition. Preferably it is 10-50 mass%. Here, solid content means the sum total of the component except a solvent in a coloring composition.
When the content of the dye and the pigment is within this range, the color density of the resulting color pattern or color filter is sufficient, and the binder polymer can be contained in the composition in a necessary amount, so that the mechanical strength is excellent. A colored pattern or a color filter can be formed.

Although it does not specifically limit as resin (B), For example, what contains alkali-soluble resin is preferable.
The alkali-soluble resin is not particularly limited, and any resin may be used. For example, the alkali-soluble resin contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 mol% or more and 38 mol% or less in all the structural units constituting the alkali-soluble resin. It is. When the content of the structural unit derived from (meth) acrylic acid is within the above range, the solubility of the non-pixel portion is improved during development. In addition, there is a tendency that the residue does not easily remain in the non-pixel portion after development.

  Examples of other monomers that derive structural units other than the structural units derived from (meth) acrylic acid constituting the alkali-soluble resin include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, and unsaturated carboxylic acid aminoalkyl esters. , Unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl at the end of the polymer molecular chain And a macromonomer having a group or a monomethacryloyl group, a unit represented by the formula (II) and a unit represented by the formula (III).

（式（ＩＩ）及び式（ＩＩＩ）中、Ｒ^８０及びＲ^８２は、それぞれ独立に、水素原子又はメチル基を表す。Ｒ^８１及びＲ^８３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。）

(In Formula (II) and Formula (III), R ⁸⁰ and R ⁸² each independently represent a hydrogen atom or a methyl group. R ⁸¹ and R ⁸³ each independently represent a hydrogen atom or a carbon number of 1 to 6). Represents an alkyl group of

Specific examples of the alkali-soluble resin 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 / constituent unit represented by formula (II) (wherein, in formula (II), R ⁸⁰ represents a methyl group, R ⁸¹ represents a hydrogen atom) ) / Benzyl methacrylate copolymer, structural unit represented by formula (II) (wherein, in formula (II), R ⁸⁰ represents a methyl group and R ⁸¹ represents a hydrogen atom) /. Benzyl methacrylate copolymer, methacrylic acid / constituent unit represented by formula (III) In the formula (III), R ⁸² represents a methyl group, and R ⁸³ represents a hydrogen atom.) / Styrene copolymer / tricyclodecyl methacrylate copolymer and the like are preferable.

In particular, an alkali-soluble resin represented by the formula (IV) is preferable in terms of curability and developability.

  An alkali-soluble resin having a structural unit represented by the formula (II), for example, methacrylic acid / a structural unit represented by the formula (II) / benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate. It can be obtained by obtaining a component polymer and reacting the obtained two-component polymer with the compound represented by the formula (V).

［式（Ｖ）及び式（ＶＩ）中、Ｒ^８１及びＲ^８３は、上記と同じ意味を表す。］ Methacrylic acid / constituent unit represented by formula (III) / styrene copolymer / tricyclodecyl methacrylate copolymer is converted into benzyl methacrylate, methacrylic acid, monomethacrylate copolymer of tricyclodecane skeleton, formula (VI) It can obtain by making the compound represented by these react.

[In Formula (V) and Formula (VI), R ⁸¹ and R ⁸³ represent the same meaning as described above. ]

The copolymerization is generally performed in a solvent using a polymerization initiator.
Examples of the polymerization initiator include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (methyl 2-methylpropionate), benzoyl peroxide and tert-butyl peroxide. A peroxide such as is used.
The solvent may be any solvent that dissolves each monomer. For example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Or the like can be used.

The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator and the boiling points of the solvent and the monomer.
The side chain of the copolymer thus obtained can be modified with a compound having a polymerizable group to form a photosensitive alkali-soluble resin. At this time, a catalyst for introducing a polymerizable group into the resin may be added.
Examples of the catalyst include trisdimethylaminomethylphenol. Moreover, you may add the additive for preventing a side reaction. Examples of the additive include hydroquinone.

Examples of the alkali-soluble resin include the following copolymers [K1] to [K4].
[K1] Unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (B1) (hereinafter sometimes simply referred to as “(B1)”) and a monomer having a cyclic ether structure having 2 to 4 carbon atoms A copolymer obtained by polymerizing (B2) (hereinafter sometimes simply referred to as “(B2)”).
[K2] A copolymer obtained by polymerizing (B1), (B2) and the monomer (B3). Here, the monomer (B3) (hereinafter sometimes simply referred to as “(B3)”) is a monomer copolymerizable with (B1) and / or (B2), and (B1) And (B2) is a different monomer.
[K3] In the copolymer of (B1) and (B3), by reacting a part of the carboxy group derived from (B1) with a C2-C4 cyclic ether structure derived from (B2). The resulting copolymer.
[K4] A copolymer of (B1) and (B3).
Especially, it is preferable that it is a copolymer formed by polymerizing at least (B1) and (B2).

Examples of (B1) include aliphatic unsaturated carboxylic acid and / or aliphatic unsaturated carboxylic acid anhydride. In particular,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; and 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-ethyl Bicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] Bicyclounsaturated compounds containing a carboxy group such as 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- Anhydrides of unsaturated dicarboxylic acids 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.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and alkali solubility.
You may use these individually or in combination of 2 or more types. In the present specification, unless otherwise specified, the exemplified compounds, components, agents and the like can be used alone or in combination of two or more.
In this 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.

  (B2) may have, for example, at least one structure selected from the group consisting of cyclic ether structures having 2 to 4 carbon atoms (for example, an oxirane structure, an oxetane structure, and a tetrahydrofuran structure). A monomer having a saturated bond is preferred.

  Examples of (B2) include a monomer having an oxiranyl group, a monomer having an oxetanyl group, and a monomer having a tetrahydrofuryl group.

The monomer having an oxiranyl group refers to, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group.
The monomer having an epoxy group is preferably a compound having at least one structure selected from the group consisting of a structure obtained by epoxidizing an alkene and a structure obtained by epoxidizing a cycloalkene and an unsaturated bond. A monomer having at least one structure selected from the group consisting of an epoxidized structure and a structure obtained by epoxidizing a cycloalkene and a (meth) acryloyloxy group is more preferable.

（式（VI')中、Ｒ^８４〜Ｒ^８６は、それぞれ独立に水素原子又は炭素原子数１〜１０のアルキル基であり、ｍ１は１〜５の整数である。）。 Specific examples of the compound having a structure obtained by epoxidizing an alkene include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and JP-A-7-248625. Examples include compounds represented by the following formula (VI ′) described in the publication.

(In formula (VI ′), R ^{84 to} R ⁸⁶ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m1 is an integer of 1 to 5).

  Examples of the compound represented by the formula (VI ′) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α- Methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4, 5-triglycidyloxymethyls Ren, 2,4,6-glycidyloxy-methylstyrene and the like.

  Examples of the monomer having a structure obtained by epoxidizing a cycloalkene include a monomer having a structure obtained by epoxidizing a monocyclic cycloalkene, and a monomer having a structure obtained by epoxidizing a polycyclic cycloalkene. Can be mentioned. The monomer having an oxirane structure includes a compound having at least one structure selected from the group consisting of a structure obtained by epoxidizing a monocyclic cycloalkene and a structure obtained by epoxidizing a polycyclic cycloalkene and an unsaturated bond Preferably having at least one structure selected from the group consisting of a structure obtained by epoxidizing a monocyclic cycloalkene and a structure obtained by epoxidizing a polycyclic cycloalkene and a (meth) acryloyloxy group The body is more preferred.

Examples of the monocyclic cycloalkene include cyclopentene, cyclohexene, cycloheptene, and cyclooctene. Especially, a C5-C7 compound is preferable.
Specific examples of the monomer having a structure obtained by epoxidizing a monocyclic cycloalkene include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.). ), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.) Etc.

Examples of the polycyclic cycloalkene include dicyclopentene, tricyclodecene, norbornene, isonorbornene, bicyclooctene, bicyclononene, bicycloundecene, tricycloundecene, bicyclododecene, and tricyclododecene. .
Especially, a C8-C12 compound is preferable.

式（VII）及び式（VIII）において、Ｒ^８７及びＲ^８８は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子はヒドロキシ基で置換されていてもよい。
Ｘ^８７及びＸ^８８は、それぞれ独立に、単結合、炭素数１〜６のアルカンジイル基又は＊−（ＣＨ_２）_ｓ−Ｘ'−（ＣＨ_２）_ｔ−を表す。
Ｘ'は、−Ｓ−、−Ｏ−又は−ＮＨ−を表す。
ｓは、１〜６の整数を表し、ｔは、０〜６の整数を表す。ただしｓ＋ｔ≦６である。
＊は、Ｏとの結合手を表す。 Examples of the monomer having a structure obtained by epoxidizing the above polycyclic cycloalkene include 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, and a formula (VII). And at least one compound selected from the group consisting of a compound and a compound represented by formula (VIII).

In Formula (VII) and Formula (VIII), R ⁸⁷ and R ⁸⁸ 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 substituted with a hydroxy group. It may be.
X ⁸⁷ and X ⁸⁸ each independently represent a single bond, an alkanediyl group having 1 to 6 carbon atoms, or * — (CH ₂ ) _s —X ′ — (CH ₂ ) _t —.
X ′ represents —S—, —O— or —NH—.
s represents an integer of 1 to 6, and t represents an integer of 0 to 6. However, s + t ≦ 6.
* Represents a bond with O.

Specific examples of R ⁸⁷ and R ⁸⁸ include a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1- Examples thereof include hydroxy-substituted alkyl groups such as a methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
Of these, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable. More preferably, they are a hydrogen atom and a methyl group.

The alkanediyl group having 1 to 6 carbon atoms representing the X ⁸⁷ and ^{X 88,} methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl, butane-1,4-diyl Group, pentane-1,5-diyl group, hexane-1,6-diyl group and the like.
Of these, a single bond, a methylene group, an ethylene group, —O—CH ₂ —, and —O— (CH ₂ ) ₂ — are preferable. More preferably a single bond, -O- _{(CH 2)} 2 - is.

式（VII’）及び式（VIII’）において、Ｒ^８９及びＲ^９０は、それぞれ前記Ｒ^８７及びＲ^８８と同義である。 At least one compound selected from the group consisting of a compound represented by formula (VII) and a compound represented by formula (VIII) is a compound represented by the following formula (VII ′) and formula (VIII ′): It is preferable that it is at least 1 type of compound chosen from the group which consists of a compound represented by these.

In formula (VII ′) and formula (VIII ′), R ⁸⁹ and R ⁹⁰ have the same meanings as R ⁸⁷ and R ⁸⁸ , respectively.

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

Examples of the compound represented by the formula (VIII) include compounds represented by the formula (VIII-1) to the formula (VIII-15). Preferably formula (VIII-1), formula (VIII-3), formula (VIII
−5), Formula (VIII-7), Formula (VIII-9), Formula (VIII-11) to Formula (VIII-15). More preferably, Formula (VIII-1), Formula (VIII-7), Formula (VIII-9), Formula (VIII-15)
It is.

  At least one compound selected from the group consisting of the compound represented by formula (VII) and the compound represented by formula (VIII) can be used alone. Moreover, it can mix in arbitrary ratios. In the case of 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 to formula (VII): formula (VIII). 80:20.

The monomer having an oxetanyl group is preferably a compound having an oxetanyl group and an unsaturated bond, and more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3- Ethyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane or 3-ethyl-3-acryloxy And ethyl oxetane.

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

As the copolymerizable monomer (B3), for example,
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (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, dicyclopenta Nyl (meth) acrylate), (meth) acrylic acid cycloalkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

  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-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Cycloalkyl unsaturated compounds;

N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide;
N-cycloalkylmaleimides such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cyclooctylmaleimide;
N-bridged carbocyclic group-substituted maleimides such as N-adamantyl maleimide, N-norbornyl maleimide;

N-arylmaleimides such as N-phenylmaleimide;
N-aralkylmaleimides such as N-benzylmaleimide;
N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide, etc. Dicarbonylimide derivatives of

  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 alkali solubility.

  Copolymers [K1] to [K4] are described, for example, in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972). Can be produced with reference to the published methods and the cited references described in the literature.

  Specifically, monomers (B1) and (B2) constituting the copolymer, and optionally a predetermined amount of (B3), a polymerization initiator and a solvent are charged into a reaction vessel, and oxygen is substituted with nitrogen. In the absence of oxygen, the polymer is obtained by stirring, heating, and keeping the temperature. Polymerization conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of production equipment, the amount of heat generated by polymerization, and the like.

As the polymerization initiator and the solvent used here, any of those usually used in the art can be used. For example, the above-described polymerization initiator and solvent can be used.
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 the above-mentioned solvent 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 copolymer [K1], the ratio of the constituent units derived from the respective monomers is preferably in the following range with respect to the total number of moles of the constituent units constituting the copolymer [K1].
(B1) 5 to 95 mol%, more preferably 10 to 90 mol%
(B2) 5 to 95 mol%, more preferably 10 to 90 mol%.

Moreover, it is preferable that the ratio of the structural unit which originates in each monomer in copolymer [K2] exists in the following ranges with respect to the sum total of the structural unit which comprises copolymer [K2].
(B1) 2 to 40 mol%, more preferably 5 to 35 mol%
(B2) 2 to 95 mol%, more preferably 5 to 80 mol%
(B3) 1 to 65 mol%, more preferably 1 to 60 mol%.

The copolymer [K3] can be produced through a two-step process.
First, (B1) and (B3) are copolymerized in the same manner as described above to obtain a copolymer.
In this case, it is preferable that the ratio of each monomer is in the following range with respect to the total of the structural units constituting the resin.
(B1) 5-50 mol%, preferably 10-45 mol%
(B3) 50 to 95 mol%, preferably 55 to 90 mol%.

Next, a part of the carboxylic acid and / or carboxylic anhydride of (B1) derived from the copolymer of (B1) and (B3) is converted to a cyclic ether (oxiranyl group, oxetanyl group or tetrahydro) derived from (B2). Furyl group).
Therefore, the atmosphere in the flask is subsequently replaced with nitrogen to air, and (B2), a reaction catalyst, a polymerization inhibitor and the like are placed in the flask, and the reaction is continued, for example, at 60 to 130 ° C. for 1 to 10 hours. 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 this case, the number of moles of (B2) is preferably from 5 to 80 mole%, more preferably from 10 to 75 mole%, still more preferably from 15 to 70 mole%, based on the number of moles of (B1). .

The reaction catalyst is preferably used as a reaction catalyst between a carboxy group and a cyclic ether (oxiranyl group, oxetanyl group or tetrahydrofuryl group). Specific examples include trisdimethylaminomethylphenol.
The amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (B1) to (B3).
Examples of the polymerization inhibitor include hydroquinone.
As for the usage-amount of a polymerization inhibitor, 0.001-5 mass% is preferable with respect to the total amount of (B1)-(B3).

In copolymer [K4], the proportion of structural units derived from each monomer is preferably in the following range with respect to the total of monomers constituting copolymer [K4].
(B1) 2 to 40 mol%, more preferably 5 to 35 mol%
(B2) 60 to 98 mol%, more preferably 65 to 95 mol%.

  The dispersity (molecular weight distribution) and [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymers [K1] to [K4] are preferably 1.1 to 6.0, more preferably 1.2 to 4.0.

  The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 5,000 to 35,000, more preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000. When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved, which is preferable.

  The acid value of the resin (B) is preferably 50 to 150, more preferably 60 to 135, and particularly preferably 70 to 135. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic acid polymer, and is usually obtained by titration with an aqueous potassium hydroxide solution. it can.

  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 the content of the resin (B) is in the above range, a pattern can be formed and the resolution and the remaining film ratio tend to be improved.

  The photopolymerizable 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 photopolymerization initiator (D) when irradiated with light. Examples thereof include compounds having a polymerizable carbon-carbon unsaturated bond.

  The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound 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 photopolymerizable compound (C) is 7-65 mass% with respect to solid content of a coloring composition, More preferably, it is 13-60 mass%, More preferably, it is 17-55. % By mass. When the content of the photopolymerizable compound (C) is in the above range, curing is sufficiently performed, the film thickness ratio before and after development is improved, and the pattern is less likely to be undercut and adhesion is improved. There is a tendency to improve.

The photopolymerization initiator (D) is a compound capable of generating an active radical, an acid and the like to polymerize the polymerizable compound (C) when irradiated with light, and is preferably a compound that generates a radical by ultraviolet rays. . As said photoinitiator (D), an active radical generator, an acid generator, etc. are mentioned.
An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like. It is done.

  An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 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) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compounds include O-acyl oxime 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-carbazole-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, nitrobenzyl tosylate And benzoin tosylate.

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

  The content of the photopolymerization initiator (D) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass with respect to the total amount of the alkali-soluble resin and the photopolymerizable compound (C). It is. When the content of the photopolymerization initiator is within the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

The colored composition of the present invention may further contain a photopolymerization initiation assistant (F). The photopolymerization initiation assistant (F) is usually used in combination with the photopolymerization initiator (D), or a compound used for accelerating the polymerization of the photopolymerizable compound whose polymerization has been initiated by the photopolymerization initiator or It is a sensitizer.
Examples of the photopolymerization initiation assistant (F) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9 , 10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.

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

  The photopolymerization initiation assistant (F) may be used alone or in combination of two or more. Moreover, as a photopolymerization start adjuvant (F), a commercially available thing can also be used, and as a commercially available photopolymerization start adjuvant (F), brand name "EAB-F" (Hodogaya Chemical Industry ( Etc.).

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (F) include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4 -Methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4'-bis (diethylamino) benzophenone, benzyl Dimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) Benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4′-bis (diethylamino Benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone and the like, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane- 1-one / 4,4′-bis (diethylamino) benzophenone.

  When using these photopolymerization initiation assistants (F), the amount used is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles per mole of the photopolymerization initiator (D). .

  A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. The above-mentioned solvents can be appropriately selected and used. The solvent (E) contained in the coloring composition is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate and 4-hydroxy-4-methyl-2-pentanone. A solvent containing is preferable, a solvent containing at least one selected from the group consisting of propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone is more preferable, and a solvent containing propylene glycol monomethyl ether acetate is more preferable. When the solvent (E) is such a solvent, the generation of foreign matters can be suppressed and a color filter with high contrast can be obtained.

  Content of the solvent (E) in a coloring composition is 70-95 mass% with respect to a coloring composition, More preferably, it is 75-92 mass%. In other words, the solid content is 5 to 30% by mass, preferably 8 to 25% by mass with respect to the colored composition. 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 optionally contain a surfactant (G) (however, different from the pigment dispersant). As the surfactant (G), a surfactant having a fluorine atom or a silicon atom is suitable. Specific examples include at least one selected from the group consisting of silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms.
Examples of the silicone 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 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK), and the like.

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFac (trade name) F142D, F171, F172, F173, F177, F183, F183, F489, F554, R30 (manufactured by DIC Corporation), Ftop (trade name) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (tradename) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie) and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, MegaFuck (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 (G) is preferably 0.0005 to 0.3 parts by mass, more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the colored composition. When the content of the surfactant (F) is in the above range, flatness tends to be good.

The coloring composition of the present invention is preferably a negative coloring composition.
The colored composition of the present invention can be suitably used for forming a color filter or a colored pattern, and obtains a favorable colored pattern and color filter such as color density, brightness, contrast, sensitivity, resolution, heat resistance, and the like. It becomes possible. Further, an optical film, an array substrate, a color filter substrate, and the like provided with these color filters or colored patterns as a part of their constituent parts, and further these color filters or colored patterns, an optical film or array substrate, a color filter substrate, etc. It can be used in a known manner for a display device provided, for example, a device related to various colored images such as a known liquid crystal display device, an organic EL device, and a solid-state imaging device.

As a method for forming a color filter or a pattern thereof using the colored composition of the present invention, for example, the colored composition of the present invention is applied to a substrate or another resin layer (for example, another layer previously formed on the substrate). No need for a photolithographic method or a method for developing a colored layer by exposing / developing the colored layer through a photomask. And a method using a simple ink jet apparatus.
The film thickness of the coating film in this case is not particularly limited, and can be appropriately adjusted depending on the material to be used, application, and the like. .

  Examples of the method for applying the coloring composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, you may apply | coat using coaters, such as a dip coater, a bar coater, a spin coater, a slit & spin coater, and a slit coater (it may also be called a die coater, a curtain flow coater, and a spinless coater). Especially, it is preferable to apply using a spin coater.

Examples of the solvent removal / drying include natural drying, ventilation drying, and drying under reduced pressure. The specific drying temperature is preferably 10 to 120 ° C, more preferably 25 to 100 ° C. The drying time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

  Hereinafter, the manufacturing method of the pigment dispersion of the present invention, the manufacturing method of the coloring composition, the color filter as the coloring pattern, and the like will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1
<Synthesis of Dye A1>
A flask equipped with a condenser and a stirrer was charged with 15 parts of the dye represented by formula A0-1 (manufactured by Chugai Kasei), 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide, and stirred at 20 ° C. While maintaining the following, 10.9 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 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. The reaction was stirred for 5 hours at the same temperature. Subsequently, the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added, and the mixture was vigorously stirred. 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, and dried under reduced pressure at 60 ° C. to obtain 11.3 parts of dye A1 (mixed dye of dye A1-1 to dye A1-8).

（式（Ａ１）中、Ｒ_ｃは、それぞれ独立に、−ＳＯ_２ＮＨ−Ｒ_ａ、−ＳＯ_３Ｈ、−ＳＯ_３ ⁻又は−Ｈを表す。Ｒ_ａは、２−エチルヘキシルを表す。）

(In formula (A1), R _c independently represents —SO ₂ NH—R _a , —SO ₃ H, —SO ₃ ^— or —H. R _a represents 2-ethylhexyl.)

Synthesis example 2
<Synthesis of Resin B1>
133 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. The temperature was raised to 100 ° C., 82.8 g (0.47 mol) of benzyl methacrylate, 37.0 g (0.43 mol) of methacrylic acid, monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22 A solution prepared by adding 3.6 g of 2,2′-azobisisobutyronitrile to a mixture consisting of 0.0 g (0.10 mol) and 164 g of propylene glycol monomethyl ether acetate was added dropwise, and stirring was continued at 100 ° C.
Next, the atmosphere in the flask was changed from nitrogen to air, 21.5 g of glycidyl methacrylate [0.15 mol, (50 mol% with respect to the carboxy group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol,. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. to obtain a resin solution B1 (solid content: 38%) having a solid content acid value of 97 mgKOH / g.

The weight average molecular weight in terms of polystyrene measured by GPC was 9.0 × 10 ³ .
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 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-1, A-2500, A-500
(Manufactured by Tosoh Corporation)

Examples 1 and 2 and Comparative Examples 1 and 2
<Manufacture of pigment dispersion>
The ingredients listed in Table 22 were sequentially added to a beaker, and all ingredients were mixed. Then, the dispersion process was performed for 5 hours with the paint shaker using the zirconia bead of 0.65 mm diameter. The obtained uniform dispersion was filtered to remove the beads to obtain a pigment dispersion.

顔料：Ｃ．Ｉ．ピグメントブルー１５：６
染料：染料Ａ１
分散剤１：Ｄｉｓｐｅｒｂｙｋ−１６１（ビックケミー社製）
分散剤２：銅フタロシアニン誘導体（ソルスパース５０００、アビシア社製）
溶媒１：プロピレングリコールモノメチルエーテルアセテート
溶媒２：乳酸エチル

Pigment: C.I. I. Pigment Blue 15: 6
Dye: Dye A1
Dispersant 1: Disperbyk-161 (manufactured by Big Chemie)
Dispersant 2: Copper phthalocyanine derivative (Solsperse 5000, manufactured by Avicia)
Solvent 1: Propylene glycol monomethyl ether acetate Solvent 2: Ethyl lactate

Examples 3-5, Comparative Examples 3-5
<Manufacture of coloring composition>
The components described in Table 23 were mixed to obtain a colored composition.

In Table 23, each component is as follows.
Photopolymerizable compound: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE01; manufactured by Ciba Specialty Chemicals)
Surfactant: Polyether-modified silicone oil (SH8400, manufactured by Toray Dow Corning Co., Ltd.)
Solvent 1: Propylene glycol monomethyl ether acetate Solvent 2: Ethyl lactate Solvent 3: 4-Hydroxy-4-methyl-2-pentanone

<Production of color filter>
The colored composition obtained above was applied onto a 2-inch square glass substrate (Eagle 2000, manufactured by Corning) by a spin coating method.
Next, it was pre-baked at 100 ° C. for 3 minutes in a clean oven. After cooling, using an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd.), the light is irradiated with an exposure amount (365 nm) of 150 mJ / cm ^{2 in} an air atmosphere, heated at 220 ° C. for 20 minutes, and colored. A filter was produced. The film thickness of the obtained color filter was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

[Evaluation of foreign matter]
The obtained color filter surface was visually confirmed. Evaluated as ◯ when there was no foreign material, △ when a small amount of foreign material was observed, × when a large amount of foreign material was observed, and XX when a uniform film could not be obtained due to a large amount of foreign material. did. The results are shown in Table 24.

[Brightness evaluation]
About the obtained color filter, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) and brightness Y were measured. The results are shown in Table 24.

[Contrast evaluation]
The obtained color filter was sandwiched between two polarizing plates (POLAX-38S; manufactured by Luceo Co., Ltd.), and a contrast measuring device (CT-1, manufactured by Aisaka Electric Co., Ltd.), luminance meter (BM-5A, (Made by Topcon Techno House Co., Ltd.), using a cold cathode F10 lamp as the light source, the brightness of the transmitted light of the sample in parallel Nicol and crossed Nicol is measured, and the brightness in parallel Nicol and crossed Nicol The ratio to the luminance (parallel Nicols / orthogonal Nicols) was used as contrast. Prior to measuring the contrast of the color filter, the intensity of the light source was adjusted so that the contrast measured without inserting the color filter was 10,000. The results are shown in Table 24.

Synthesis example 3
<Synthesis of Dye A2>
After adding 75 parts of water to 7.7 parts of 2-amino-4-nitrophenol (manufactured by Wako Pure Chemical Industries, Ltd.), 2.0 parts of sodium hydroxide was added and dissolved. Under ice cooling, 9.5 parts of 35% aqueous sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution was added, then 30.0 parts of 35% hydrochloric acid was added little by little to dissolve, and the mixture was stirred for 2 hours. A suspension containing was obtained. Then, an aqueous solution in which 8.9 parts of amidosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 36 parts of water was slowly added to quench excess sodium nitrite.
Subsequently, 13 parts of 3-methyl-1- (3′-sulfamoyl) -5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 100 parts of water, and the pH was adjusted to 8. with sodium hydroxide. Adjusted to zero. 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 17.9 parts (yield 85%) 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 12.8 parts of the compound represented by the formula (z-1) ( 60%).

  18 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.), 170 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), 1.0 part of camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 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.

Identification of compound represented by formula (g-1) (mass spectrometry) ionization mode = ESI +: m / z = 575.3 [M-Cl ⁻ ] ⁺
Exact Mass: 610.3

4025 parts of methanol was added to 253 parts of the compound represented by the formula (z-1) to prepare a solution (s1). Further, 1080 parts of methanol was added to 153 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 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 at 60 ° C. under reduced pressure to obtain 263 parts (yield) of the compound (dye A2) represented by the formula (1-1). 65%) was obtained.
The structure of the compound represented by Formula (1-1) was determined by elemental analysis. As an analytical instrument, an ICP emission analyzer (ICPS-8100; manufactured by Shimadzu Corporation) was used.
C55.6 H4.7 N12.0 Cr3.57

Synthesis example 4
<Synthesis of Dye A3>
200 parts of water was added to 10.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), and then adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 11.1 parts of sodium nitrite was added and stirred for 30 minutes. After adding 39.0 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 10.1 parts of amidosulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  14.0 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-2), 125 parts of water and 25. N-methylpyrrolidone. After adding 0 parts, the solution was adjusted to pH 8-9 with 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours 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 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 21.4 parts (yield 87%) of the compound represented by the formula (d-3).

Compound (d-3) 0.35 g was dissolved in N, N-dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, cell length is 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax = 433 nm.

  Into a flask equipped with a condenser and a stirrer, 5.0 parts of compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were added, while maintaining at 20 ° C. or lower with stirring. 2.4 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 40 ° C., the reaction was continued for 2 hours at the same temperature, and then cooled to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water with stirring and then stirred for 30 minutes. The precipitated yellow crystals were separated by filtration, washed well with tap water, and dried at room temperature for 1 hour. Prepare a flask equipped with a condenser and a stirrer separately, add 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone, and adjust in advance while maintaining the temperature at 20 ° C. or lower with stirring. The yellow crystals obtained were added over 1 hour. After adding the yellow solid, the liquid temperature was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After adding 40 parts of methanol to the reaction solution and stirring, this mixed solution 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 exchange water, and dried under reduced pressure at 60 ° C. to obtain 3.9 parts (yield 69%) of the compound represented by the formula (III-3).

Compound (III-3) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.3 (arbitrary unit) at λmax = 431 nm.

The following reaction was performed in a nitrogen atmosphere. To 2.0 parts of compound (III-3), 4.0 parts of N-methylpyrrolidone was added and stirred for 30 minutes to prepare a reaction solution. While stirring the reaction solution at room temperature, 0.1 part of sebacic acid chloride was added dropwise. After completion of dropping, the mixture was further stirred for 8 hours. The reaction solution was poured into 300 parts of water, 80 parts of ethyl acetate was added, and the mixture was stirred for 30 minutes. The organic phase was separated using a separatory funnel, and further washed with 500 parts of water, 500 parts of a 10% aqueous sodium carbonate solution, 500 parts of a 10% aqueous acetic acid solution, and 500 parts of ion-exchanged water. The separated organic phase was evaporated to obtain 2.0 parts of dye A3 represented by formula (I-6). Yield 85%.

The structure of compound (I-6) was determined by mass spectrometry. As the mass spectrometer, JMS-700 (manufactured by JEOL Ltd.) was used.
Mass spectrometry: ionization mode = FD +: m / z = 1200

Compound (I-6) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm).
This compound showed an absorbance of 2.2 (arbitrary unit) at λmax = 431 nm.

Synthesis example 5
<Synthesis of Resin Solution B2>
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to form a nitrogen atmosphere, 935 parts by mass of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 140 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the following formula (I-1-1) and a formula (I-1 The compound represented by -2) is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 140 parts by mass of ethyl lactate, and the solution is added using a dropping funnel. It was dripped in the flask kept at 70 degreeC over 4 hours. On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. did. After completion of dropping of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature. The weight average molecular weight Mw was 9.0 × 10 ³ , the solid content was 26% by mass, and the solution acid value was A resin solution B2 of 32 mg-KOH / g was obtained.

Synthesis Example 6
<Synthesis of Resin Solution B3>
250 parts by mass of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas introduction tube. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the temperature of the solution in the flask was raised to 100 ° C., 152.6 parts by mass of benzyl methacrylate, 41.7 parts by mass of methacrylic acid, 1.5 parts by mass of azobisisobutyronitrile, and 150 parts by mass of propylene glycol monomethyl ether acetate. The mixture consisting of was dropped into the flask using a dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further continued at 100 ° C. for 2.5 hours to obtain a resin solution B3 having a weight average molecular weight Mw of 2.3 × 10 ⁴ , a solid content of 34% by mass, and a solution acid value of 47 mg-KOH / g. It was.

Examples 6 and 7
<Manufacture of pigment dispersion>
The ingredients listed in Table 25 were sequentially charged into a beaker and all ingredients were mixed. Then, the dispersion process was performed for 5 hours with the paint shaker using the zirconia bead of 0.65 mm diameter. The obtained uniform dispersion was filtered to remove the beads, and pigment dispersions 5 and 6 were obtained.

顔料２：Ｃ．Ｉ．ピグメントレッド２５４
顔料３：Ｃ．Ｉ．ピグメントグリーン５８
分散剤３：アクリル系顔料分散剤
溶媒１：プロピレングリコールモノメチルエーテルアセテート

Pigment 2: C.I. I. Pigment Red 254
Pigment 3: C.I. I. Pigment Green 58
Dispersant 3: Acrylic pigment dispersant Solvent 1: Propylene glycol monomethyl ether acetate

Examples 8 and 9
<Manufacture of coloring composition>
The components described in Table 26 were mixed to obtain a colored composition.

In Table 26, each component is as follows.
Photopolymerizable compound: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE01; manufactured by BASF Japan)
Surfactant: Polyether-modified silicone oil (SH8400, manufactured by Toray Dow Corning Co., Ltd.)
Solvent 1: Propylene glycol monomethyl ether acetate Solvent 4: Cyclohexanone

<Production of color filter>
The coloring composition was applied by spin coating on a 2-inch square glass substrate (Eagle 2000, manufactured by Corning).
Next, it was pre-baked at 100 ° C. for 3 minutes in a clean oven. After cooling, using an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd.), in an air atmosphere, irradiated with light at an exposure amount (365 nm) of 150 mJ / cm ² and heated at 230 ° C. for 30 minutes to produce a color A filter was produced.
About the obtained color filter, it carried out similarly to Example 5, and evaluated the foreign material and the brightness.

[Contrast evaluation]
The obtained color filter was sandwiched between two polarizing plates (POLAX-38S; manufactured by Luceo Co., Ltd.), and a contrast measuring device (CT-1, manufactured by Aisaka Electric Co., Ltd.), luminance meter (BM-5A, (Made by Topcon Techno House Co., Ltd.), using a cold cathode F10 lamp as the light source, the brightness of the transmitted light of the sample in parallel Nicol and crossed Nicol is measured, and the brightness in parallel Nicol and crossed Nicol The ratio to the luminance (parallel Nicols / orthogonal Nicols) was used as contrast. Prior to measuring the contrast of the color filter, the intensity of the light source was adjusted so that the contrast measured without sandwiching the color filter would be 30000. The results are shown in Table 27.

In the colored compositions of Examples 3 to 5, 8 and 9, good color filters with few foreign matters were obtained. Also, excellent brightness and contrast were confirmed.
On the other hand, in Comparative Examples 3 to 5, a large amount of foreign matter was generated. Further, the value of x was large, the chromaticity was strong with reddishness, and the contrast was inferior. In particular, in Comparative Example 5, since there were many foreign substances, normal evaluation could not be performed.

  Since the method for producing the pigment dispersion of the present invention can uniformly disperse the dye and the pigment by a simple method, various colored compositions used in various production processes as well as semiconductor production processes and the like. It can be used extensively when producing colored members and the like.

Claims (8)

Including a step of uniformly dispersing a dye and a pigment simultaneously in a solvent,
It said dye is a dye containing the azo compound represented by the following formula (2-1), a manufacturing method of a pigment dispersion liquid.

[In Formula (2-1),
Z ¹ , Z ² and Z ³ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a halogen atom, and are included in Z ¹ , Z ² and Z ³ . more -CH ₂ - may be replaced by -CO- or -O-.
R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, a C 1-16 monovalent aliphatic hydrocarbon group optionally having an alkoxy group having 1 to 8 carbon atoms or a carboxy group, or The C2-C18 acyl group which may have a C1-C8 alkoxy group or a carboxy group is represented.
A ¹ and A ² each independently have a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group. Represents a C6-C14 divalent aromatic hydrocarbon group which may be present.
B ¹ and B ² may each independently have a hydroxy group, an oxo group, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, a cyano group, an amino group, or an N-substituted amino group. A monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms, or a hydroxy group, an oxo group, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, a cyano group, an amino group, or an N-substituted amino group. A monovalent aromatic heterocyclic group having 3 to 14 carbon atoms which may be present. ]   The method for producing a pigment dispersion according to claim 1, wherein the dye and the pigment are contained in a mass ratio of dye: pigment = 1: 99 to 99: 1. The pigment is C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The method for producing a pigment dispersion according to claim 1 or 2 , wherein the pigment dispersion contains at least one selected from the group consisting of CI Pigment Red 254. The pigment is C.I. I. The method for producing a pigment dispersion according to any one of claims 1 to 3 , which is a pigment containing CI Pigment Blue 15: 6. A pigment dispersion obtained by the method for producing a pigment dispersion according to any one of claims 1 to 4 , and at least one selected from the group consisting of a solvent, a resin, a photopolymerizable compound, and a photopolymerization initiator. The manufacturing method of the coloring composition including the process to mix. The coloring pattern formed using the coloring composition obtained by the manufacturing method of the coloring composition of Claim 5 . A color filter comprising the colored pattern according to claim 6 . The liquid crystal display device comprising a color filter according to claim 7 wherein.