KR20120112121A - A salt for dye - Google Patents

Abstract

PURPOSE: A salt for dye is provided to enhance spectral concentration showing color depth of unit concentrate and to use the dye for a color filter. CONSTITUTION: A salt of formula (0) contains anion of formula (A1) and cation of formula (A2). The anion (A1) is selected according to the color of a target color filter. The salt containing the anion (A1) is enough dissolved in a solvent.

Description

Salt for dyes {A SALT FOR DYE}

The present invention relates to salts useful as dyes.

As a dye of a metal complex salt compound, C. I. Solvent Yellow 21 represented by the following formula which is a dye of the chromium complex which makes an azo compound a ligand in Industrial Dyes Chemistry, Properties, Applications, WILEY-VCH, 2003 is known, for example.

In C. I. Solvent Yellow 21, the spectral concentration was not always satisfactory enough.

The present invention is the following [1]? [10] will provide.

[1] A salt represented by formula (0).

[In formula (0), R <^1> is C1-C? The monovalent saturated hydrocarbon group of 8 is represented, and the hydrogen atoms contained in the saturated hydrocarbon group are -OR ⁸ , -COOR ⁸ , -OCOR ⁸ , -CONR ⁸ R ⁹ , and 6? It may be substituted by the 10 monovalent aromatic hydrocarbon group or the halogen atom, and -CH ₂ -contained in the saturated hydrocarbon group may be substituted by -CO-.

R ² represents a hydrogen atom, —CN or —CONH ₂ .

R ³ is C 1? The alkyl group of 4 is shown.

R ⁴ ? R ⁷ is each independently -R ⁸ , -OR ⁸ , -COOR ⁸ , -COR ⁸ , -OCOOR ⁸ , -OCOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, -SO ₂ NR ⁸ R ⁹ or -NR ¹¹ R ¹² or R ⁴ and R ⁵ , R ⁵ and R ⁶ and R ⁶ and R ⁷ are bonded to each other to contain carbon of the benzene ring 6? Forms a seven-membered ring.

R ⁸ and R ⁹ each independently represent a hydrogen atom and 1? Monovalent aliphatic hydrocarbon group of 8, carbon number 7? 12 aralkyl group or C6? The monovalent aromatic hydrocarbon group of 10 is represented, and the hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group, and the aromatic hydrocarbon group may be substituted with -OR ¹⁰ .

R ¹⁰ is a hydrogen atom, carbon number 1? Monovalent saturated hydrocarbon groups of 8 or 6? 10 monovalent aromatic hydrocarbon group is shown.

R ¹¹ and R ¹² each independently represent a hydrogen atom and 1? Monovalent aliphatic hydrocarbon group of 8, carbon number 2? Or an acyl group or tetrahydrofurfuryl group of 8, or R ¹¹ and R ¹² are bonded to each other to form a ring containing a nitrogen atom.

The ring Z ¹ and the ring Z ² each independently represent an aromatic ring which may have a substituent, and R ²¹ and R ²² independently of each other may have a substituent having 1 to 4 carbon atoms. An aliphatic hydrocarbon group of 12 or a hydrogen atom, and R ²³ and R ²⁴ independently of each other may have a C 1? Or an aliphatic hydrocarbon group of 12 or a hydrogen atom, or R ²³ and R ²⁴ are combined to form an alkanediyl group. R ²⁵ and R ²⁶ may each independently have a substituent. Or an aliphatic hydrocarbon group of 12 or a hydrogen atom, or R ²⁵ and R ²⁶ become one to form an alkanediyl group. R ²⁷ and R ²⁸ independently of each other may have a substituent of 1? Or an aliphatic hydrocarbon group of 12 or a hydrogen atom, or R ²⁷ and R ²⁸ become one to form an alkanediyl group. X ¹ represents a hydrogen atom or a chlorine atom.]

[2] R ⁴ ? R ⁷ independently of one another is -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K or -SO ₂ NR ⁸ R ⁹ The salt as described in phosphorus [1].

[3] The carbon number of R ¹ which may be substituted with -OH or -OCOR ⁸ ? The salt as described in [1] or [2] which is a monovalent saturated hydrocarbon group of 8.

[4] R ⁴ ? [1] wherein at least three of R ⁷ are hydrogen atoms? The salt according to any one of [3].

[5] [1], where R ² is —CN? The salt as described in any one of [4].

[6] R ²³ ? R ²⁶ independently from each other C 1? [1] being a monovalent aliphatic hydrocarbon group of 8? The salt as described in any one of [5].

[7] [1], wherein R ²¹ and R ²² are methyl groups; The salt as described in any one of [6].

[8] [ ¹ ], wherein Z ¹ and Z ² are benzene rings which may be substituted with a methyl group; The salt as described in any one of [7].

[9] [1] Dye which uses the salt as described in any one of [8] as an active ingredient.

[10] A colored resin composition containing the dye, the resin and the solvent according to [9].

Salts of the present invention exhibit good spectral concentrations.

The salt of this invention is represented by the anion represented by the following formula (A1) (hereinafter may be called "anion (A1)"), and the cation represented by the following formula (A2) (hereinafter referred to as "cation (A2)" It may be a salt (hereinafter sometimes referred to as "salt (0)") consisting of).

R ⁴ in salt (0)? R ⁷ independently of one another is -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K or -SO ₂ NR ⁸ R ⁹ Is preferably.

Also included in the present invention are tautomers of the salts of the present invention.

Anion A1 can be selected according to the color of the color filter made into the objective. It is preferable that the salt containing anion (A1) fully melt | dissolves in a solvent. Moreover, it is preferable to melt | dissolve an anion (A1) to the extent which can pattern-form in the developing solution used for pattern formation.

In anion (A1), it is C1-C1 in R <^1> and R <^10> . Examples of the monovalent saturated hydrocarbon group of 8 include straight chains such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group. Type saturated hydrocarbon group;

Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethyl Butyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl , 1-propylbutyl group, 1- (1-methylethyl) butyl group, 1- (1-methylethyl) -2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group , 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-n-propylpentyl group , 2-propylpentyl group, 1- (1-methylethyl) pentyl group, 1-butylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl-3-methylbutyl group, 1- (1,1 -Dimethylethyl) butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethyl Butyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3, 3-dimethylpentyl group, 3,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1- Methylbutyl group, 2-ethyl-3-methylbutyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5- Dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl Real group, 3, 5- dimethylhexyl group, 4, 4- dimethylhexyl group, 4, 5- dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3- methylpentyl group, 1-ethyl- 4-methylpentyl group, 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl- 1-methylpentyl group, 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methyl moiety Methyl group, 1-propyl-2-methylbutyl group, 1-propyl-3-methylbutyl group, 1- (1-methylethyl) -1-methylbutyl group, 1- (1-methylethyl) -2-methylbutyl Branched chain saturated hydrocarbon groups such as groups, 1- (1-methylethyl) -3-methylbutyl group, 1,1-diethylbutyl group and 1,2-diethylbutyl group;

Cyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, are mentioned.

In anion (A1), C1-C8 in R <^8> and R <^9> . As monovalent aliphatic hydrocarbon group of 8, a vinyl group, a propenyl group, an isopropenyl group, butenyl group, 2-methylpropenyl group etc. are mentioned besides the group illustrated by the said linear saturated hydrocarbon group and the branched chain saturated hydrocarbon group. have.

Carbon number at R ⁸ and R ⁹ 7? Examples of the 12 aralkyl group include benzyl group, phenylethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, diphenylmethyl group and the like.

Carbon number at R ⁸ , R ⁹ and R ¹⁰ ? Examples of the 10 monovalent aromatic hydrocarbon group include a phenyl group, toluyl group, xylyl group, naphthyl group, biphenyl group, fluorenyl group and anthryl group.

Examples of the saturated hydrocarbon group in which -CH ₂ -is substituted with -CO- include, for example, an acetyl group, 3-oxobutyl group, 2-oxobutyl group, 3-oxopentyl group, 2-oxopentyl group, and 3-oxo Oxo group containing saturated hydrocarbon groups, such as a hexyl group;

Penacyl group, 2-oxo-2-naphthylethyl group, 2-oxo-2-hydroxyphenylethyl group, 2-oxo-2-hydroxynaphthylethyl group, 2-oxo-2-methoxyphenylethyl group, 2-oxo The aromatic hydrocarbon group, oxo group containing saturated hydrocarbon group, etc. of a 2-methoxy naphthyl ethyl group, 2-oxo-3-phenylpropyl group, and 2-oxo-3- naphthylpropyl group are mentioned.

As a saturated hydrocarbon group in which a hydrogen atom is substituted by the halogen atom, for example, a fluoromethyl group, trifluoromethyl group, fluoroethyl group, fluoropropyl group, fluorobutyl group, chloromethyl group, chloroethyl group, chloropropyl group, chloro A butyl group, bromomethyl group, bromoethyl group, bromopropyl group, bromobutyl group, iodomethyl group, iodoethyl group, iodopropyl group, iodobutyl group, etc. are mentioned.

As -OR <^8> , For example, a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, phenoxy A time period, a benzyloxy group, a benzoyloxy group, etc. are mentioned.

As -OR ⁸ substituted with -OR ¹⁰ , for example, a methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, 1-ethoxypropyl group, 2-ethoxy Propyl group, 1-ethoxy-1-methylethyl group, 1-methyl-2-ethoxyethyl group, 1- (1-methylethoxy) propyl group, 2- (1-methylethoxy) propyl group, 1- ( 1-methylethoxy) -1-methylethyl group, 2- (1-methylethoxy) -1-methylethyl group, 3-ethoxypropyl group, etc. are mentioned.

Saturated hydrocarbon group that is substituted with a hydrogen atom is -OR ⁸ may be, for example, hydroxy methyl, hydroxy ethyl, hydroxy propyl, hydroxy butyl, hydroxy, methoxy-methyl, 2-hydroxy-ethoxy-methyl, Hydroxyl group-containing saturated hydrocarbon groups such as 2-hydroxymethoxyethyl group, 2- (2-hydroxyethoxy) ethyl group and 2-oxo-4-hydroxybutyl group;

Methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, 2-oxo-4-methoxybutyl group, etc. Alkoxy group-containing saturated hydrocarbon group;

Methoxymethoxymethyl group, 2-methoxyethoxymethyl group, ethoxymethoxymethyl group, 2-ethoxyethoxymethyl group, propoxymethoxymethyl group, 2-propoxyethoxymethyl group, 2-methoxymethoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2-ethoxymethoxyethyl group, 2- (2-ethoxyethoxy) ethyl group, 2-propoxymethoxyethyl group, 2- (2-propoxyethoxy) Alkoxyalkyl group containing saturated hydrocarbon groups, such as an ethyl group;

Phenyloxymethyl group, 1-naphthyloxymethyl group, 2-naphthyloxymethyl group, hydroxyphenyloxymethyl group, hydroxynaphthyloxymethyl group, methoxyphenyloxymethyl group, methoxynaphthyloxymethyl group, 3-phenoxy-2 Aryloxy group-containing saturated hydrocarbon groups such as oxopropyl group;

Ar such as benzyloxymethyl group, naphthylmethoxymethyl group, hydroxybenzyloxymethyl group, hydroxynaphthylmethoxymethyl group, methoxybenzyloxymethyl group, methoxynaphthylmethoxymethyl group, phenyloxyethoxymethyl group, naphthyloxyethoxymethyl group Alkyloxy group containing saturated hydrocarbon group etc. are mentioned.

Roneun -COOR ^8, for example, a methoxycarbonyl group, and on the like ethoxycarbonyl group, a benzyloxycarbonyl group.

Saturated hydrocarbon group that is substituted with a hydrogen atom is -COOR ^8, for example, carboxymethyl group, carboxyethyl group, carboxypropyl group, a carboxy-butyl carboxyl group-containing saturated hydrocarbon group and the like;

Methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxycarbonylmethyl group, propoxycarbonylethyl group, butoxycarbonylmethyl group, butoxycarbonylethyl group, phenoxy Alkoxycarbonyl group-containing saturated hydrocarbon groups such as methoxycarbonylmethyl group, 2-hydroxyethoxycarbonylmethyl group and 2-methoxyethoxycarbonylmethyl group;

Aryloxycarbonyl group-containing saturated hydrocarbon groups such as phenoxycarbonylmethyl group and naphthyloxycarbonylmethyl group;

Aralkyloxycarbonyl group-containing saturated hydrocarbon groups such as benzyloxycarbonylmethyl group and naphthylmethoxycarbonylmethyl group;

2-oxopropoxycarbonylmethyl group, 2- (2-oxopropoxycarbonyl) ethyl group, 3- (2-oxopropoxycarbonyl) propyl group, 2-oxobutoxycarbonylmethyl group, 2- (2- Oxobutoxycarbonyl) ethyl group, 3- (2-oxobutoxycarbonyl) propyl group, 2-oxopentyloxycarbonylmethyl group, 2- (2-oxopentyloxycarbonyl) ethyl group, 3- (2-oxo Pentyloxycarbonyl) propyl group, 3-oxobutoxycarbonylmethyl group, 2- (3-oxobutoxycarbonyl) ethyl group, 3- (3-oxobutoxycarbonyl) propyl group, 3-oxopentyloxycarbon Bonylmethyl group, 2- (3-oxopentyloxycarbonyl) ethyl group, 3- (3-oxopentyloxycarbonyl) propyl group, 2-oxohexyloxycarbonylmethyl group, 2- (2-oxohexyloxycarbon A saturated hydrocarbon group containing an alkoxycarbonyl group in which -CH ₂ -such as a nil) ethyl group and a 3- (2-oxohexyloxycarbonyl) propyl group are substituted with -CO-;

3-methoxycarbonyl-2-oxopropyl group, 4-methoxycarbonyl-3-oxobutyl group, 5-methoxycarbonyl-4-oxopentyl group, 3-ethoxycarbonyl-2-oxopropyl Group, 4-ethoxycarbonyl-3-oxobutyl group, 5-ethoxycarbonyl-4-oxopentyl group, 3-propoxycarbonyl-2-oxopropyl group, 4-propoxycarbonyl-3- Oxobutyl group, 5-propoxycarbonyl-4-oxopentyl group, 4-methoxycarbonyl-2-oxobutyl group, 4-methoxycarbonyl-3-oxopentyl group, 5-methoxycarbonyl- 4-oxohexyl group, 4-ethoxycarbonyl-2-oxobutyl group, 4-ethoxycarbonyl-3-oxopentyl group, 5-ethoxycarbonyl-4-oxohexyl group, 4-propoxycar It contains alkoxycarbonyl groups such as a carbonyl-2-oxobutyl group, 4-propoxycarbonyl-3-oxopentyl group, and 5-propoxycarbonyl-4-oxohexyl group, and -CH ₂ -is substituted with -CO-. The saturated hydrocarbon group etc. which were used are mentioned.

Saturated hydrocarbon group that is substituted with a hydrogen atom is -CONR ⁸ R ⁹ is, for example, N- methyl-aminocarbonyl-methyl, N- methyl-aminocarbonyl group, N, N- dimethyl-aminocarbonyl group, N, N- Alkyl group substituted carbamoyl group-containing saturated hydrocarbon groups such as dimethylaminocarbonylethyl group, N, N-ethylmethylaminocarbonylmethyl group and N, N-ethylmethylcarbonylethyl group;

Aryl group-substituted carbamoyl group-containing saturated hydrocarbon groups such as N-phenylaminocarbonylmethyl group, N, N-phenylmethylcarbonylmethyl group, N, N-diphenylcarbonylmethyl group and N, N-phenylbenzylcarbonylmethyl group;

And aralkyl group-substituted carbamoyl group-containing saturated hydrocarbon groups such as N-benzylaminocarbonylmethyl group, N, N-dibenzylcarbonylmethyl group, and N, N-bis (2-phenylethyl) carbonylmethyl group.

-OCOR ⁸ roneun, for example, there may be mentioned acetyl-oxy group, acryloyloxy group kicking blood, benzoyloxy group and the like.

Saturated hydrocarbon group that is substituted with a hydrogen atom -OCOR ^8, for example, acetyloxy group, acetyloxy group, ethyl carbonyloxy group, ethyl carbonyloxy group, propyl carbonyloxy group, propyl carbonyloxy group, Butylcarbonyloxymethyl group, butylcarbonyloxyethyl group, hexanoyloxyethyl group, 2-ethylbutyryloxyethyl group, 2-ethylhexanoyloxyethyl group, 2-propylhexanoyloxyethyl group, pivaloyloxyethyl group, 2-methyl Alkylcarbonyloxy group-containing saturated hydrocarbon groups such as propionyloxyethyl group;

Benzoyloxymethyl group, benzoyloxyethyl group, naphthyloxycarbonylmethyl group, benzylcarbonyloxymethyl group, naphthylmethylcarbonyloxymethyl group, methylbenzoyloxymethyl group, 2-methylbenzoyloxyethyl group, 4-methylbenzoyloxyethyl group, 3, Aromatic hydrocarbon groups such as 4-dimethylbenzoyloxyethyl group, hydroxybenzoyloxymethyl group, methoxybenzoyloxymethyl group, 4-methoxybenzoyloxyethyl group, 3,4-dimethoxybenzoyloxyethyl group and carbonyloxy group-containing saturated hydrocarbon group Etc. can be mentioned.

Examples of -COR ⁸ include an acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, and the like.

As -OCOOR ⁸ , a methoxycarbonyloxy group, an ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyloxy group, iso part, for example Oxycarbonyloxy group, sec-butoxycarbonyloxy group, n-pentyloxycarbonyloxy group, phenoxycarbonyloxy group, etc. are mentioned.

Hydrogen atom has 6 carbon atoms? As a saturated hydrocarbon group substituted by the 10 aromatic hydrocarbon group, a benzyl group, the 1-naphthyl methyl group, 2-naphthyl methyl group, group represented by a following formula etc. are mentioned, for example.

In anion (A1), as R <^1> , C1-C? Monovalent aliphatic hydrocarbon group of ⁸ , the hydrogen atom is substituted by -OR ⁸ Monovalent aliphatic hydrocarbon group of ⁸ , having 1 to 4 carbon atoms where the hydrogen atom is substituted with -COOR ⁸ ; Monovalent aliphatic hydrocarbon group of ⁸ , having 1 to 4 carbon atoms where the hydrogen atom is substituted with -OCOR ⁸ ; The monovalent aliphatic hydrocarbon group of 8 is preferable, and a formula (f-1)? Groups respectively represented by formula (f-16) are more preferable, and groups respectively represented by formula (f-1), formula (f-7), formula (f-15) and formula (f-16) are more preferable. If R <^1> is the said group, the compound of this invention tends to show high solubility in an organic solvent. Formula (f-1)? In formula (f-16), * represents a bonding position with a nitrogen atom on the pyridone ring.

R ² is a hydrogen atom, —CN or —CONH ₂ . Especially, -CN is preferable at the point which obtains a raw material easily.

R ³ may be substituted with a hydrogen atom or a halogen atom. 4 is an alkyl group.

Carbon number 1? As an alkyl group of 4, a methyl group, an ethyl group, n-propyl group, isopropyl group, N-butyl group, sec-butyl group, tert- butyl group etc. are mentioned, for example.

1 to 3 carbon atoms substituted by halogen atoms As an alkyl group of 4, a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned, for example.

As R ³ , a methyl group and a trifluoromethyl group are preferable, and a methyl group is more preferable.

R ⁴ ? R ⁷ are each independently —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K, —SO ₂ NR ⁸ R ⁹ Or -NR ¹¹ R ¹² , and -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K or -SO _2, more preferably from NR ⁸ R ^9. R ⁴ ? More preferably, at least three of R ⁷ are hydrogen atoms. R ⁴ ? When R <^7> is the said group, there exists a tendency for the color density of a salt to become high.

R ⁴ ? As -NR ¹¹ R ¹² in R ⁷ , for example, N-methylamino group, N, N-dimethylamino group, N-ethylamino group, N, N-diethylamino group, N-propylamino group, N, N- Dipropylamino group, N-butylamino group, N, N-dibutylamino group, N-pentylamino group, N-acetylamino group, etc. are mentioned.

Examples of -NR ¹¹ R ¹² in which R ¹¹ and R ¹² combine with each other to form a ring containing a nitrogen atom include 1-pyrazolyl group, pyrrolidino group, piperidino group, and morpholino group. .

Especially, N-acetylamino group is preferable at the solubility with respect to an organic solvent.

R ⁴ ? Roneun -SO ₂ NR ⁸ R ⁹ in R ^7, there may be mentioned an unsubstituted sulfamoyl group, N-1 substituted sulfamoyl and N, N-2-substituted sulfamoyl group.

As an N-1 substituted sulfamoyl group, For example, 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-sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl 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-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group , N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N- Octyl sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexyl sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, Fats such as N-allyl sulfamoyl group Of a hydrocarbon-substituted N-1 substituted sulfamoyl group;

N- (2-hydroxyethyl) sulfamoyl group, N- (3-hydroxypropyl) sulfamoyl group, N- (2-hydroxypropyl) sulfamoyl group, N- (2,3-dihydroxypropyl A) hydroxyl group such as sulfamoyl group, N- (2-hydroxybutyl) sulfamoyl group, N- (4-hydroxybutyl) sulfamoyl group, N- (1-hydroxymethylethyl) sulfamoyl group N-1 substituted sulfamoyl group substituted with aliphatic hydrocarbon group;

N- (2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N-methoxypropylsulfamoyl group, N- Ethoxypropyl sulfamoyl group, N-propoxypropyl sulfamoyl group, N-isopropoxypropyl sulfamoyl group, N-hexyloxypropyl sulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N N substituted with an alkyl group or cycloalkyl group having an alkoxy group such as-(3-tert-butoxypropyl) sulfamoyl group, N- (4,4-dimethoxybutyl) sulfamoyl group, N-methoxyhexylsulfamoyl group -1 substituted sulfamoyl group;

N-1 substituted sulfamoyl groups substituted with aliphatic hydrocarbon groups having an alkoxyalkyl group such as N- [1- (2-ethoxyethoxy) propyl] sulfamoyl group;

N-1 substituted sulfamoyl groups substituted with aryl groups such as N-phenylsulfamoyl group and N- (1-naphthyl) sulfamoyl group;

N-benzyl sulfamoyl 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) sulphate N-1 substituted sulfamoyl groups substituted with aralkyl groups such as pamoyl group and N- (3-phenyl-1-methylpropyl) sulfamoyl group;

N- (3,4,5-trimethoxybenzyl) sulfamoyl group, N- [2- (3,4-dimethoxyphenyl) ethyl] sulfamoyl group, N- [2- (2-ethoxyphenyl) N-1 substituted sulfamoyl group substituted with an aralkyl group having a substituent such as ethyl] sulfamoyl group;

Examples of the N, N-2 substituted sulfamoyl group include N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, and N, N-propylmethyl Sulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamo N, N-substituted sulfamoyl group substituted by two aliphatic hydrocarbon groups, such as a diary and N, N-heptylmethyl sulfamoyl group;

Substitutions such as N, N-bis (2-hydroxyethyl) sulfamoyl group, N, N-bis (2-methoxyethyl) sulfamoyl group, N, N-bis (2-ethoxyethyl) sulfamoyl group N, N-2 substituted sulfamoyl group etc. which were substituted by the aliphatic hydrocarbon group which has these are mentioned.

Roneun -SO ₂ R ⁸ and R ⁹ in NR ⁸ R ^9, C 6? 8, branched chain alkyl group, allyl group, phenyl group, carbon number 8? 10 aralkyl group, 2? 8 hydroxyl group containing alkyl group or aryl group, or C2? The alkoxy group-containing alkyl group or aryl group of 8 is preferable, and it is more preferable that it is 2-ethylhexyl group.

It is preferable that the salt containing cation (A2) fully melt | dissolves in a solvent. In addition, it is preferable that the salt containing cation (A2) is melt | dissolved in the developing solution used for pattern formation mentioned later so that the said pattern formation can be carried out.

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

In cation (A2), ring Z ¹ and ring Z ² represent an aromatic ring which may have a substituent independently of each other. As said aromatic ring, a benzene ring or a naphthalene ring is preferable.

As a substituent of the said benzene ring and the said naphthalene ring, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, sec-butyl group, tert- butyl group, pentyl group, isopentyl group Aliphatic hydrocarbon groups such as neopentyl group and tert-pentyl group;

Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group and p-cumenyl group;

Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and pentyloxy group;

Aryloxy groups such as phenoxy group;

Aralkyloxy groups such as benzyloxy group;

Acyloxy groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group;

Methyl sulfamoyl group, dimethyl sulfamoyl group, ethyl sulfamoyl group, diethyl sulfamoyl group, n-propyl sulfamoyl group, di-n-propyl sulfamoyl group, isopropyl sulfamoyl group, diisopropyl sulfamoyl group, alkyl sulfamoyl groups such as n-butyl sulfamoyl group and di-n-butyl sulfamoyl group;

Alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group and tert-butylsulfonyl group;

Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;

Nitro group and cyano group are mentioned.

In addition, when such a substituent has a hydrogen atom, the hydrogen atom is halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, for example; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group Alkoxy groups such as butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and pentyloxy group; aryloxy groups such as phenoxy group and benzyloxy group; phenyl group, o-tolyl group, m-tolyl group, An aromatic hydrocarbon group such as p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group; carboxyl group, cyano group, nitro group or the like may be substituted.

In view of solubility, the ring Z ¹ and the ring Z ² are each preferably a benzene ring which may be substituted, and more preferably an unsubstituted benzene ring.

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

In cation (A2), R ²¹ and R ²² may have a substituent. In the case of an aliphatic hydrocarbon group of 12, as the aliphatic hydrocarbon group, for example, methyl group, ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2- Propynyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1 -Methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, and octyl group.

As a substituent in this aliphatic hydrocarbon group, a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m- cumenyl group, p-cume Aromatic hydrocarbon groups, such as a nil group;

And alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and benzyloxy group.

Halogen groups such as fluoro group, chloro group, bromo group and iodo group;

Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.

In cation (A2), R <^21> and R <^22> may mutually independently have a C1-C? It is a 12 aliphatic hydrocarbon group or a hydrogen atom, Preferably it is C1-C1 which does not have a substituent. It is an aliphatic hydrocarbon group of 8, More preferably, it is C1-C1 which does not have a substituent. It is an alkyl group of 4, More preferably, it is n-butyl group. It is preferable that R ²¹ and R ²² are the same group. When R ²¹ and R ²² are the same group, the molar extinction coefficient tends to be better.

For cation (A2), R ²³ ? Carbon number which R ²⁸ may have a substituent? In the case of an aliphatic hydrocarbon group or a hydrogen atom of 12, as the aliphatic hydrocarbon group, for example, methyl group, ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-prop Phenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert- Pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group.

Examples of the substituent in the aliphatic hydrocarbon group include a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, Alkoxy groups, such as a phenoxy group and the benzyloxy group, are mentioned.

Halogen groups such as fluoro group, chloro group, bromo group and iodo group;

Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.

As the alkanediyl group, for example, methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-di Diary, hexane-1,6-diyl group.

For cation (A2), R ²³ ? Carbon number which R ²⁸ may have a substituent independently of each other? When showing the aliphatic hydrocarbon group or hydrogen atom of 12, Preferably it is C1-C? Which may have a substituent. It is an alkyl group of 3, More preferably, it is a methyl group which may have a substituent, More preferably, it is a methyl group which does not have a substituent. It is preferable that R <^23> and R <^24> , R <^25> and R <^26> , R <^27> and R <^28> are the same group.

In cation (A2), R <^23> and R <^24> become one and C1-C? When forming the alkanediyl group of 12, As said alkanediyl group, Preferably it is C4? It is an alkanediyl group of 7, More preferably, it is a pentane- 1, 5- diyl group.

In cation (A2), R <^25> and R <^26> become one and C1-C? When forming the alkanediyl group of 12, As said alkanediyl group, Preferably it is C4? It is an alkanediyl group of 7, More preferably, it is a pentane- 1, 5- diyl group.

As a hydrocarbon ring formed with the said alkanediyl group, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, etc. are mentioned. Moreover, the said hydrocarbon ring may have a substituent, As a specific example of a substituent, C3 or less alkyl groups, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, are mentioned.

In cation (A2), R <^27> and R <^28> become one and C1-C? When forming the alkanediyl group of 12, As said alkanediyl group, Preferably it is C3-C. It is an alkanediyl group of 5, More preferably, it is a propane-1, 3- diyl group.

As a hydrocarbon ring formed from the said alkanediyl group, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, etc. are mentioned. Moreover, the said hydrocarbon ring may have a substituent, As a specific example of a substituent, C3 or less alkyl groups, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, are mentioned.

In compound (0), as cation (A2), it is a formula (II-1)? The cation represented by (II-36) is preferable.

As salt (0), it is salt (I-1)? Salt (I-300) etc. are mentioned. A ⁺ represents cation (A2). In Table 1, the column of A ⁺ describes the number of the formula of the cation illustrated above. ⁿ Bu represents an n-butyl group and Et represents an ethyl group. In addition, when a formula number is described in R <^1> column, the formula number of the group shown above is described.

As an aspect of the salt of this invention, the following are mentioned, for example.

The compound represented by a formula (0-A).

[Wherein,

R ^{1 -A} has 1? C1-C1 substituted by monovalent saturated hydrocarbon group of 3, hydroxyl group A monovalent saturated hydrocarbon group of 3 or a carbon atom substituted with -OCOR ^{8 - A} ; A monovalent saturated hydrocarbon group of 3 (where R ^{8 -A} represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms),

R ^5-A represents a hydrogen atom, -OR ^{8 -B} (where R ^{8 -B} represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms), or -NHR ^11-A (where R ^{11 -A} represents 1 to 8 carbon atoms) To a monovalent aliphatic hydrocarbon group).

R ^{6 -A} represents a hydrogen atom or -OR ^{8 -B} (wherein R ^{8 -B} represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms),

R ^21-A has 1? 4 monovalent saturated hydrocarbon group,

R ^{22 -A} has 1? 4 monovalent saturated hydrocarbon group,

R ^{100 -A} represents a hydrogen atom or a methyl group.]

Salts (I-1), salts (I-2), salts (I-286) and salts (I-299) are preferred because their spectral concentrations are particularly high.

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

Salt (0) forms the salt containing anion (A1) using the compound represented by Formula (d) (hereinafter may be called "compound (d)"), and a chromium compound, and then anion ( It can manufacture by salt-exchange reaction of the salt containing A1) and the salt containing cation (A2).

[In formula (d), R <^1> ? R ⁷ represents the same meaning as in formula (0)]

The compound (d) can be produced, for example, by diazo coupling of the method described in JP-A-7-88633, that is, a diazonium salt and a pyridone compound.

Specifically, a compound (d) can be manufactured by diazo coupling the diazonium salt represented by Formula (b) and the pyridone compound represented by Formula (c). The diazonium salt represented by Formula (b) can be obtained by diazotizing the amine represented by Formula (a) with nitrous acid, nitrite, or nitrite ester, for example.

[In Formula (a), Formula (b), and Formula (c), R <^1>- ? R ⁷ represents the same meaning as that in formula (0). A ¹ represents an inorganic or organic anion]

As said inorganic anion, fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, etc. are mentioned, for example. As the organic anion, for example, CH ₃ -COO ^-, and the like ^-, C ₆ H ₅ -COO. Preferably, chloride ion, bromide ion, CH ₃ -COO ^- a.

Compound (d) can be manufactured by making the diazonium salt represented by Formula (b) and the pyridone compound represented by Formula (c) react in an aqueous solvent. The reaction temperature is -5 ℃? 60 degreeC is preferable and 0 degreeC? 30 degreeC is more preferable. The reaction time is 1 hour 12 hours is preferred, 1 hour? 4 hours is more preferable. As said aqueous solvent, N-methylpyrrolidone etc. are mentioned, for example.

As a method of acquiring the compound (d) which is a target compound from a reaction mixture, the method of mixing a reaction mixture with an acid (for example, acetic acid etc.) and water, and filtering the precipitated crystal | crystallization are mentioned, for example. Can be. It is preferable that the said acid adds the reaction mixture to the said aqueous solution, after preparing the aqueous solution of an acid previously. The temperature at the time of adding a reaction mixture is 10 degreeC or more and 50 degrees C or less normally, Preferably they are 20 degreeC or more and 50 degrees C or less, Preferably they are 20 degreeC or more and 30 degrees C or less. Moreover, after adding a reaction mixture to the aqueous solution of an acid, it is 0.5? It is preferable to stir for about 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

The salt containing anion (A1) is a compound (d) and a chromium compound in an aqueous solvent (for example, N, N-dimethylformamide, N-methylpyrrolidone, etc.), preferably 70? At 150 ° C., 3? It can manufacture by reacting for 10 hours.

Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, chromium fluoride, chromium ammonium sulfate, and the like, and chromium formate, chromium ammonium sulfate, and the like are preferable.

The amount of the chromium compound used is 0.5? To 1 mol of the compound (d). It is preferable that it is 1 mol.

Moreover, an inorganic base can also coexist in order to accelerate the reaction.

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

Next, the manufacturing method of salt (0) is demonstrated. Salt (0) can be manufactured by carrying out the salt exchange reaction of the salt containing anion (A1), and the salt containing cation (A2) in a solvent. The salt containing anion (A1) represented by a following formula (II '), and the salt containing cation (A2) are 1: 1? It is preferable to make it react in the molar ratio of 1: 4.

In formula (II '), R <^21> ? R ² has the same meaning as described above. A ¹ represents an inorganic or organic anion]

As A ¹ , halide ions such as fluoride ions, chloride ions, and bromide ions are preferable.

As a method of acquiring the salt (0) which is the target compound from the reaction mixture, for example, a method of mixing the reaction mixture with an inorganic salt (for example, salt) and water and filtering out precipitated crystals Can be mentioned. It is preferable that the said inorganic salt adds the reaction mixture to the said aqueous solution, after preparing the aqueous solution of an inorganic salt previously. The temperature at the time of adding a reaction mixture becomes like this. Preferably it is 10 degreeC or more and 50 degrees C or less, More preferably, it is 10 degreeC or more and 40 degrees C or less, More preferably, it is 10 degreeC or more and 25 degrees C or less. Moreover, after adding a reaction mixture to the aqueous solution of an inorganic salt, it is 0.5 degreeC at the same temperature. It is preferable to stir for about 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

The salt of the present invention thus obtained is useful as a dye. Since the salt of this invention has high spectral density, it is useful as a dye used for color filters, fiber materials, etc. of display apparatuses, such as a liquid crystal display device, which display color using reflected light or transmitted light.

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

The colored resin composition of this invention contains the dye, resin (B), and solvent (E) of this invention as a coloring agent (Hereinafter, it may be called "coloring agent (A)."). It is preferable that the colored resin composition of this invention contains a polymeric compound (C) and a polymerization initiator (D) further.

The coloring agent (A) may contain the pigment and / or dye different from the dye of this invention in addition to the dye of this invention.

As dyes different from the dyes of the present invention, in the Color Index (Published by The Society of Dyers and Colourists), Solvent, Acid, Basic, Reactive, Direct And dyes classified into Direct, Disperse, or Bat. More specifically, although the dye of the following color index (C.I.) numbers is mentioned, It is not limited to these.

C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;

C. I. acid yellow 7, 23, 25, 42, 65, 76;

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

C. I. Direct Yellow 4, 28, 44, 86, 132;

C. I. Disperse Yellow 54, 76;

C. I. Solvent Orange 41, 54, 56, 99;

C. I. acid orange 56, 74, 95, 108, 149, 162;

C. I. Reactive Orange 16;

C. I. Direct Orange 26;

C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;

C. I. Acid Violet 102;

C. I. Solvent Green 1, 5;

C. I. acid green 3, 5, 9, 25, 28;

C. I. Basic Green 1;

C. I. Bat Green 1 etc.

As a pigment, the organic pigment or inorganic pigment normally used for a pigment dispersion resist is mentioned. Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony or A composite metal oxide can be mentioned.

Moreover, as an organic pigment and an inorganic pigment, the compound classified by Pigment can be mentioned specifically, in Color Index (The Society of Dyers and Colourists). More specifically, although the pigment of the following color index (C.I.) numbers is mentioned, It is not limited to these.

C. I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;

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

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

C. I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C. I. Pigment Green 7, 10, 15, 25, 36, 47 and 58 and the like.

The content of the colorant (A) is preferably 5? To solid content in the colored resin composition. 60 mass%. Here, solid content means the sum total of the component except a solvent in a colored resin composition.

Content of the dye of this invention contained in a coloring agent (A) becomes like this. 100 mass%.

Dye and pigment different from the dye of this invention may be used independently, respectively, and may be used together with the dye of this invention in combination of 2 or more type.

It does not specifically limit as resin (B), You may use what kind of resin.

It is preferable that resin (B) is alkali-soluble resin, and it is more preferable that it is resin containing the structural unit guide | induced from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

Specifically as resin (B), methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate air A copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenyl maleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, etc. are mentioned.

The polystyrene reduced weight average molecular weight of resin (B) is 5,000? 35,000 is preferable, More preferably, it is 6,000? 30,000.

The acid value of the resin (B) is 50? 150 mg-KOH / g is preferable, More preferably, it is 60? 135 mg-KOH / g.

The content of the resin (B) is preferably 7? With respect to the solid content of the colored resin composition. 65 mass%, More preferably, it is 13? 60 mass%.

A polymerizable compound (C) will not be specifically limited if it is a compound which can superpose | polymerize with the active radical, the acid, etc. which generate | occur | produced from the polymerization initiator (D). For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned.

As said polymeric compound (C), it is preferable that it is a photopolymerizable compound which has 3 or more of polymeric groups. As a photopolymerizable compound which has three or more polymerizable groups, for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, diphenyl, Pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned. The said photopolymerizable compound (C) may be used independently, or may be used in combination of 2 or more type.

Content of a polymeric compound (C) is 5? With respect to solid content of a colored resin composition. It is preferable that it is 65 mass%, More preferably, it is 10? 60 mass%.

As said polymerization initiator (D), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by the action of heat or light. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, oxime compounds, and the like.

As said alkylphenone compound, 2-methyl-2- morpholino-1- (4-methylsulfanylphenyl) propane-1-one, 2-hydroxy-2-methyl-1-phenyl propane, for example. -1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, and the like. Can be.

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro, for example 4-propoxy thioxanthone etc. are mentioned.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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 (trichloro Methyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino -2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3 , 5-triazine and the like.

Examples of the oxime compound 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) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyl Oxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like.

As the active radical generator, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound Etc. may be used.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene Sulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoro antimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfo Onium salts, such as a nitrate and diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzoin tosylate, etc. are mentioned.

The said polymerization initiator (D) may be used independently or may be used in combination of 2 or more type.

The content of the polymerization initiator (D) is preferably 0.1? To 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 30 mass parts, More preferably, it is 1? 20 parts by mass. When content of a polymerization initiator exists in said range, it is preferable at the point which becomes high sensitivity, an exposure time is shortened, and productivity improves.

As a solvent (E), ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, etc. are mentioned, for example.

As said ether, For example, tetrahydrofuran, tetrahydropyran, 1, 4- dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mother Nobutyl ether acetate, and the like.

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and 4-hydroxy-4-methyl-2. -Pentanone, cyclopentanone, cyclohexanone, etc. are mentioned.

As said alcohol, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, etc. are mentioned, for example.

As said ester, For example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters , Methyl lactate, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl butyl acetate, methyl ethoxyacetate, ethoxyacetate, 3-methoxypropionate, methyl 3-methoxypropionate, 3 Methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2- Methyl methoxy-2-methyl propionate, 2-ethoxy-2-methyl ethyl propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, acetoacetate Ethyl, and 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ- lactone butynyl.

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like.

These solvents may be used independently or may be used in combination of 2 or more type.

Content of the solvent (E) in a colored resin composition becomes like this. 95 mass%, More preferably, it is 75? 90 mass%.

The colored resin composition of this invention may contain various additives, such as surfactant, a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

Salts of the present invention are useful as dyes. Moreover, since the salt of this invention has a high absorbance, the spectral density which shows the darkness of a color per unit concentration becomes high, and it is especially useful as a dye used for color filters of display apparatuses, such as a liquid crystal display device.

Moreover, the colored resin composition containing the salt of this invention is various, such as a display apparatus (for example, a well-known liquid crystal display device, organic electroluminescent apparatus, etc.), a solid-state image sensor, etc. which comprise a color filter as a part of the component. It can be used with a well-known aspect for the apparatus regarding the coloring image of an eggplant.

Example

Next, an Example is given and this invention is demonstrated further more concretely.

In Examples and Comparative Examples,% and parts indicating content to amount of use are based on mass unless otherwise specified.

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

Example 1

170 parts of water was added to 17.0 parts of anthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and then 5.4 parts of sodium hydroxide were added to dissolve it. Under ice cooling, 25.5 parts of sodium nitrite was added, followed by 79.5 parts of 35% hydrochloric acid in small portions. Thereafter, the mixture was stirred under ice cooling for 2 hours, in order to quench the excess nitrous acid, 250 parts of 9% aqueous amic sulfuric acid solution was slowly added and stirred for about 10 minutes to obtain a suspension containing a diazonium salt.

Subsequently, 24.1 parts of the compound represented by the formula (c-1) were suspended in 170 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. Here, in the suspension containing the diazonium salt, the pH of the suspension is 8.0? It was dripped at the pump over about 30 minutes, maintaining at 9.5. After completion of dropping, a yellow suspension was obtained by further stirring at room temperature for 2 hours. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 39.9 parts were obtained for the compound represented by a formula (d-1). ^The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by formula (d-1)

To 10 parts of the compound represented by the formula (d-1), 200 parts of N-methylpyrrolidone was added and dissolved by heating to 80 ° C, followed by addition of 3.7 parts of chromium formate n hydrate and stirring at 135 ° C for about 2 hours, followed by 80 The temperature was lowered to 0 ° C, 1.2 parts of sodium carbonate was added, followed by further stirring at 135 ° C for about 2 hours to obtain a dark orange solution. 7.5 parts of compounds represented by Formula (f-1) were obtained by pouring this solution in 1000 parts of 1N hydrochloric acid aqueous solution, filtering the obtained orange solid, washing twice with 80 parts of water, and vacuum drying at 60 degreeC.

Identification of the compound represented by formula (f-1)

(Mass spectrometry) ionization mode = ESI-: m / z = 700.1 [M-Na ⁺ ] ^?

                              Exact Mass: 723.1

To 63 parts of 2,3,3-trimethyl-3H-indole (manufactured by Wako Pure Chemical Industries, Ltd.), 65 parts of methyl iodide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and heated to reflux at 140 ° C. for 6 hours. After cooling, 120 parts of diethyl ether was added, and the precipitate formed was collected by filtration, washed with cold acetone, and dried under reduced pressure to obtain 102 parts of 1-methyl-2,3,3-trimethyl-3H-indoleium iodide (86 %). Subsequently, together with 470 parts of pyridine and 64 parts of triethylamine, 100 parts of 1-methyl-2,3,3-trimethyl-3H-indoleium iodide and 64 parts of ethyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) were heated at 120 ° C for 1 hour. Reacted. After cooling, a precipitate obtained by gradually adding 800 parts of diethyl ether is obtained by filtration. After recrystallizing this solid using ethanol, 145 parts of compounds represented by a formula (g-1) were obtained by drying under reduced pressure at 60 degreeC for 24 hours (90%).

Identification of the compound represented by formula (g-1)

(Mass Spec.) Ionization mode = ESI +: m / z = 357.3 [MI -] +

                               Exact Mass: 484.1

200 parts of N-methylpyrrolidone was added to 34 parts of compounds represented by a formula (f-1), and the solution (s1) was adjusted. Moreover, 110 parts of N-methylpyrrolidone was added to 23 parts of compounds represented by Formula (g-1), and the solution (t1) was adjusted. Thereafter, the solution (s1) and the solution (t1) were mixed at room temperature, stirred for about 1 hour, and then poured into 1280 parts of water. The red solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 37 parts (yield 72%) of salts represented by Formula (I-1) were obtained.

Identification of salts represented by formula (I-1);

(Elemental Analysis) C 65.0 H 5.2 N 12.6 Cr 4.6

[Example 2]

88 parts of water was added to 5.5 parts of anthranilic acid, followed by 3.2 parts of sodium hydroxide to obtain a yellow suspension. Under ice-cooling, 8.9 parts of sodium nitrite was added, followed by the addition of 33.2 parts of 35% hydrochloric acid little by little. Thereafter, the mixture was stirred under ice cooling for 3 hours, in order to quench excess nitrous acid, 100 parts of 9% amid sulfuric acid aqueous solution was slowly added and stirred for about 10 minutes to obtain a suspension containing a diazonium salt.

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

Next, 8.5 parts of compounds represented by Formula (c-2) were suspended in 77 parts of water, and pH was adjusted to 9.0 using sodium hydroxide. Here, in the suspension containing the diazonium salt, the pH of the suspension is 8.0? While maintaining at 9.5, it was dripped by the pump over about 1 hour. After completion of dropping, the mixture was further stirred at room temperature for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 11.2 parts were obtained for the compound represented by a formula (d-2). ^The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by formula (d-2)

100 parts of N, N-dimethylformamide, 7.7 parts of ammonium chromium sulfate, and 2.6 parts of sodium acetate were added to 10 parts of compounds represented by formula (d-2), and it stirred at 135 degreeC for about 6 hours, and obtained the dark orange solution. This solution was poured into 20% saline solution, and the obtained orange solid was filtered, and then 18 parts of compounds represented by the formula (f-2) were obtained by vacuum drying at 60 ° C.

Identification of the compound represented by formula (f-2)

(Mass spectrometry) ionization mode = ESI-: m / z = 732.1 [M-Na ⁺ ] ^-

                             Exact Mass: 755.1

Except for using 2,3,3,5-tetramethylindolenin instead of 2,3,3-trimethyl-3H-indole used for the synthesis of the compound represented by formula (g-1), the following formula (g The compound represented by -2) was synthesize | combined.

Identification of the compound represented by formula (g-2)

(Mass Spec.) Ionization mode = ESI +: m / z = 385.3 [MI -] +

                               Exact Mass: 512.2

100 parts of N-methylpyrrolidone was added to 12.2 parts of compounds represented by Formula (f-2), and solution (s2) was adjusted. In addition, 80 parts of methanol was added to 8.1 parts of the compound represented by formula (g-2) to adjust the solution (t2). Thereafter, the solution (s2) and the solution (t2) were mixed at room temperature, stirred for about 1 hour, and then poured into 800 parts of water. The red solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 12.1 parts (yield 66%) of salts represented by Formula (I-2) were obtained.

Identification of salt represented by formula (I-2)

(Elemental Analysis) C 63.6 H 5.1 N 12.3 Cr 4.6

[Example 3]

80 parts of water was added to 19.4 parts of 5- (N-acetylamino) entranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.4 parts of sodium hydroxide was added to dissolve it. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve, followed by stirring for 2 hours to obtain a suspension containing a diazonium salt.

Subsequently, 20.4 parts of the compound represented by the formula (c-2) were suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. Here, the suspension containing the diazonium salt was dripped at the pump over 15 minutes. After completion of dropwise addition, a yellow suspension was obtained by stirring for 30 minutes. Stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 39.1 parts of compounds which are represented by a formula (d-3) were obtained.

Next, 32.5 parts of the acid chloride (made by Wako Pure Chemical Industries, Ltd.) represented by Formula (e-1) were added to 39.9 parts of compounds represented by Formula (d-3), and it is 70 degreeC in N-methylpyrrolidone. And stirred for 3 hours. After the reaction was completed, 50.1 parts of a compound obtained by occupying with water and represented by the formula (d-4) was obtained. The obtained compound showed orange, and the maximum absorption wavelength ((lambda) max) was measured in the ethyl lactate solvent, and showed 459 nm. Moreover, the structure was confirmed by <^1> H-NMR.

150 parts of N, N-dimethylformamide, 7.7 parts of ammonium chromium sulfate, and 2.6 parts of sodium acetate were added to 10.0 parts of compounds represented by the formula (d-4), and stirred at 135 ° C for about 6 hours to obtain a dark orange solution. This solution was poured into 20% saline solution, and the obtained orange solid was filtered, and then 4.9 parts of the compound represented by the formula (f-3) were obtained by vacuum drying at 60 ° C.

Identification of the compound represented by formula (f-3)

(Mass spectrometry) ionization mode = ESI-: m / z = 1098.3 [M-Na ⁺ ] ^-

                             Exact Mass: 1121.34

110 parts of N-methylpyrrolidone was added to 18.9 parts of compounds represented by Formula (f-3), and solution (s3) was adjusted. Moreover, 80 parts of N-methylpyrrolidone was added to 8.8 parts of cyanine compounds represented by Formula (g-1), and solution (t3) was adjusted. Thereafter, the solution (s3) and the solution (t3) were mixed at room temperature, stirred for about 1 hour, and then poured into 1300 parts of water. The red solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 19.8 parts (yield 71%) of salts represented by Formula (I-286) were obtained.

Identification of salts represented by formula (I-286)

(Elemental Analysis) C 63.8 H 6.1 N 11.2 Cr 3.4

Example 4

32.4 parts of benzoyl chloride (made by Wako Pure Chemical Industries, Ltd.) was added to 30.0 parts of compounds represented by a formula (d-3), and it stirred at 70 degreeC in N-methylpyrrolidone for 3 hours. After the completion of the reaction, 35.8 parts of the compound which was occupied by water and represented by the formula (d-5) was obtained. The obtained compound showed orange, and the maximum absorption wavelength ((lambda) max) was measured in the ethyl lactate solvent, and showed 459 nm. Moreover, the structure was confirmed by <^1> H-NMR.

Next, 150 parts of N, N-dimethylformamide, 7.7 parts of ammonium chromium sulfate, and 2.6 parts of sodium acetate were added to 9.6 parts of the compound represented by the formula (d-5), and stirred at 135 ° C. for about 6 hours to give a dark orange solution. Got it. This solution was poured into 20% saline solution, and the obtained orange solid was filtered, and then 7.1 parts of compounds represented by the formula (f-4) were obtained by vacuum drying at 60 ° C.

150 parts of N-methylpyrrolidone was added to 15.1 parts of compounds represented by a formula (f-4), and the solution (s4) was adjusted. Moreover, 75 parts of N-methylpyrrolidone was added to 8.1 parts of compounds represented by a formula (g-2), and the solution (t4) was adjusted. Thereafter, the solution (s4) and the solution (t4) were mixed at room temperature, stirred for about 1 hour, and then poured into 1250 parts of water. The red solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 15.9 parts (yield: 77%) of the salt represented by Formula (I-299) were obtained.

Identification of salt represented by formula (I-299)

(Elemental Analysis) C 64.4 H 4.9 N 11.7 Cr 3.5

<Measurement of absorbance>

0.35 g of salt was dissolved in ethyl lactate to make a volume of 250 cm 3, 2 cm 3 of which was diluted with ethyl lactate to 100 cm 3, and a solution having a concentration of 0.028 g / L was adjusted. For the solution, using an ultraviolet visible spectrophotometer (V-650DS; manufactured by Nippon Spectroscopy Co., Ltd.) (quartz cell, optical path length; 1 cm) at the maximum absorption wavelength (λ max) and the maximum absorption wavelength (λ max) The absorbance of was measured. The results are shown in Table 2.

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

[Example 7]

[Preparation of Colored Photosensitive Resin Composition]

(A) Colorant: salt (I-1): 20 parts of the salt synthesized in Example 1

(B-1) resin: methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, acid value 70 mg-KOH / g) 70 parts

(C-1) Polymerizable Compound: 30 parts of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

(D-1) Polymerization initiator: Benzyldimethyl ketal (Irgacure (registered trademark) 651; made by BASF Japan) 15 parts

And

(E-1) Solvent: 680 parts of ethyl lactates are mixed, and a colored resin composition is obtained.

<Production of color filter>

On glass, the colored resin composition obtained above is apply | coated by the spin coat method, and a volatile component is volatilized. After cooling, light irradiation is performed using a quartz glass photomask having a pattern and an exposure machine. After light irradiation, it develops with aqueous potassium hydroxide solution and heats to 200 degreeC in oven, and obtains a color filter.

[Example 8]

A colored resin composition and a color filter are obtained in the same manner as in Example 7 except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-2) synthesized in Example 2.

[Example 9]

A colored resin composition and a color filter are obtained in the same manner as in Example 7 except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-3) synthesized in Example 3.

[Example 10]

A colored resin composition and a color filter are obtained in the same manner as in Example 7 except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-4) synthesized in Example 4.

[Example 11]

A colored resin composition and a color filter were obtained in the same manner as in Example 7 except that the salt (I-1) synthesized in Example 1 was changed to the salt (I-286) synthesized in Example 5.

[Example 13]

A colored resin composition and a color filter were obtained in the same manner as in Example 7 except that the salt (I-1) synthesized in Example 1 was changed to the salt (I-299) synthesized in Example 6.

<Synthesis of Resin B1 Solution>

Nitrogen was poured into a flask equipped with a stirrer, a thermometer, a reflux cooler and a dropping funnel at 0.02 L / min to form a nitrogen atmosphere, and 305 parts of ethyl lactate was added thereto and heated to 70 ° C while stirring. Subsequently, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the following formula (b-1) and a compound represented by the formula (b-2), in molar ratio, 50:50) and 240 parts of ethyl lactate were dissolved, to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C over 4 hours using a dropping funnel. On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 parts of ethyl lactates was dripped in the flask over 4 hours using the other dropping funnel. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was maintained at 70 ° C for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw was 1.3 × 10 ⁴ , solid content 33 mass%, and solution acid value 34 mg-KOH / g. A resin B1 solution was obtained. Calculated from the solid content, the solution acid value, and the like, the solid acid value of the resin B1 was 100 mg-KOH / g.

About the measurement of the polystyrene conversion weight average molecular weight of the said resin, it implemented on the following conditions 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 solids concentration; 0.001? 0.01%

Injection volume; 50 μl

Detector; RI

Calibration standard substance; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

Example 14

[Preparation of Colored Photosensitive Resin Composition]

(A) Colorant: salt (I-1): 30 parts of the salt synthesized in Example 1

(B-2) Resin: Resin B1 (Solid Content) 40 Parts

(C-2) Polymerizable Compound: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD® DPHA; manufactured by Nippon Gunpowder Co., Ltd.)

                                                                  60 parts

(D-2) Polymerization initiator: 12 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure® OXE 01; produced by BASF Japan)

(D-3) Polymerization initiator: 6 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure® 369; produced by BASF Japan)

(D2) Polymerization start adjuvant: 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)

(E-2) Solvent: Propylene glycol monomethyl ether acetate 528 parts

(E-3) Solvent: Propylene glycol monomethyl ether 69 parts

And

(F) Surfactant: 0.09 part of polyether modified silicone oil (Tore silicone SH8400; manufactured by Torre Dow Corning Co., Ltd.) is mixed, and a coloring photosensitive resin composition is obtained. Moreover, using it, it is carried out similarly to Example 7, and obtains a color filter.

From the result of Table 2, it turns out that the salt of this invention shows high spectral density from the high absorbance point. Moreover, the colored resin composition containing the said compound has the outstanding color performance, and it is possible to manufacture a high quality color filter.

Industrial availability

The compounds of the present invention are useful as dyes. Since the salt of this invention has high absorbance, the spectral density which shows the intensity | strength of the color per unit density | concentration becomes high, and it is especially useful as a dye used for color filters of display apparatuses, such as a liquid crystal display device.

Claims (10)

Salt represented by Formula (0).

[In formula (0), R <^1> is C1-C? The monovalent saturated hydrocarbon group of 8 is represented, and the hydrogen atoms contained in the saturated hydrocarbon group are -OR ⁸ , -COOR ⁸ , -OCOR ⁸ , -CONR ⁸ R ⁹ , and 6? It may be substituted by the 10 monovalent aromatic hydrocarbon group or the halogen atom, and -CH ₂ -contained in the saturated hydrocarbon group may be substituted by -CO-.
R ² represents a hydrogen atom, —CN or —CONH ₂ .
R ³ is C 1? The alkyl group of 4 is shown.
R ⁴ ? R ⁷ is each independently -R ⁸ , -OR ⁸ , -COOR ⁸ , -COR ⁸ , -OCOOR ⁸ , -OCOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, -SO ₂ NR ⁸ R ⁹ or -NR ¹¹ R ¹² or R ⁴ and R ⁵ , R ⁵ and R ⁶ and R ⁶ and R ⁷ are bonded to each other to contain carbon of the benzene ring 6? Forms a seven-membered ring.
R ⁸ and R ⁹ each independently represent a hydrogen atom and 1? Monovalent aliphatic hydrocarbon group of 8, carbon number 7? 12 aralkyl group or C6? The monovalent aromatic hydrocarbon group of 10 is represented, and the hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group, and the aromatic hydrocarbon group may be substituted with -OR ¹⁰ .
R ¹⁰ is a hydrogen atom, carbon number 1? Monovalent saturated hydrocarbon groups of 8 or 6? 10 monovalent aromatic hydrocarbon group is shown.
R ¹¹ and R ¹² each independently represent a hydrogen atom and 1? Monovalent aliphatic hydrocarbon group of 8, carbon number 2? Or an acyl group or tetrahydrofurfuryl group of 8, or R ¹¹ and R ¹² are bonded to each other to form a ring containing a nitrogen atom.
The ring Z ¹ and the ring Z ² each independently represent an aromatic ring which may have a substituent, and R ²¹ and R ²² independently of each other may have a substituent having 1 to 4 carbon atoms. An aliphatic hydrocarbon group of 12 or a hydrogen atom, and R ²³ and R ²⁴ independently of each other may have a C 1? Or an aliphatic hydrocarbon group of 12 or a hydrogen atom, or R ²³ and R ²⁴ are combined to form an alkanediyl group. R ²⁵ and R ²⁶ may each independently have a substituent. Or an aliphatic hydrocarbon group of 12 or a hydrogen atom, or R ²⁵ and R ²⁶ become one to form an alkanediyl group. R ²⁷ and R ²⁸ independently of each other may have a substituent of 1? Or an aliphatic hydrocarbon group of 12 or a hydrogen atom, or R ²⁷ and R ²⁸ become one to form an alkanediyl group. X ¹ represents a hydrogen atom or a chlorine atom.] The method of claim 1,
R ⁴ ? R ⁷ independently of one another is -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K or -SO ₂ NR ⁸ R ⁹ Phosphorus salts. The method of claim 1,
R ¹ may be substituted with —OH or —OCOR ⁸ . A salt that is a monovalent saturated hydrocarbon group of 8. The method of claim 1,
R ⁴ ? Salts wherein at least three of R ⁷ are hydrogen atoms. The method of claim 1,
Salts wherein R ² is -CN. The method of claim 1,
R ²³ ? R ²⁶ independently from each other C 1? A salt that is a monovalent aliphatic hydrocarbon group of 8. The method of claim 1,
A salt wherein R ²¹ and R ²² are methyl groups. The method of claim 1,
A salt wherein Z ¹ and Z ² are a benzene ring which may be substituted with a methyl group. The dye which uses the salt as described in any one of Claims 1-8 as an active ingredient. The colored resin composition containing the dye, resin, and solvent of Claim 9.