JP2013133395A - Coloring composition, inkjet recording ink, and inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a coloring composition that sufficiently satisfies both image fastness such as ozone resistance, light resistance, and an excellent hue; an inkjet recording ink comprising the coloring composition; and an inkjet recording method using the inkjet recording ink.SOLUTION: The coloring composition comprises, for example, a compound (1A) and a compound (2A).

Description

  The present invention relates to a coloring composition comprising a compound having a specific xanthene skeleton and a specific heteryl azo compound, an ink for ink jet recording, and an ink jet recording method.

  As is well known, the ink jet recording method is a method of performing printing by causing a small droplet of ink to fly and adhere to a recording medium such as paper. This printing method is capable of printing high-resolution, high-quality images at high speed and easily with an inexpensive apparatus. In particular, in color printing, technical development has recently been carried out as an image forming method that can replace photographs. .

  When forming a color image using an inkjet recording method, it is common to use at least yellow ink, magenta ink, cyan ink, and black ink. Conventionally, water-based inks are mainly used for these ink-jet inks from the viewpoint of safety such as odor and fire hazard. These inks have physical properties such as viscosity and surface tension within an appropriate range, nozzle clogging, excellent storage stability, and high density recording images, and light resistance, ozone resistance, Properties such as excellent water resistance and moisture resistance are required.

  Many of these performances are satisfied by using water or a water-based ink containing a mixture of water and a water-soluble organic solvent as a main solvent, but color tone, vividness, light resistance, ozone resistance, water resistance Moisture resistance depends largely on the colorant, and various dyes have been studied in the past.

  Conventionally, as a magenta dye for inkjet, an acid dye having good color development and high water solubility, such as C.I. I. Acid Red 52, 249, 289, etc. are known, but when these dyes are used alone, although they are highly water-soluble, nozzle clogging is less likely to occur, but ozone resistance and light resistance performance are very high. It was low.

  Patent Document 1 discloses C.I., a xanthene derivative. I. Acid Red 289 and C.I. I. A water-based ink for ink-jet recording containing a dye comprising a xanthene derivative having more sulfo groups than Acid Red 289 is described.

  In addition, azo dyes are also known as magenta dyes for ink jet. As an azo dye having a good hue, Patent Document 2 discloses a good hue by using a heteryl azo dye having a specific substituent. And a coloring composition having fastness to light and ozone.

  Patent Document 3 describes an ink in which a xanthene compound and an azo compound are used in combination.

British Patent No. 2134129 JP 2006-143989 A US Patent Application Publication No. 2011/0067598 Specification

However, dyes specifically described in Patent Document 1 are required to further improve ozone resistance and light resistance. Further, the dye described in Patent Document 2 has good fastness such as light resistance and ozone resistance, but has left room for further improvement in hue. That is, in any case, the fastness and the hue are not sufficiently compatible. Similarly, Patent Document 3 also requires further improvement in performance.
An object of this invention is to provide the coloring composition which fully balances image fastness, such as ozone resistance and light resistance, and favorable hue. Another object of the present invention is to provide an ink jet recording ink containing the coloring composition, and an ink jet recording method using the ink jet recording ink.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that a colored composition containing a compound having a xanthene skeleton into which a specific number of sulfo groups have been introduced and a specific heteryl azo compound has an image such as ozone resistance and light resistance. The inventors have found that the performance related to fastness and hue is better than expected and have completed the present invention.

  That is, the present invention is as follows.

[1]
A coloring composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (4).

  In general formula (1), D represents the residue remove | excluding n hydrogen atoms from the compound represented by the following general formula (2), and n represents the number of 3-6. M represents a hydrogen atom or a counter cation. M may be the same or different.

In general formula (2), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represents a monovalent substituent, R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom or a monovalent substituent, and n 101 and n102 represents the number of 0-5 each independently, and n103 represents the number of 0-4. n101, if n102 and n103 represents the number of 2 or more, respectively, a plurality of ^{R 101, R 102,} and ^{R 103} may be different even in the same.

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ²³ and R ²⁴ are not both hydrogen atoms.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
Each group of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ and Q may further have a substituent.
However, general formula (4) has at least one ionic hydrophilic group.
[2]
The coloring composition according to [1], wherein n in the general formula (1) is 4.
[3]
The coloring composition according to [1] or [2], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

In General Formula (3), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent a monovalent substituent, n201 and n202 each independently represent a number from 0 to 4, and n203 is a number from 0 to 4 Represents. n201, n202, and if n203 represents the number of 2 or more, respectively, a plurality of ^{R 201, R 202,} and ^{R 203} may be different even in the same. M represents a hydrogen atom or a counter cation. M may be the same or different.
[4]
The colored composition according to any one of [1] to [3], wherein R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represents an alkyl group or an acylamino group. object.
[5]
Wherein ^{R 101, R 102, R 103} , R 201, R 202, and ^{R 203} are each independently represents an alkyl group having 1 to 6 carbon atoms, according to any one of the above [1] to [4] Coloring composition.
[6]
The colored composition according to any one of [1] to [5], wherein n101, n102, n201, and n202 each independently represent a number of 2 to 4.
[7]
The colored composition according to any one of [1] to [6], wherein n103 and n203 represent 0.
[8]
The colored composition according to any one of [1] to [7], wherein the salt of the compound represented by the general formula (1) is a lithium salt, a sodium salt, or a potassium salt.
[9]
Any of the above [1] to [8], wherein the ionic hydrophilic group in the general formula (4) is at least one group selected from a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. The coloring composition according to one item.
[10]
The coloring composition according to any one of [1] to [9], wherein R ²³ and R ²⁴ each independently represent a hydrogen atom, an aromatic group, or a hetero group in General Formula (4).
[11]
The coloring composition as described in any one of said [1]-[10] containing 1-10 mass% of compounds or its salt represented by General formula (1).
[12]
The coloring composition as described in any one of said [1]-[11] containing 1-10 mass% of compounds represented by General formula (4).
[13]
Any one of the above [1] to [12], wherein the mass ratio of the compound represented by the general formula (1) and the compound represented by the general formula (4) is 1/9 to 9/1. The coloring composition as described.
[14]
Ink for inkjet recording containing the coloring composition as described in any one of said [1]-[13].
[15]
An inkjet recording method for forming an image using the colored composition according to any one of [1] to [13] or the inkjet recording ink according to [14].

  According to the present invention, there is provided a coloring composition that sufficiently satisfies both image fastness such as ozone resistance and light resistance and a good hue. Also provided are an ink jet recording ink containing the coloring composition and an ink jet recording method using the ink jet recording ink. The colored composition of the present invention is particularly useful as a magenta ink.

FIG. 1 is a diagram showing a ¹ H NMR spectrum of compound (1A), which is an example of the compound represented by general formula (1) in the present invention, in deuterated dimethyl sulfoxide.

Hereinafter, the present invention will be described in detail.
First, in the present invention, the substituent group A is defined.

(Substituent group A)
Halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto Group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, Job aryloxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group, an ionic hydrophilic group mentioned as an example. These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, for example.

Examples of the alkyl group include linear, branched, and cyclic substituted or unsubstituted alkyl groups, and include cycloalkyl groups, bicycloalkyl groups, and tricyclo structures having many ring structures. An alkyl group (for example, an alkyl group of an alkoxy group or an alkylthio group) in a substituent described below also represents such an alkyl group.
As the alkyl group, an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, 2- Examples thereof include a chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group, etc. The cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group, a cyclopentyl group, 4 -N-dodecylcyclohexyl group and the like, and the bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Removed monovalent groups such as bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2 2] octan-3 yl group.

  Examples of the aralkyl group include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. For example, a benzyl group and a 2-phenethyl group can be mentioned.

Examples of the alkenyl group include linear, branched, and cyclic substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups.
Preferred examples of the alkenyl group include substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms such as vinyl group, allyl group, prenyl group, geranyl group, and oleyl group. Preferred examples of the cycloalkenyl group include Is a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as a 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group and the like. As the bicycloalkenyl group, a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a double bond A monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one of, for example, bicyclo [2,2,1] Hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group and the like.

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as an ethynyl group, a propargyl group, and a trimethylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group, and the like. Can be mentioned.

  The heterocyclic group is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a carbon number. Examples thereof include 3 to 30 5- or 6-membered aromatic heterocyclic groups such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

  The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group. Etc.

  The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group etc. are mentioned.

  Preferred examples of the silyloxy group include substituted or unsubstituted silyloxy groups having 0 to 20 carbon atoms such as a trimethylsilyloxy group and a diphenylmethylsilyloxy group.

  Preferred examples of the heterocyclic oxy group include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, such as a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group.

  The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as an acetyloxy group, Examples include a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, and a p-methoxyphenylcarbonyloxy group.

  The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N , N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group and the like.

  The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group. Etc.

  The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxy. Examples include phenoxycarbonyloxy group.

  The amino group includes an alkylamino group, an arylamino group, and a heterocyclic amino group, preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms. Examples of the substituted anilino group include a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, and a triazinylamino group.

  The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as an acetylamino group, Examples include pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

  The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a carbamoylamino group, N, N-dimethylaminocarbonylamino group, or N, N-diethylaminocarbonylamino group. And a morpholinocarbonylamino group.

  The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino. Group, N-methyl-methoxycarbonylamino group and the like.

  The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxy. Examples thereof include a carbonylamino group.

  The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn- Examples include octylaminosulfonylamino group.

The alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as a methylsulfonylamino group. Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, and the like.
Preferred examples of the alkylthio group include substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, and an n-hexadecylthio group.

  Preferred examples of the arylthio group include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms such as a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.

  Preferred examples of the heterocyclic thio group include substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms, such as a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.

  The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfuryl group. Examples include a famoyl group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, and an N- (N′-phenylcarbamoyl) sulfamoyl group.

  The alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group or an ethylsulfinyl group. , Phenylsulfinyl group, p-methylphenylsulfinyl group and the like.

  The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group or an ethylsulfonyl group. , Phenylsulfonyl group, p-methylphenylsulfonyl group and the like.

  The acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 2 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridyl Examples thereof include a carbonyl group and a 2-furylcarbonyl group.

  The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt- A butylphenoxycarbonyl group etc. are mentioned.

  The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.

  The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, or an N, N-di-n-octyl group. Examples thereof include a carbamoyl group and an N- (methylsulfonyl) carbamoyl group.

  The aryl or heterocyclic azo group is preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo and the like.

  Preferred examples of the imide group include an N-succinimide group and an N-phthalimide group.

  The phosphino group is preferably a substituted or unsubstituted phosphino group having 0 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, and the like.

  The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like.

  Preferred examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 0 to 30 carbon atoms such as a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

  The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 0 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group.

  Preferred examples of the silyl group include substituted or unsubstituted silyl groups having 0 to 30 carbon atoms such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group.

  Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group. Particularly preferred are a sulfo group and a carboxyl group. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. Cation (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) is included, lithium salt, sodium salt, potassium salt, ammonium salt is preferable, sodium salt or mixed salt containing sodium salt as main component Are more preferred, and sodium salts are most preferred.

  In the present invention, when the compound is a salt, the salt is dissociated into ions in the water-soluble ink.

  The coloring composition of the present invention comprises a compound having a specific xanthene skeleton represented by the general formula (1) or a salt thereof, and a specific heteryl azo compound represented by the general formula (4).

[Compound represented by the general formula (1)]
The coloring composition of the present invention contains a compound represented by the following general formula (1).

  In general formula (1), D represents the residue remove | excluding n hydrogen atoms from the compound represented by the following general formula (2), and n represents the number of 3-6. M represents a hydrogen atom or a counter cation. M may be the same or different.

In general formula (2), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represents a monovalent substituent, R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom or a monovalent substituent, and n 101 and n102 represents the number of 0-5 each independently, and n103 represents the number of 0-4. n101, if n102 and n103 represents the number of 2 or more, respectively, a plurality of ^{R 101, R 102,} and ^{R 103} may be different even in the same.

  The compound represented by the general formula (1) is a xanthene dye in which 3 to 6 hydrogen atoms are substituted with a sulfo group in the compound represented by the general formula (2), and is represented by the general formula (4) described later. In combination with the compound, the ozone resistance is improved because both have excellent ozone resistance, and the xanthene dye represented by the general formula (1) is represented by the general formula (4). The light resistance is improved by energy transfer to the compound, and the compound represented by the general formula (4) having a poor hue is averaged by the excellent hue of the xanthene dye represented by the general formula (1). It is thought that it can be set as the coloring composition excellent in a hue.

  In general formula (1), n represents the number of 3-6, 4-6 are preferable from a synthetic viewpoint, 4 or 5 is more preferable, and 4 is still more preferable.

In General Formula (2), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represent a monovalent substituent.
Examples of the monovalent substituent represented by R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ include a substituent selected from the substituent group A. From the viewpoints of availability of raw materials and ease of synthesis, a halogen atom, aryl Group, alkoxy group, alkyl group and acylamino group are preferred, alkyl group and acylamino group are more preferred, and alkyl group is still more preferred.

When R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ represent an alkyl group, from the viewpoint of availability of raw materials, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is preferable. More preferred. Moreover, it is preferable that it is a linear or branched alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a t-butyl group, and a methyl group, an ethyl group, or an i-propyl group is preferable, and a methyl group Or an ethyl group is more preferable, and a methyl group is still more preferable.
The alkyl group may have a substituent, and examples of the substituent include a halogen atom and a hydroxyl group.
The alkyl group is preferably an unsubstituted alkyl group.

When R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ represent an acylamino group, the acyl group in the acylamino group is preferably an aliphatic acyl group from the viewpoint of availability of raw materials and color developability, and has 2 to 6 carbon atoms. More preferably, it is an aliphatic acyl group. Specific examples include an acetylamino group, a propionylamino group, a butyrylamino group, and the like, and an acetylamino group is particularly preferable.
The acylamino group is preferably a monoacylamino group.

In the general formula (2), R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom or a monovalent substituent.
When R ¹⁰⁴ and R ¹⁰⁵ represent a monovalent substituent, examples of the monovalent substituent include a substituent selected from the substituent group A, and a substituted or unsubstituted alkyl group is preferable. The alkyl group is more preferable.
From the viewpoints of absorption characteristics and ozone resistance, R ¹⁰⁴ and R ¹⁰⁵ are preferably hydrogen atoms.

In general formula (2), n101 and n102 each independently represents a number of 0 to 5. From the viewpoint of availability of raw materials and ease of synthesis, n101 and n102 are preferably 1 to 5, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 2 or 3.
n101, and if n102 represents the number of 2 or more, respectively, a plurality of ^{R 101,} and ^{R 102} may be different even in the same.

In general formula (2), n103 represents the number of 0-4. From the viewpoint of availability of raw materials, n103 is preferably a number of 0 to 3, more preferably a number of 0 to 2, still more preferably 0 or 1, and particularly preferably 0.
If n103 represents the number of 2 or more, plural R ¹⁰³ may be different even in the same.

In the general formula (1), M represents a hydrogen atom or a counter cation. M may be the same or different.
In the general formula (1), when M is a hydrogen atom, it is in the form of a free acid, and when M is a counter cation, it is in the form of a salt.
Examples of counter cations that form salts include monovalent counter cations, and alkali metal ions, ammonium ions, organic cations, and the like are preferable.
Examples of the organic cation include tetramethylammonium ion, tetramethylguanidinium ion, and tetramethylphosphonium.
From the viewpoint of the availability of raw materials, the water solubility of dyes, and the suppression of gloss generation when creating secondary colors with other dyes when used as inkjet inks, alkali metal ions are preferred, lithium ions, sodium ions, Potassium ions are more preferred. In particular, sodium ion is preferable because it is inexpensive.
In the present invention, from the viewpoint of ease of synthesis (easy handling as a dye powder), the compound represented by the general formula (1) is preferably in the form of a salt, such as a lithium salt, a sodium salt, Or it is more preferable that it is a potassium salt, and it is still more preferable that it is a sodium salt.
In the general formula (1), M may be the same or different. That is, the compound represented by the general formula (1) is in the form of a salt when all the sulfo groups are in the form of a salt and when some of the sulfo groups are in the form of a free acid. This includes the case where a part of the sulfo group is a salt. Moreover, the counter cation forming the salt may be one kind or plural kinds.
In the present invention, from the viewpoint of ease of synthesis (easy handling as a dye powder), the compound represented by the general formula (1) is preferably in the form of a salt, and all sulfo groups are salts. Is more preferable.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (3).
The compound represented by the following general formula (3) can inhibit the attack of oxidizing gas (oxygen or ozone) on the nitrogen atom due to the steric hindrance of the sulfo group introduced adjacent to the nitrogen atom. It is considered particularly excellent in terms of ozone resistance and light resistance.

In General Formula (3), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent a monovalent substituent, n201 and n202 each independently represent a number from 0 to 4, and n203 is a number from 0 to 4 Represents. n201, n202, and if n203 represents the number of 2 or more, respectively, a plurality of ^{R 201, R 202,} and ^{R 203} may be different even in the same. M represents a hydrogen atom or a counter cation. M may be the same or different.

Specific examples and preferred ranges of R ²⁰¹ , R ²⁰² , R ²⁰³ , n203, and M in the general formula (3) are specific examples of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , n103, and M in the general formula (2) and This is the same as the preferred range.
N201 and n202 in the general formula (3) each independently represent a number of 0 to 4, and from the viewpoint of availability of raw materials and ease of synthesis, a number of 1 to 4 is preferable, and a number of 2 to 4 is preferable. 2 or 3 is more preferable.

  Although the specific example of a compound represented by General formula (1) below is given, it is not necessarily limited to these. In the following specific examples, Me represents a methyl group, Et represents an ethyl group, i-Pr represents an isopropyl group, t-Bu represents a tertiary butyl group, and Ac represents an acetyl group.

A method for synthesizing the compound represented by the general formula (1) will be described.
After synthesizing a xanthene dye according to a conventionally known method for synthesizing xanthene dyes, or using a commercially available xanthene dye and chlorosulfonylating with a combination of chlorosulfonic acid / phosphorus oxychloride, followed by alkaline hydrolysis Can be synthesized (see scheme below). Details will be described in Examples described later.

[Compound represented by formula (4)]

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ²³ and R ²⁴ are not both hydrogen atoms.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
Each group of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ and Q may further have a substituent.
However, general formula (4) has at least one ionic hydrophilic group.

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.

(Hammett's substituent constant σp value)
Hammett's substituent constant σp value used in this specification will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it can be found in the above-mentioned book and is limited only to a substituent having a known value in the literature. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule.

The electron-withdrawing group of Z ^{1 is} an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less.

  Specific examples of the electron withdrawing group having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy Group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, heterocyclic group, halogen atom, azo group, selenocyanate group, and other electron withdrawing groups with a σp value of 0.20 or more The aryl group I can get lost.

Z ¹ is preferably a cyano group, a nitro group, or a halogen atom from the viewpoint of hue and fastness, more preferably a halogen atom or a cyano group, and most preferably a cyano group.

In General Formula (4), Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
Examples of the aliphatic group include an alkyl group and a cycloalkyl group.
Examples of the aromatic group include an aryl group.
Moreover, an aralkyl group is mentioned as a group applicable to an aromatic group and an aliphatic group.

The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples include a methyl group, an ethyl group, a butyl group, an isopropyl group, t -A butyl group etc. are mentioned.
The alkyl group may have a substituent, and examples of the substituent include the above-mentioned substituent group A, and are preferably a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. .
Examples of the alkyl group having a substituent include a hydroxyethyl group, a methoxyethyl group, a cyanoethyl group, a trifluoromethyl group, a 3-sulfopropyl group, and a 4-sulfobutyl group.

The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms, and examples thereof include a cyclohexyl group.
The cycloalkyl group may have a substituent, and examples of the substituent include the substituent group A described above, and an ionic hydrophilic group is preferable.

As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms is preferable, and examples thereof include a benzyl group and a 2-phenethyl group.
The aralkyl group may have a substituent, and examples of the substituent include the aforementioned substituent group A, and an ionic hydrophilic group is preferable.

As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group and a naphthyl group.
The aryl group may have a substituent, and examples of the substituent include the substituent group A described above, an amide group, a sulfonamide group, an ester group, and the like. An alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and the like. It is preferably a group, an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxy group, an ester group, or an ionic hydrophilic group.
Examples of the aryl group having a substituent include a p-tolyl group, a p-methoxyphenyl group, o-chlorophenyl, and m- (3-sulfopropylamino) phenyl group.

The heterocyclic group (heterocyclic group) is preferably a 5-membered or 6-membered heterocyclic group. Examples thereof include a 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2- Examples thereof include a benzoxazolyl group and a 2-furyl group.
The heterocyclic group may have a substituent, and examples of the substituent include the above-described substituent group A, amide group, sulfonamido group, ester group, and the like. Amido group, carbamoyl group, sulfamoyl group, sulfone An amide group, a hydroxy group, an ester group and an ionic hydrophilic group are preferred.

As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable, and examples thereof include an acetyl group and a benzoyl group.
The acyl group may have a substituent, and examples of the substituent include the aforementioned substituent group A, and an ionic hydrophilic group is preferable.

Z ² is preferably an alkyl group or an aryl group, and is an alkyl group having 3 to 4 carbon atoms (preferably an isopropyl group or a t-butyl group), a phenyl group, or the 2-position, 4-position or the pyrazole mother nucleus side. More preferred is a phenyl group having a further substituent at any of the 6-positions, and even more preferred is a t-butyl group.

In general formula (4), R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl. Represents a group, an arylsulfonyl group, or a sulfamoyl group.
Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
Examples of the aromatic group include an aryl group.
Moreover, an aralkyl group is mentioned as a group applicable to an aromatic group and an aliphatic group.
However, R ²³ and R ²⁴ are not both hydrogen atoms.

Examples of the alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, and acyl group include the groups described for Z ² above.
Each group may further have a substituent, and examples of the substituent are the same as the examples described for Z ² above.

As the alkenyl group, an alkenyl group having 5 to 12 carbon atoms is preferable, and examples thereof include a vinyl group and an allyl group.
The alkenyl group may have a substituent, and examples of the substituent include the aforementioned substituent group A, and an ionic hydrophilic group is preferable.

Examples of the alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, and alkynyl group include the groups described in Substituent Group A described above.
Each group may further have a substituent, and examples of the substituent include the substituent group A described above.

R ²³ and R ²⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aromatic group, heterocyclic group, sulfonyl group, acyl group, or carbamoyl group from the viewpoint of hue. And more preferably a hydrogen atom, an alkyl group, an aralkyl group, an aromatic group, a heterocyclic group, a sulfonyl group, or an acyl group, and a hydrogen atom, an aromatic group, or a heterocyclic group. Is more preferable.
It is particularly preferable that R ²³ is a hydrogen atom or a heterocyclic group, and R ²⁴ is an aromatic group.
As the heterocyclic group, a benzoxazolyl group or a benzothiazolyl group is particularly preferable, and more specifically, a benzothiazolyl group substituted with an unsubstituted or sulfo group (including a salt state) is preferable.
The aromatic group is preferably an aryl group substituted with at least one group selected from an alkyl group and a sulfo group (including a salt state), and at least one group selected from an alkyl group and a sulfo group is substituted. A phenyl group is particularly preferred.
Specific examples and preferred ranges of the counter cation when the sulfo group is in a salt state are the same as the specific examples and preferred ranges when the compound represented by the general formula (1) is a salt.

In the general formula (4), R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryl Oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group , Heterocyclic amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl Represents an arylthio group, an alkyl- or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
Examples of the aromatic group include an aryl group.
Moreover, an aralkyl group is mentioned as a group applicable to an aromatic group and an aliphatic group.

Specific examples of the groups represented by R ²¹ and R ²² include the groups described in the substituent group A described above.
Each group may further have a substituent, and examples of the substituent include the substituent group A described above.

R ²¹ and R ²² are preferably a hydrogen atom, an alkyl group, a carbamoyl group, or a cyano group from the viewpoint of ease of synthesis, light resistance, and ozone resistance. More preferably, it is an alkyl group, a carbamoyl group, or a cyano group. In particular, it is preferable that R ²¹ is a hydrogen atom and R ²² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (most preferably a methyl group).

In General Formula (4), R ²⁵ and R ²⁹ each independently represent an alkyl group, an alkoxy group, or a halogen atom. When R ²⁵ and R ²⁹ are both alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.

Specific examples of the alkyl group, alkoxy group, and halogen atom include the groups described in Substituent Group A described above.
The alkyl group and alkoxy group may further have a substituent, and examples of the substituent include the substituent group A described above.

R ²⁵ and R ²⁹ are preferably alkyl groups from the viewpoint of light resistance and ozone resistance, and each is an alkyl group having 1 to 3 carbon atoms (preferably a methyl group, an ethyl group, or an isopropyl group). Is preferred. However, the total number of carbon atoms constituting the alkyl group of R ²⁵ and R ²⁹ is 3 or more, and the total number of carbon atoms is preferably an alkyl group which may be substituted and has 3 to 5 carbon atoms. The total is more preferably an unsubstituted alkyl group having 4 to 5 carbon atoms.

In the general formula (4), R ²⁶ , R ²⁷ , and R ²⁸ are each independently synonymous with R ²¹ and R ^22, and are mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ^29. May be.
Specific examples of R ²⁶ , R ²⁷ , and R ²⁸ are the same as the specific examples of R ²¹ and R ²² , and the preferred ranges are also the same, but as R ²⁶ , R ²⁷ , and R ²⁸ , a hydrogen atom, an alkyl group Or a sulfo group (including a salt state) is preferable, and a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (most preferably a methyl group), or a sulfo group is more preferable.
Specific examples and preferred ranges of the counter cation when the sulfo group is in a salt state are the same as the specific examples and preferred ranges when the compound represented by the general formula (1) is a salt.

In general formula (4), Q represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
Examples of the aliphatic group include an alkyl group, a cycloalkyl group, and an alkenyl group.
Examples of the aromatic group include an aryl group.
Moreover, an aralkyl group is mentioned as a group applicable to an aromatic group and an aliphatic group.

Specific examples of the alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, and heterocyclic group include the groups described in R ²³ and R ²⁴ described above.
Each group may further have a substituent, and examples of the substituent are the same as the examples described in the above R ²³ and R ²⁴ .

Q is preferably an aryl group or a heterocyclic group substituted with an electron-withdrawing group or a sulfo group (including a salt state). Specific examples and preferred ranges of the counter cation when the sulfo group is in a salt state are the same as the specific examples and preferred ranges when the compound represented by the general formula (1) is a salt.
The electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less.
Specific examples of the electron withdrawing group having a σp value of 0.20 or more include the electron withdrawing group described in Z ¹ above, and preferably a cyano group, a nitro group, and a halogen atom.

The compound represented by the general formula (4) has at least one ionic hydrophilic group.
The ionic hydrophilic group is preferably at least one group selected from a sulfo group, a carboxyl group, a phosphono group and a quaternary ammonium group from the viewpoint of water solubility.
As the ionic hydrophilic group, at least one group selected from a sulfo group, a carboxyl group, and a phosphono group is preferable, and among them, a carboxyl group and a sulfo group are preferable. In particular, at least one is most preferably a sulfo group. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable. Among alkali metal salts, potassium ion, sodium ion, and lithium ion are preferable, lithium ion and sodium ion are more preferable, and sodium ion is most preferable.

  The compound represented by the general formula (4) preferably has 3 or more and 6 or less ionic hydrophilic groups in its molecule from the viewpoint of water solubility, and has 3 or more and 6 or less sulfo groups. More preferably, it has 3 or more and 5 or less sulfo groups.

  The compound represented by the general formula (4) is preferably a compound represented by the following general formula (4 ').

In General Formula (4 ′), Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , and R ₄₃ are each independently a hydrogen atom, aliphatic Represents a group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or an ionic hydrophilic group.
M ₁ and M ₂ each independently represents an oxygen atom or a sulfur atom.
Each group of Z ² , R ²¹ and R ²² may further have a substituent.
However, the general formula (4 ′) has at least one ionic hydrophilic group.

In general formula (4 ′), Z ² , R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ are respectively Z ² , R ²¹ , R ^{22 in} general formula (4). ^{R 25, R 26, R 27} , R 28, and has the same meaning as ^{R 29,} it is the same specific examples and preferred ranges.

In general formula (4 ′), R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , and R ₄₃ are respectively Independently, hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, or ionic hydrophilic group Represents. Specific examples of these groups are the same as those described for R ²³ and R ²⁴ in the general formula (4). The ionic hydrophilic group is as described above.
R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , and R ₄₃ are a hydrogen atom, an alkyl group, or a sulfo group It is preferable that

In General Formula (4 ′), M ₁ and M ₂ each independently represent an oxygen atom or a sulfur atom, and preferably a sulfur atom.

  A method for synthesizing the compound represented by the general formula (4) will be described. Here, the manufacturing method of the compound represented by the following general formula (4-R1) or (4-R2) among the compounds represented by the general formula (4) will be described.

In the general formula (4-R1), Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ are each represented by the general formula ( It is synonymous with Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ in 4). Q ₁ represents an aliphatic group, an aromatic group or a heterocyclic group.
In the general formula (4-R2), Z ¹ , Z ² , R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ are each represented by the general formula (4). ^{Z 1, Z 2, R 21} , R 22, R 24, R 25, R 26, R 27, R 28, and the same meaning as ^{R 29.} Q ₁ and Q ₂ each independently represents an aliphatic group, an aromatic group, or a heterocyclic group.

The compound of the general formula (4-R1) can be obtained by any of the following methods, <1> and / or <2>.
Method <1>
(A) a step of reacting an aminopyrazole represented by the following general formula (4-1) with a diazotizing agent to form a diazonium salt;
(B) The diazonium salt formed in the step (a) is reacted with a coupling agent represented by the following general formula (4-2) to form a compound represented by the following general formula (4-H1). And (c) in the presence of a base, the compound formed in the step (b) is reacted with an alkylating agent, an arylating agent or a heterylating agent, and is represented by the general formula (4-R1). A method comprising the step of forming a compound.

In the general formulas (4-1), (4-2), and (4-H1), Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are each represented by Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ^{29 in the} general formula (4). It is synonymous.

  Method <2> is a method including a step of introducing a water-soluble group into the compound represented by the general formula (4-R1) by electrophilic reaction. Furthermore, the method described in detail below is preferable for the electrophilic reaction.

  In the method <1>, it is preferable to use a dilute hydrochloric acid aqueous solution of sodium nitrite as the diazotizing agent used in the step (a). In addition, isopentyl nitrite and nitrosylsulfuric acid can also be used as diazotizing agents.

In method <1>, the coupling agent used in step (b) is most preferably a nitrogen-containing 6-membered heterocyclic coupler represented by the general formula (4). Preferred examples of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ^{29 in} the general formula (4) are those of the general formula (4). Same as the case.

  In the method <1>, the alkylating agent, arylating agent, or heterylating agent used in the step (c) is represented by the following general formulas (5), (6), and (7).

In the general formula (5), R represents an optionally substituted alkyl group, and X represents a halogen atom or OSO ₂ R ′. R ′ represents an alkyl group or an aryl group such as a phenyl group.
In the general formula (6), Ar represents a phenyl group substituted with an electron withdrawing group, and is preferably substituted with a substituent having a total Hammett σp value of 0.2 or more. X represents a halogen atom or OSO ₂ R ′. R ′ represents an alkyl group or an aryl group such as a phenyl group.
In the general formula (7), Het represents a heterocyclic ring, and a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a triazyl group, and a 2-furyl group are preferable. X represents a halogen atom or OSO ₂ R ′. R ′ represents an alkyl group or an aryl group such as a phenyl group.
As the base used in the step (c), an organic base such as diisopropylethylamine and an inorganic base such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide can be used. .

The electrophilic reaction in the above method <2> includes sulfonation, Mannich reaction, and Friedel-Crafts reaction. Of these, sulfonation is preferred.
As a method of sulfonating the general formula (4-R1), sulfonation is performed using a sulfonating agent such as concentrated sulfuric acid, 10% to 60% fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, amidosulfuric acid and the like. Can do. A solvent may be used, and as the solvent, acetic acid, acetic anhydride, sulfolane, ethyl acetate, ether, carbon tetrachloride, acetonitrile, or the like may be used.
In formula ^{_{(4-R1), Q 1}} , R 23, R 24, R 26 (R 28), it is preferred ^{that R 27} is _{^{sulfonation, Q 1, R 23, R}} 24, R 26 (R 28 ), When the substituent of R ²⁷ has a plurality of reactive sites capable of being sulfonated, sulfonated dyes having different substitution positions may be mixed.
In this case, a sulfonated dye having a different substitution position in the range of 0.1% to 50% by HPLC area% may be mixed with the main sulfonated dye. The reaction temperature (Celsius) is desirably from -5 degrees to 80 degrees, and more desirably from 10 degrees to 70 degrees. The reaction time is preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours.

  In the production method of the general formula (4-R1) or the general formula (4-R2), the deoxygenation condition is preferably produced by filling the reaction system with an inert gas such as nitrogen or argon, It is preferable to bubble the reaction solution with these inert gases.

  Aminopyrazole represented by general formula (4-1), which is a starting material used in step (a) of method <1>, is disclosed in U.S. Pat. No. 3,336,285 and Heterocycles, 20,519 (1983) and Japanese Patent Publication No. 6-19036.

  Pyridine couplers (coupling agents represented by general formula (4-2)) used in step (b) of method <1> are disclosed in JP-A-51-83931, JP-A-49-74718, It can be synthesized by the method described in Japanese Patent Publication No. 52-46230.

  The azo dye represented by the general formula (4) can be synthesized by the production method of the present invention described above. Specific examples of the azo dye of the present invention are shown below, but are not limited to the following examples. In the following specific examples, the sulfo group may be in a salt state.

(Coloring composition)
The coloring composition of the present invention contains at least one compound represented by the above general formula (1) of the present invention and at least one compound represented by the above general formula (4) of the present invention. The synergistic effect of the compound represented by the general formula (1) and the compound represented by the general formula (4) makes it possible to achieve both good fastness and good hue.
The coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The coloring composition of the present invention can be prepared by dissolving and / or dispersing the compound of the present invention in a lipophilic medium or an aqueous medium as a medium. Preferably, an aqueous medium is used. The coloring composition of the present invention includes an ink composition excluding a medium.

  In the present invention, the content of the compound of the present invention contained in the colored composition is the kind of substituents in the general formula (1) and general formula (4) used, and the solvent used for producing the colored composition. The content of the compound represented by the general formula (1) in the colored composition is preferably 1 to 20% by mass with respect to the total mass of the colored composition, although it is determined depending on the type of component and the like. It is more preferable that 10 mass% is contained, and it is still more preferable that 2-6 mass% is contained.

  By making the content of the compound represented by the general formula (1) contained in the coloring composition 1% by mass or more, it is possible to improve the color developability of the ink on the recording medium when printed, and it is necessary. Image density can be ensured. Moreover, when the total amount of the compounds represented by the general formula (1) contained in the colored composition is 20% by mass or less, the dischargeability of the colored composition can be improved when used in the ink jet recording method. In addition, it is possible to obtain an effect such that the inkjet nozzle is not easily clogged.

  From the viewpoint of hue, the content of the compound represented by the general formula (4) in the colored composition is preferably 1 to 18% by mass with respect to the total mass of the colored composition, and is preferably 1 to 10% by mass. More preferably it is included.

  In the coloring composition, the mass ratio of the compound represented by the general formula (1) and the compound represented by the general formula (4) is preferably 9/1 to 1/9, and 2/8 to 8 /. 2 is more preferable, and 2/8 to 6/4 is still more preferable. By setting the mass ratio within the above range, it is preferable from the viewpoint of light resistance, ozone resistance, and hue balance.

  The coloring composition of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of other additives include additives that can be used in ink jet recording inks described later.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described.
The present invention also relates to an inkjet recording ink containing the coloring composition of the present invention.
The ink for inkjet recording can be prepared by dissolving and / or dispersing the compound (mixture) of the present invention in an oleophilic medium or an aqueous medium. Preferably, the ink uses an aqueous medium.
If necessary, other additives can be contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

  The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink for ink jet recording at the ink ejection port of the nozzle used in the ink jet recording method.

  As the drying inhibitor, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  The penetration accelerator is preferably used for the purpose of allowing the ink for ink jet recording to penetrate better into paper. As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants and the like can be used. . If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  The ultraviolet absorber is used for the purpose of improving image storability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, U.S. Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-21114, Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8 No. -502911, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, the neutralizing agent (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the ink for ink jet recording, the pH adjusting agent is preferably added so that the ink for ink jet recording has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10. preferable.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the ink for ink jet recording of the present invention is preferably 25 to 70 mN / m. Furthermore, 25-60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

  When the compound of the present invention is dispersed in an aqueous medium, as described in JP-A Nos. 11-286637, 2000-78491, 2000-80259, 2000-62370, and the like, Colored fine particles containing a compound and an oil-soluble polymer are dispersed in an aqueous medium, or as described in Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, and 2000-203857. It is preferable that the compound of the present invention dissolved in a high boiling point organic solvent is dispersed in an aqueous medium. The specific method for dispersing the compound of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above-mentioned patent publications. be able to. Alternatively, the compound of the present invention may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the ink jet recording ink preparation method described above is disclosed in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used to prepare the ink for inkjet recording of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

  In 100 parts by mass of the inkjet recording ink of the present invention, the compound of the present invention is preferably contained in an amount of 0.2 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 6 parts by mass or less. In addition, in the ink for inkjet recording of the present invention, other dyes may be used in combination with the compound of the present invention. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

  The ink for inkjet recording of the present invention preferably has a viscosity of 30 mPa · s or less. The surface tension is preferably 25 mN / m or more and 70 mN / m or less. Viscosity and surface tension are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.

  The ink for inkjet recording of the present invention can be used not only for forming a single color image but also for forming a full color image. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Any applicable yellow dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); for example, coupler components Azomethine dyes having open-chain active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

  Any applicable magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. And dyes.

  Any applicable cyan dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Examples include polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or a quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
Applicable black materials include disazo, trisazo, tetraazo dyes, and carbon black dispersions.

  The ink composition of the present invention can be used in recording methods such as printing, copying, marking, writing, drawing, stamping, and the like, and is particularly suitable for use in an inkjet recording method.

[Inkjet recording method]
The present invention also relates to an inkjet recording method for forming an image using the colored composition or the inkjet recording ink of the present invention.
In the ink jet recording method of the present invention, energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic paper, cloth, glass, metal, ceramics, etc. To do.

  When forming an image, a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the polymer latex to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition place may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, Japanese Patent Application Nos. 2000-363090, 2000-315231, 2000-354380, 2000-343944, 2000-268952, 2000-299465, 2000-297365, etc. The method described in the specification can be preferably used.

Hereinafter, a recording paper and a recording film used for ink jet printing using the ink of the present invention will be described.
The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheets may be used. The thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m 2.
The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used as the support.
It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,283,853, 4,282,305, It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

  The water-proofing agent is effective for making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

  Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzotriazole ultraviolet absorbers such as benzophenone. Of these, zinc sulfate is particularly preferred.

  The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826. Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

  The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

  The ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, a drop-on-demand system (pressure) that uses the vibration pressure of a piezo element. Pulse method), acoustic ink jet method that converts electrical signal into acoustic beam and irradiates ink and uses ink to discharge ink, and thermal ink jet that heats ink to form bubbles and uses generated pressure Used for systems. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited to these Examples at all. Unless otherwise specified, “%” and “part” in the examples are mass% and part by mass.

(Synthesis example)
Synthesis of Compound (1A) In a 150 mL three-necked flask, 60 g of chlorosulfonic acid (manufactured by Acros) and 6.2 g of phosphorus oxychloride (manufactured by Fischer) are added and stirred at room temperature. 9.54 g (manufactured by CHUGAI AMINOL FAST PINKR) was carefully added, then heated to 70 ° C. and reacted for 1 hour. The reaction solution was cooled to room temperature, quenched with 300 g of ice water, and the precipitated crystals were separated by filtration and washed with cold saturated brine. The obtained crystals were dispersed in 150 mL of water, and the dropwise addition was continued using 2 mol / L sodium hydroxide until the pH became constant at 9.0. When there is no change in pH, the pH is adjusted to 8.5 using dilute hydrochloric acid of 0.2 mol / L, desalting is performed using a dialysis tube, and dust removal is performed using a GF / F filter (Whatman). And dried with a blow dryer at 60 ° C. to obtain 6 g of green glossy crystals. The absorption maximum wavelength in the diluted aqueous solution was 529 nm. In the LC-MS spectrum measured under the following conditions, three components having a retention time of 7.12 minutes, 8.32 minutes, and 10.08 minutes were observed, and the molecular weight thereof was 894 (Posi: 895 [M + 1]). ⁺ , Nega: 446.2 [M-2H] ²⁻ ).

(LC-MS conditions)
Column Genesis C18 (100 x 4.6 mm)
Temperature 40 ℃
Eluent A 10 mM ammonium acetate aqueous solution eluent B 10 mM ammonium acetate acetonitrile / water (90/10) solution gradient 0 min (B concentration 5%), 2 min (B concentration 5%), 25 min (B concentration 50%), 30 minutes (B concentration 95%), 31 minutes (B concentration 5%), 40 minutes (B concentration 5%)
Flow rate 1.0 mL / min Detection wavelength 200-700 nm
MS (range) 200-1200
Injection volume 10μL

FIG. 1 shows a ¹ H NMR spectrum of compound (1A) in deuterated dimethyl sulfoxide.

  Other exemplary compounds can also be synthesized according to the above method.

[Example 1]
Deionized water was added to the following components to make 100 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / L, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.25 μm to prepare a magenta ink liquid.

Compound of general formula (1) (the following compound (1A)) 0.5 g
Compound of general formula (4) (the following compound (2A)) 3.0 g
Diethylene glycol 10.65g
Glycerin 14.70g
Diethylene glycol monobutyl ether 12.70g
Triethanolamine 0.65g
Olfin E1010 (Nissin Chemical Industry Co., Ltd.) 0.9g

[Examples 2 to 15 and Comparative Examples 1 to 3]
Ink solutions of Examples 2 to 15 and Comparative Examples 1 to 3 were prepared in the same manner as the preparation of the ink solutions of Example 1, except that the dyes and dye addition amounts were changed as shown in Table 1 below. As a comparative dye, C.I. I. Acid Red 289 (AR289) was used.

(Image recording and evaluation)
The following evaluation was performed on the inks for ink jet recording of the above Examples and Comparative Examples. The results are shown in Table 1.
In addition, in Table 1, ozone resistance and light resistance are obtained by using a photo glossy paper (PM photo paper <Glossy> manufactured by EPSON Co., Ltd .; PM-700C) for each ink jet recording ink using an ink jet printer (manufactured by EPSON Co., Ltd .; PM-700C). KA420PSK, EPSON)) and then evaluated after recording the image.

<Ozone resistance>
While passing dry air through a double glass tube of a Siemens type ozonizer, an AC voltage of 5 kV was applied, and this was used to put the image in a box set at an ozone gas concentration of 5 ± 0.1 ppm, room temperature, in a dark place. The formed photo glossy paper was allowed to stand for 7 days, and the image density before and after being left under ozone gas was measured using a reflection densitometer (X-Rite 310TR) and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.

<Light resistance>
After measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 7 days using a weather meter (Atlas C.165), and the image density Cf was measured again. The dye residual ratio ({(Ci−Cf) / Ci} × 100%) was calculated and evaluated from the difference in image density before and after the xenon light irradiation. The image density was measured using a reflection densitometer (X-Rite 310TR).
The dye residual ratio was measured at three points with reflection densities of 1, 1.5 and 2.0. At any concentration, the evaluation was made in three stages: A when the dye residual ratio was 80% or more, B as 1 or 1 or 2 points less than 80%, and C as less than 80% at all concentrations.

<Hue>
The hue was visually evaluated in three stages: best, good and poor. The evaluation results are shown in Table 1 below. In Table 1 below, A indicates that the hue is the best, B indicates that the hue is good, and C indicates that the hue is poor.

  As is apparent from the results in Table 1, the inks of the examples using the coloring composition of the present invention have extremely high performances in terms of ozone resistance, light resistance and hue as compared with the inks of the comparative examples. I understand that.

Claims (15)

A coloring composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (4).

In general formula (1), D represents the residue remove | excluding n hydrogen atoms from the compound represented by the following general formula (2), and n represents the number of 3-6. M represents a hydrogen atom or a counter cation. M may be the same or different.

In general formula (2), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represents a monovalent substituent, R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom or a monovalent substituent, and n 101 and n102 represents the number of 0-5 each independently, and n103 represents the number of 0-4. n101, if n102 and n103 represents the number of 2 or more, respectively, a plurality of ^{R 101, R 102,} and ^{R 103} may be different even in the same.

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ²³ and R ²⁴ are not both hydrogen atoms.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. R ²¹ and R ²³ , or R ²³ and R ²⁴ may combine to form a 5- or 6-membered ring.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
Each group of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ and Q may further have a substituent.
However, general formula (4) has at least one ionic hydrophilic group.   The coloring composition according to claim 1, wherein n in the general formula (1) is 4. The colored composition according to claim 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

In General Formula (3), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent a monovalent substituent, n201 and n202 each independently represent a number from 0 to 4, and n203 is a number from 0 to 4 Represents. n201, n202, and if n203 represents the number of 2 or more, respectively, a plurality of ^{R 201, R 202,} and ^{R 203} may be different even in the same. M represents a hydrogen atom or a counter cation. M may be the same or different. The coloring composition according to any one of claims 1 to 3, wherein each of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ²⁰¹ , R ²⁰² , and R ²⁰³ independently represents an alkyl group or an acylamino group. The colored composition according to claim 1, wherein R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent an alkyl group having 1 to 6 carbon atoms. object.   The coloring composition according to any one of claims 1 to 5, wherein each of n101, n102, n201, and n202 independently represents a number of 2 to 4.   The colored composition according to claim 1, wherein n103 and n203 represent 0.   The coloring composition as described in any one of Claims 1-7 whose salt of the compound represented by the said General formula (1) is lithium salt, sodium salt, or potassium salt.   The ionic hydrophilic group in the general formula (4) is at least one group selected from a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. The coloring composition as described. In the general formula (4), the R ²³ and R ²⁴ are each independently a hydrogen atom, an aromatic group, or a coloring composition according to any one of claims 1 to 9 which represent a hetero group.   The coloring composition as described in any one of Claims 1-10 which contains 1-10 mass% of compounds or its salt represented by General formula (1).   The coloring composition as described in any one of Claims 1-11 which contains 1-10 mass% of compounds represented by General formula (4).   The color ratio according to any one of claims 1 to 12, wherein the mass ratio of the compound represented by the general formula (1) and the compound represented by the general formula (4) is 1/9 to 9/1. Composition.   Ink for inkjet recording containing the coloring composition as described in any one of Claims 1-13.   The inkjet recording method of forming an image using the coloring composition as described in any one of Claims 1-13, or the ink for inkjet recording of Claim 14.

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