JP2016069585A - Compound having xanthene skeleton, colored composition, ink for inkjet recording, inkjet recording method, inkjet printer cartridge, inkjet recorded matter, color filter, color toner, transfer ink, and textile printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound that can further improve printing density, light fastness, ozone resistance, moisture resistance, and ink storage stability, a colored composition and an ink for inkjet recording containing the compound, an inkjet recording method using the ink for inkjet recording, an inkjet printer cartridge, an inkjet recorded matter, a color filter, a color toner, a transfer ink, and a textile printing method using the compound.SOLUTION: The compound is represented by general formula (1). In the formula, Rrepresents H, an alkyl group, an aryl group, or a heterocyclic group; Rrepresents an alkyl group, an aryl group, or a heterocyclic group; R, R, Rand Reach independently represent an alkyl group; Rto Reach independently represent a substituent; M represents H or a counter cation; n1 and n2 each independently represent 0 or 1; n3 represents 0 to 4; n4 and n5 each independently represent 0 to 3; and at least one in SOM present in the compound is dissociated and is present as SO.SELECTED DRAWING: None

Description

  The present invention relates to a compound having a xanthene skeleton, a coloring composition containing the above compound, an ink for ink jet recording, an ink jet recording method, an ink jet printer cartridge, an ink jet recorded material, a color filter, a color toner, a transfer ink, and a textile printing 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 a high density recording image, 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.

Patent Document 1 describes a compound having a xanthene skeleton in which an alkylsulfamoyl group having a specific substituent containing a triazine ring is substituted.
Patent Documents 2 and 3 describe compounds having a xanthene skeleton substituted with an alkylsulfamoyl group.

JP 2013-49776 A JP 2013-116956 A International Publication No. 2000/64988

  However, in the field of dyes, further improvement in performance is required, it has excellent print density, and further improves image fastness such as light resistance, ozone resistance, moisture resistance, and ink storage stability. There is a need for compounds that can be used.

  An object of the present invention is to provide a compound having an excellent printing density and capable of further improving light resistance, ozone resistance, moisture resistance, and ink storage stability. Another object of the present invention is to provide a coloring composition containing the above compound, an ink jet recording ink, an ink jet recording method using the ink for ink jet recording, an ink jet printer cartridge, and an ink jet recorded matter. Furthermore, it aims at providing the color filter, color toner, and transfer ink containing the said compound. Another object of the present invention is to provide a printing method using the above compound and a fabric printed by the above printing method.

As a result of intensive studies, the present inventors have found that the above problem can be solved by the compound represented by the general formula (1).
The compound represented by the general formula (1) is a xanthene derivative having a sulfamoyl group substituted with a bulky substituent. Although the mechanism of action is unknown, it is considered that the existence state of the xanthene compound is changed by using a sulfamoyl group as the sultone ring site, and the above problems can be solved. Moreover, it is considered that a sultam ring can be stably present without being closed by introducing a bulky substituent into the sulfamoyl group.

  That is, the present invention relates to the following items.

<1>
A compound represented by the following general formula (1).

In general formula (1), R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, R ² has at least one SO ₃ M or COOM as a substituent. When R ¹ represents a hydrogen atom, R ² represents a substituted or unsubstituted secondary or tertiary alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ¹ and R ² may combine with each other to form a ring.
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a substituted or unsubstituted alkyl group. R ⁷ , R ⁸ and R ⁹ each independently represents a substituent.
M represents a hydrogen atom or a counter cation. M may be the same or different. n1 and n2 each independently represents 0 or 1.
n3 represents the number of 0-4. n4 and n5 each independently represents a number from 0 to 3.
When n3, n4 and n5 each represent a number of 2 or more, the plurality of R ⁷ , R ⁸ and R ⁹ may be the same or different.
However, any one of SO ₃ M or COOM present in the general formula (1) is dissociated to SO ₃ ^- are present as ^- or COO.
<2>
<1> The compound according to <1>, wherein R ² has at least one SO ₃ M as a substituent.
<3>
The compound according to <1> or <2>, wherein M represents a lithium ion, a sodium ion, a potassium ion, or an ammonium ion.
<4>
The coloring composition containing the compound of any one of <1>-<3>.
<5>
<1>-<3> The ink for inkjet recording containing the compound of any one of <3>.
<6>
An ink jet recording method using the ink for ink jet recording according to <5>.
<7>
An inkjet printer cartridge filled with the inkjet recording ink according to <5>.
<8>
An ink jet recorded matter in which a colored image is formed on a recording material using the ink for ink jet recording described in <5>.
<9>
A textile printing method including the following steps (1) to (4).
(1) A step of adjusting the color paste by adding the colored composition according to <4> to a liquid containing at least a polymer compound and water. (2) Printing the color paste of (1) on a fabric. Step (3) Step of applying to steam printed fabric (4) Step of washing and drying printed fabric <10>
A textile printing method comprising the following steps (11) to (14).
(11) A step of applying a paste containing at least a polymer compound and water to the fabric (12) A step of printing the ink for inkjet recording according to <5> on the fabric by an inkjet method (13) A fabric printed with steam (14) Washing and drying the printed fabric <11>
The textile printing method according to <9> or <10>, wherein the fabric contains polyamide.

  According to the present invention, it is possible to provide a compound that has an excellent printing density and can further improve light resistance, ozone resistance, moisture resistance, and ink storage stability. Moreover, the coloring composition containing the said compound, the ink for inkjet recording, the inkjet recording method using the inkjet recording ink, an inkjet printer cartridge, and an inkjet recorded matter can be provided. Furthermore, a color filter, a color toner, and a transfer ink containing the above compound can be provided. Further, it is possible to provide a printing method using the above compound and a fabric printed by the above printing method.

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. Examples of non-aromatic heterocyclic groups include morpholinyl groups.

  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 the sodium salt is most preferred.

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

[Compound represented by the general formula (1)]
The compound represented by the following general formula (1) will be described.

In general formula (1), R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, R ² has at least one SO ₃ M or COOM as a substituent. When R ¹ represents a hydrogen atom, R ² represents a substituted or unsubstituted secondary or tertiary alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ¹ and R ² may combine with each other to form a ring.
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a substituted or unsubstituted alkyl group. R ⁷ , R ⁸ and R ⁹ each independently represents a substituent.
M represents a hydrogen atom or a counter cation. M may be the same or different. n1 and n2 each independently represents 0 or 1.
n3 represents the number of 0-4. n4 and n5 each independently represents a number from 0 to 3.
When n3, n4 and n5 each represent a number of 2 or more, the plurality of R ⁷ , R ⁸ and R ⁹ may be the same or different.
However, any one of SO ₃ M or COOM present in the general formula (1) is dissociated to SO ₃ ^- are present as ^- or COO.

R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. It is preferably a substituted aryl group, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group.

R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and when R ¹ represents a hydrogen atom, R ² represents a substituted or unsubstituted 2 It represents a primary or tertiary alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
R ² is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and more preferably a substituted or unsubstituted alkyl group.

When R ¹ and R ² represent an alkyl group, the alkyl group may be linear, branched, or cyclic, preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 7 carbon atoms. More preferred is an alkyl group having 2 to 6 carbon atoms. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, and a methyl group and an ethyl group are preferable. .
When R ¹ represents a hydrogen atom, R ² preferably represents a secondary alkyl group or a tertiary alkyl group, more preferably a secondary alkyl group.
The “secondary alkyl group” refers to an alkyl group in which a carbon atom bonded to a nitrogen atom is a secondary carbon atom bonded to two carbon atoms, and the “tertiary alkyl group” refers to An alkyl group in which the carbon atom bonded to the nitrogen atom is a tertiary carbon atom bonded to three carbon atoms.
Examples of the secondary alkyl group or tertiary alkyl group include branched or cyclic alkyl groups. Examples of the branched secondary alkyl group include isopropyl group, sec-butyl group, 1-ethylpropyl group, 1-ethylpropyl group, Examples thereof include a methylisobutyl group, a 1-methylisopentyl group, a 1-methyloctyl group, and a 1-ethyl-3-methylbutyl group, and an isopropyl group and a sec-butyl group are preferable.
Examples of branched tertiary alkyl groups include tert-butyl, tert-pentyl, 1,1-dimethylbutyl, 1,1-dimethylpentyl, 1,1-dimethylhexyl, 1,1-dimethylheptyl. Group, 1,1-dimethyloctyl group, 1-ethyl-1-methylpropyl group, 1,1,3,3-tetramethylbutyl group, etc., tert-butyl group, tert-pentyl group, 1,1 , 3,3-tetramethylbutyl group is preferable, and tert-butyl group and 1,1,3,3-tetramethylbutyl group are more preferable.
Examples of the cyclic secondary alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. A cyclopentyl group and a cyclohexyl group are preferable, and a cyclohexyl group is more preferable.
Examples of the cyclic tertiary alkyl group include an adamantyl group, a norbornane group, a tetracyclododecanyl group, a tricyclodecanyl group, a diamantyl group, and the like, and an adamantyl group is preferable.

R ² has at least one SO ₃ M or COOM as a substituent. When R ² has SO ₃ M or COOM, water solubility can be imparted, and it can exist stably without precipitation of crystals in an aqueous solution.
R ² is preferably substituted with at least one SO ₃ M. Moreover, it is preferable that 2 or more of SO ₃ M or COOM is substituted.
Any one of SO ₃ M and COOM present in the general formula (1) is dissociated and exists as SO ₃ ⁻ or COO ⁻ , and one of SO ₃ M substituted for R ² is dissociated. Thus, SO ₃ ⁻ is preferable.

The reason why R ¹ and R ² are secondary alkyl groups or tertiary alkyl groups is excellent in printing density and can improve light resistance is unknown in detail, but is estimated as follows. . That is, when R ¹ and R ² are a secondary alkyl group or a tertiary alkyl group, the sulfamoyl group containing R ¹ and R ² becomes bulky. As a result, steric hindrance occurs, and repulsion caused by bulky substituents suppresses intermolecular interaction between the compounds represented by the general formula (1), thereby causing an excited state (for example, an excited dimer, which is a starting point of photolysis). (Formation) is presumed to be mitigated.

In addition, when R ^{1 of the} compound represented by the general formula (1) is a hydrogen atom, as shown in the following equilibrium reaction formula, there is a colorless ring-closed isomer, which is caused by steric hindrance of R ¹ . It is estimated that the generation of colorless ring closures is suppressed. Note that R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , M, n1, n2, n3, n4, and n5 in the following equilibrium reaction formula are in the general formula (1). ^{R 2, R 3, R 4} , R 5, R 6, R 7, R 8, R 9, M, n1, n2, n3, n4, are the same as n5.

When R ¹ and R ² represent an aryl group, an aryl group having 6 to 14 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and an aryl group having 6 carbon atoms is still more preferable. The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

When R < ¹ >, R < ² > represents a heterocyclic group, a C5-C10 heterocyclic group is preferable, a C5-C8 heterocyclic group is more preferable, and a C5-C6 heterocyclic group is still more preferable. . The hetero ring group is preferably a piperidyl group, a tetrahydrofuryl group, a thienyl group, a furyl group, or a pyridyl group, and more preferably a 4-piperidyl group.

R ¹ and R ² may be bonded to each other to form a ring, and the formed ring is preferably a piperidine ring, a piperazine ring, or a pyrrolidine ring.

When R ¹ and R ² represent an alkyl group, an aryl group, or a heterocyclic group, or when bonded to each other to form a ring, these may be further substituted with a substituent. Examples of the further substituent include a substituent selected from the above substituent group A. An alkyl group, an aryl group, an amino group, a hydroxyl group, a halogen atom, an ionic hydrophilic group, and the following general formula (2) The substituents represented are preferred and these may be further substituted.

In general formula (2), R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. * Represents a bond.

When R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ represent an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
When R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ represent an aryl group, an aryl group having 6 to 10 carbon atoms is preferable, and an aryl group having 6 carbon atoms is more preferable.
When R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ represent an alkyl group or an aryl group, these may have a substituent, such as a hydroxyl group, a carboxyl group, a sulfo group, etc. Is mentioned.

In the general formula (1), —NR ¹ R ² is preferably —NHR ¹² or —NR ¹¹ R ¹³ from the viewpoints of availability of raw materials, ease of synthesis, and stability. R ¹² represents a secondary or tertiary alkyl group substituted with a group having SO ₃ M or COOM, and R ¹¹ and R ¹³ are each independently 1 substituted with a group having SO ₃ M or COOM. Represents a secondary alkyl group. However, R ¹¹ and R ¹³ may be connected to each other to form a ring.

Preferred specific examples of —NHR ¹² are shown below. In specific examples, n1 and n2 represent 1 to 2, ^{L 1} represents a (n1 + 1) -valent linking group, ^{L 2} represents a (n2 + 1) -valent linking group. A ¹ and A ² each independently represents SO ₃ M or COOM.
n1 and n2 preferably represent 1.
As the (n1 + 1) -valent linking group and the (n2 + 1) -valent linking group, an alkylene group, an alkenylene group, and an arylene group are preferable.

Preferred specific examples of —NR ¹¹ R ¹³ are shown below. In the following specific examples, n1 and n2 represent 1 to 2, L1 represents a (n1 + 1) -valent linking group, and L2 represents a (n2 + 1) -valent linking group. A ¹ and A ² each independently represents SO ₃ M or COOM.
n1 and n2 preferably represent 1.
As the (n1 + 1) -valent linking group and the (n2 + 1) -valent linking group, an alkylene group, an alkenylene group, and an arylene group are preferable.

From the viewpoint of light resistance, it is preferable that R ¹ is a hydrogen atom and R ² is a secondary alkyl group or a tertiary alkyl group, and —NR ¹ R ² in the general formula (1) represents —NHR ¹² It is more preferable.

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a substituted or unsubstituted alkyl group. When R ³ , R ⁴ , R ^5, and R ⁶ are substituted or unsubstituted alkyl groups, a compound having excellent hue and vivid magenta color is obtained.
R ³ , R ⁴ , R ⁵ and R ⁶ are preferably an alkyl group having 1 to 6 carbon atoms and more preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of availability of raw materials. 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, a t-butyl group, and the like. 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.

Examples of the substituent represented by R ⁷ , R ⁸ and R ⁹ include a substituent selected from the above substituent group A. From the viewpoint of availability of raw materials and ease of synthesis, a halogen atom, aryl group, alkoxy Group, alkyl group, acylamino group, alkyl or arylsulfonylamino group, alkyl or arylureido group are preferred, alkyl group and acylamino group are more preferred, and alkyl group is still more preferred.

When R ⁷ , R ⁸ , and R ⁹ 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, a t-butyl group, and the like. 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 ⁷ , R ⁸ , and R ⁹ 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 printing density, 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, an isobutyrylamino group, a pivaloylamino group, a cyclohexanoylamino group, and the isobutyrylamino group is particularly preferable.
The acylamino group is preferably a monoacylamino group.

When R ⁷ , R ⁸ , and R ⁹ represent an alkyl or arylsulfonylamino group, from the viewpoint of availability of raw materials, a mesylamino group, a benzenesulfonylamino group, and a p-tosylamino group are preferable, and a mesylamino group, a p-tosylamino group Are more preferable, and a mesylamino group is particularly preferable.

When R ⁷ , R ⁸ , and R ⁹ represent an alkyl or aryl ureido group, an alkyl ureido group or a phenyl ureido group having 1 to 6 carbon atoms is preferable, and an isopropyl ureido group is particularly preferable from the viewpoint of availability of raw materials.

R ⁷ and R ⁸ are preferably substituted at the ortho position and / or the para position with respect to the nitrogen atom, and —SO ₃ M in the phenyl group having R ⁷ and R ⁸ is meta-position or with respect to the nitrogen atom. Substitution at the para position is preferred.

n3 represents the number of 0-4. From the viewpoint of availability of raw materials, n3 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.
n4 and n5 each independently represents a number from 0 to 3. From the viewpoints of availability of raw materials and ease of synthesis, n4 and n5 are preferably 1 to 3, more preferably 2 to 3, and particularly preferably 3.
When n3, n4 and n5 each represent a number of 2 or more, a plurality of R ⁷ , R ⁸ and R ⁹ may be the same or different.

In 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), Ms may be the same or different. That is, the compound represented by the general formula (1) is in a salt form when all the sulfo groups are in the form of a salt, and 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.

  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.

Next, a method for synthesizing the compound represented by the general formula (1) will be described. The compound represented by the general formula (1) can be synthesized, for example, by the following synthesis route. A compound represented by the general formula (c) was obtained by reacting the compound represented by the general formula (a) with the compound represented by the general formula (b) in the presence of a Lewis acid (for example, aluminum chloride). Thereafter, the compound represented by the general formula (c) and the compound represented by the general formula (d) are reacted in the presence of a Lewis acid (for example, magnesium oxide or zinc chloride) to thereby react the general formula (e The compound represented by general formula (b) and the compound represented by general formula (d) are the same compound (that is, R ⁴ = R ⁵ , n ⁴ = n ⁵ ), the compound represented by the general formula (e) is directly synthesized from the general formula (a) without synthesizing the general formula (c)). Further, the obtained general formula (e) is reacted with a chlorinating agent (for example, phosphorus oxychloride or thionyl chloride) to synthesize a compound represented by the general formula (f), which is represented by the general formula (g). The general formula (h) is synthesized by reacting the compound to be synthesized. Finally, the compound represented by the general formula (1) can be obtained by sulfonating the obtained general formula (h) using a sulfonating agent (for example, fuming sulfuric acid or chlorosulfonic acid). In the general formula (a), general formula (b), general formula (c), general formula (d), general formula (e), general formula (f), general formula (g), R in the general formula (h) ¹ , R ² , R ³ , R ⁴ , R ⁵ , M, n ³ , n ⁴ , n ⁵ are R ¹ , R ² , R ³ , R ⁴ , R ⁵ , M, n in the general formula (1). ³ , n ⁴ and n ⁵ are the same, and preferred examples are also the same. X in the general formula (f) represents a chlorine atom. Specific examples are illustrated in the examples.

  The compound represented by the general formula (a) can be obtained by a conventionally known method (for example, the method described in Journal of the American Chemical Society 2012, Vol. 134, No. 48, pages 19, 588 to 19,591).

General formula (b) and general formula (d) are obtained as commercially available reagents (for example, Tokyo Kasei catalog number T0467) or by a conventionally known method (for example, a method described in DE 2,412,578 (1974)). be able to.
General formula (g) can be obtained as a commercially available reagent (for example, Tokyo Kasei catalog number T0143 etc.).

(Coloring composition)
The coloring composition of the present invention contains at least one compound represented by the above general formula (1). 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 represented by the general formula (1) in a lipophilic medium or an aqueous medium as a medium. it can. 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 determined by the type of substituent in the general formula (1) used, the type of solvent component used for producing the colored composition, and the like. However, it is preferable that content of the compound represented by General formula (1) in a coloring composition is contained 1-20 mass% with respect to the gross mass of a coloring composition, and 1-10 mass% is contained. It is more preferable, and it is still more preferable that 2-6 mass% is contained.

  By setting the content of the compound represented by the general formula (1) contained in the coloring composition to 1% by mass or more, it is possible to improve the print density 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 coloring composition is 10% by mass or less, the discharging property of the coloring 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.

  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 ink for inkjet recording of the present invention contains the compound of the present invention.
The ink for inkjet recording can be produced by dissolving and / or dispersing the compound represented by the general formula (1) 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 solvents 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). Two or more kinds of the water-miscible organic solvents may be used in combination.

  It is preferable to contain 0.2 to 10 parts by mass of the compound represented by the general formula (1) in 100 parts by mass of the inkjet recording ink of the present invention, and 1 to 6 parts by mass is preferably contained. Is more preferable. In addition, in the ink for inkjet recording of the present invention, other dyes may be used in combination with the compound represented by the general formula (1). When using 2 or more types of pigment | dyes together, it is preferable that the sum total of content of a pigment | dye is the said 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 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, for example, 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 co-paper, fabric, 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.

[Inkjet printer cartridge and inkjet recording]
The ink cartridge for ink jet recording of the present invention is filled with the ink for ink jet recording of the present invention described above. Further, the ink-jet recorded matter of the present invention is obtained by forming a colored image on a recording material using the above-described ink for ink-jet recording of the present invention.

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, 4,2,387,305, 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-resistant 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.

The coloring composition for dyeing or printing of the present invention (hereinafter also referred to as “coloring composition”) contains a compound represented by the general formula (1). Moreover, only 1 type may be used for the compound represented by General formula (1), and it may use it in combination of 2 or more type.
The coloring composition of the present invention may contain only the compound represented by the general formula (1) as a colorant, but is still other colorant as long as the effects of the present invention are not impaired. May be contained. Examples of the colorant that may be used in combination include known dyes such as dyeing notes (24th edition issued by Color Dyeing Co., Ltd., the same applies hereinafter), dyes on pages 33 to 121, and pigments on pages 124 to 130. Etc.

The content of the compound represented by the general formula (1) in the coloring composition is preferably 1 to 20% by mass, and more preferably 1 to 10% by mass.
When the content of the compound represented by the general formula (1) contained in the coloring composition is 1% by mass or more, the print density of the ink on the recording medium when printed can be improved, and is required. Image density can be secured. In addition, when the total amount of the compounds represented by the general formula (1) contained in the coloring composition is 20% by mass or less, when used in printing methods such as dip dyeing, screen printing, roller printing, etc. It is possible to prevent the precipitation of the dye, and it is easy to adjust to an appropriate concentration. When used in the ink jet textile printing method, the dischargeability of the colored composition can be improved, and the ink jet nozzle is less likely to be clogged.
The colored composition in the present invention generally contains a solvent in addition to the compound of the general formula (1). The type and amount of the solvent vary depending on the type of the compound of the general formula (1), the dyeing concentration, and the dyeing method, but it is preferable to contain 40% by mass or more of the solvent with respect to the total amount of the colored composition. As a solvent, it is preferable to contain water, and it is preferable to contain 50 mass% or more of water with respect to the solvent whole quantity. Moreover, it is preferable to contain 30 mass% or more of water with respect to the whole quantity of a coloring composition.

[Coloring composition for dyeing or printing and dyeing or printing method]
The use form of the coloring composition for dyeing or printing of the present invention is not limited as long as it is a coloring composition for dyeing fibers. The dyeing method for fibers is roughly divided into a dip dyeing method and a printing method. Dipping is a process in which a dyed cloth or yarn is immersed in a dye solution in which a dye is dissolved or dispersed in a solvent, adsorbed uniformly on the fiber surface, the dye diffuses inside the fiber, and is dyed by bonding. is there. Textile printing is a dyeing method in which dyes and pigments are applied onto a fabric to give a pattern shape, and dyed pigments are dyed or fixed to make a dyed product with a pattern. The pattern effect is developed on the fabric to be dyed. Industrially, screen printing using a plate, roller printing, transfer printing using transfer paper, and ink-jet printing without plate making are performed.

[[Coloring composition for dip dyeing and method using the same]]
The dip dyeing comprises a step of immersing a fabric or thread in a dye solution to dye the dye, a washing step of washing away unfixed dye that is not dyed on the fiber, and a drying step. When the coloring composition of the present invention is used for dip dyeing, the coloring composition is used as a dyeing solution capable of immersing a fabric. In this case, the dyeing solution may contain a solvent, a leveling assistant, a pH adjuster, an inorganic neutral salt, a dispersant and the like in addition to the dye. In general, water is used as the solvent. As additives such as leveling assistants, known additives can be used. For example, wetting agents and penetrating agents described in pages 134 to 145 of dyeing notes, metal ion encapsulants described in pages 147 to 154 of dyeing notes, Dyeing notes described on pages 216 to 222, leveling agents described on pages 230 to 255, dyeing notes on pages 285 to 286, dyeing notes on pages 279 to 284 Agents, dye fixing agents described on pages 304 to 321 of dyeing notes, dyeing fastness improvers, pH adjusting agents described on pages 322 to 334 of dyeing agents, and the like. In order to uniformly dye the dye at a high concentration, in addition to using an additive, the dye concentration, dye bath pH, salt concentration, dyeing temperature, dyeing time, pressure, and liquid flow can be adjusted.
In the washing step, water in the range of room temperature to 100 ° C. or hot water is generally used. The water to be washed may contain a soaping agent. By completely removing the unfixed coloring material, good results can be obtained in various water resistances such as washing fastness and sweat fastness.
Specifically, in the drying step, the washed fabric is squeezed or dehydrated and then dried or dried using a dryer, heat roll, iron, or the like.

[[Coloring composition for screen printing, roller printing, or transfer printing, and printing method using the same]]
When the coloring composition of the present invention is used in screen printing, roller printing, or transfer printing, the coloring composition is used as a color paste for printing on a cloth via a plate or transfer paper.
The textile printing method of the present invention includes at least the following steps (1) to (4).
(1) A step of adjusting the color paste by adding the colored composition of the present invention to a liquid containing at least a polymer compound and water (2) A step of printing the color paste of (1) on a fabric (3) ) The process of applying steam to the fabric printed (4) The process of washing and drying the printed fabric Colored paste is suitable for printing and printing suitable for printing on plates It is required to meet the necessary printing suitability.
Therefore, for the purpose of imparting printing suitability and printing suitability, the color paste can contain a paste, a solvent, a dyeing auxiliary agent and the like in addition to the dye. The paste is a medium for the coloring composition, and a water-soluble polymer is used. Examples of the water-soluble polymer include known natural water-soluble polymers such as starches, seaweeds, natural gums, cellulose derivatives, sodium alginate, protein substances, tannin substances, and lignin substances. In addition, known synthetic polymers such as polyvinyl alcohol compounds, polyethylene oxide compounds, acrylic acid-based aqueous polymers, styrene-based aqueous polymers, and maleic anhydride-based aqueous polymers are also used as the paste. For example, the printing paste described in pages 349 to 361 of the dyeing note can be used. Further, the printing paste modifier described in Dyeing notes on pages 367 to 369 may be used in combination. Two or more kinds of pastes may be mixed and used. As the solvent, a water-soluble solvent is preferably used, and it is most preferable to use a solvent containing at least water.
Coloring agents such as acids and alkalis, dye solubilizers, wetting agents, hygroscopic agents, deep dyeing agents, anti-reduction agents, metal ion sealing agents, UV absorbers, dispersants, anti-dyeing agents, and discharging Agents, antiseptics, antifungal agents, antioxidants, migration inhibitors, dye fixing agents, antifoaming agents and the like.
As the dyeing assistant, known ones can be used. For example, the solubilizers and solubilizers described in the dyeing notes on pages 336 to 338, the thick dyes and leveling agents described in the dyeing notes on pages 339 to 345, Penetration agent, antifoaming agent described in dyeing notes on pages 346 to 348, metal ion sealing agent described on dyeing notes on pages 147 to 154, dispersing agent on dyeing notes on pages 216 to 222, dyeing notes on pages 370 to 374 Dyeing notes, dyeing notes described on pages 375 to 381, dyeing notes antiseptics, antifungal agents described on pages 362 to 363, migration inhibitors described on dyeing notes on pages 279 to 284, dyeing notes 426 Examples thereof include dye fixing agents described on pages 429 to 429, wet fastness improvers described in JP-A-6-166969, and light fastness improvers described in US Pat. No. 5,336,443.
A dyeing assistant is added to a paste solution in which a paste is dissolved or dispersed in a solvent, and a dye solution in which a dye is dissolved or dispersed in a solvent is added and stirred to prepare a color paste (step of preparing a color paste).

  In the printing method, unlike the dip dyeing method, after the color paste is printed on the fabric (the step of printing the color paste on the fabric), the color material printed on the fabric is dyed onto the fiber. This is called a coloring process, and there are a method using heated air, a method using normal pressure saturated steam and superheated steam, and a method using normal pressure saturated steam is preferred. In the present invention, a process of applying to the fabric printed with steam is performed. In the process of applying to the fabric printed with steam, the temperature and time to be treated with steam vary depending on the type of the colored composition and the type of the fabric, but the temperature is preferably 100 ° C to 108 ° C, and the time is preferably 1 to 60 minutes. 1 to 30 minutes is more preferable. After the process applied to the fabric printed with steam, a printed product is obtained through a washing process and a drying process similar to the dip dyeing.

[[Coloring composition for inkjet printing and method using the same]]
When the coloring composition of the present invention is used in ink jet printing, the coloring composition is used as an ink for ink jet printing. Compared with the conventional textile printing method, the inkjet textile printing method has the advantage of being able to quickly form an image with excellent gradation, and has the advantages of shortening the delivery time, dealing with small-lot and multi-product production, and eliminating the need for a plate making process. Yes. Further, since only a necessary amount of ink is used as a formed image, it can be said that this is an excellent image forming method having environmental advantages such as less waste liquid compared to the conventional method.
Ink for inkjet printing, when the viscosity of the ink is increased by evaporation of water or an aqueous organic solvent from the nozzle tip, or when a solid dye is deposited, the nozzle of the inkjet head is clogged. There is a need for inks with higher color development than textile printing. In addition, it is required to provide ink suitability such as ink storage stability and ejection stability, printing quality such as bleeding prevention and contamination prevention, and image fastness such as light resistance, water resistance and washing resistance.
The inkjet textile printing method of the present invention includes at least the following steps (11) to (14).
(11) A step of applying a paste containing at least a polymer compound and water to a fabric (12) A step of printing the colored composition of the present invention on a fabric by an ink jet method (13) A step of applying to a fabric printed with steam 14) Process of washing printed fabric with water and drying Inkjet printing method will clog the nozzles when using the color paste used in the conventional printing method, so before applying the paste to the fabric in advance A treatment step (a step of applying a paste containing at least a polymer compound and water to the fabric) is required. By performing the pretreatment step, the fabric can be easily handled. Specifically, a pretreated fabric is obtained by attaching a paste solution containing a paste, a solvent and a hydrotropic agent to the fabric and drying it.
As the paste, the same paste as used in screen printing or the like can be used. As the solvent, a water-soluble solvent is preferably used, and a solvent containing at least water is most preferably used.
The hydrotropic agent generally serves to increase the color density of an image when the fabric to which the ink composition is applied is heated under steam. For example, urea, alkylurea, ethyleneurea, propyleneurea, thiourea, guanidate, halogen-valent tetraalkylammonium and the like are usually used. Moreover, a well-known thing can also be used and the dye fixing agent of dyeing | staining notes pp. 426-429, etc. are mentioned. The content of the hydrotropic agent with respect to the total solid content of the paste solution is preferably 0.01% by mass to 20% by mass.
The paste solution may further contain a pH adjuster, an aqueous (water-soluble) metal salt, a water repellent, a surfactant, a migration inhibitor, a microporous forming agent, and the like as necessary. As these additives, known ones can be used. For example, the solubilizers and solubilizers described in dyeing notes on pages 336 to 338, and the deep dyes and leveling agents described in dyeing notes on pages 339 to 345 are used. , Penetrating agent, metal ion sealing agent described in dyeing notes on pages 147 to 154, dyeing prevention agent on dyeing notes on pages 370 to 374, discharge agent on dyeing notes on pages 375 to 381, dyeing notes on pages 362 to 363 Preservatives, antifungal agents described in pages, migration inhibitors described in dyeing notes on pages 279 to 284, microporous forming agents described in JP-A-7-316991, wet fastness improvers described in JP-A-6-166969, Examples include light fastness improvers described in US Pat. No. 5,336,443. Also, those described in JP-A-2013-209786, paragraphs [0096] to [0101] can be used.
In the pretreatment, it is preferable to put the paste solution in the range of 5% to 150%, preferably 10% to 130%.
In the pretreatment, a method for incorporating the respective paste solutions into the fabric is not particularly limited, and examples include a usual dipping method, pad method, coating method, screen method, spray method, transfer method, and ink jet method. .

Next, the pretreated fabric is printed using an ink for inkjet printing.
The ink for inkjet textile printing can be produced by dissolving and / or dispersing the compound (mixture) represented by the general formula (1) in a solvent.
The solvent is determined depending on the type of substituent in the general formula (1) used, the type of solvent component used to produce the colored composition, the type of fabric to be dyed, and the like, but is preferably water or water-soluble Organic solvents are used.
Examples of the water-soluble organic solvent that can be contained in the ink composition of the present invention include amines, monohydric alcohols, alkyl ethers of polyhydric alcohols, in addition to polyhydric alcohols such as diethylene glycol and glycerin. Moreover, each compound mentioned as an illustration of the water-miscible organic solvent of Paragraph [0076] of Unexamined-Japanese-Patent No. 2002-371079 is suitable.

The content of the organic solvent in the ink composition of the present invention is preferably 10% by mass or more and 60% by mass or less with respect to the total mass of the ink composition for inkjet textile printing.
As the surfactant, any of cationic, anionic, amphoteric and nonionic surfactants can be used. Examples of the cationic surfactant include aliphatic amine salts and aliphatic quaternary ammonium salts. Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, and the like. Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, acetylene glycol, acetylene alcohol and the like. Surfactants listed as examples of the surface tension adjusting agent described in paragraph [0073] of JP-A-2002-371079, and surfactants described in JP-A-2008-266466 and JP-A-11-269939 are preferably used. .
Moreover, the ink for inkjet textile printing of this invention can contain another additive in the range which does not impair the effect of this invention as needed. Other additives include, for example, anti-drying (wetting agent), anti-fading agent, emulsion stabilizer, penetration enhancer, ultraviolet absorber, infrared absorber, preservative, anti-oxidant, pH adjuster, surface tension adjuster. , Known additives such as antifoaming agents, viscosity modifiers, dispersants, dispersion stabilizers, rust inhibitors, cleansing agents, anti-reducing agents, antioxidants, antistatic agents, and fluorescent brighteners. 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 an oil phase or an aqueous phase may be added during the preparation. When the oil-soluble dye is made into a dispersion, a dispersant can be used. For example, the dispersant described in pages 216 to 222 of the dyeing note is used.
As the anti-drying agent, anti-fading agent, ultraviolet absorber, anti-mold agent, pH adjuster, surface tension adjuster, antifoaming agent, and keeping agent, those described in JP-A-2014-5462 [0224] to [0231] are applied. it can. Moreover, the wet fastness improving agent described in JP-A-6-166969 and the light fastness improving described in US Pat. No. 5,336,443 can also be contained.
The penetration accelerator is preferably used for the purpose of allowing the ink for ink jet textile printing to penetrate and fix inside the fiber better. As the penetration enhancer, known ones can be used. For example, wetting agents, penetrating agents, leveling agents, loose printing agents, ethanol, isopropanol, butanol, di (tri) ethylene described in dyeing notes on pages 223 to 255. Alcohols such as glycol monobutyl ether and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants, branched polyhydric alcohols described in WO10 / 109867 and JP-A-6-57644, etc. it can. If these are contained in the ink in an amount of 5 to 35% by mass, they are usually effective, and it is preferable to use them in a range of addition amounts that do not cause bleeding after dyeing and back leakage of the ink.

When the compound of the present invention is dispersed in an aqueous medium, it can be dispersed by the method described in JP 2014-5462 A [0232] to [0233].
In the present invention, the content of the compound represented by the general formula (1) contained in the colored composition is the kind of the substituent in the general formula (1) 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. More preferably, it is contained in an amount of 10 to 10% by mass.
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 textile printing 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 hue ink, a cyan hue ink, and a yellow hue ink can be used, and a black hue ink may be further used to adjust the hue. Examples of the applicable dye include those described in JP 2014-5462 A [0237] to [0240].

  Fabrics printed by the ink jet method are dried and then subjected to a color development step, a washing step, and a drying step in the same manner as other printing methods to obtain a printed matter. A preferred method of the color development step to the drying step is the same as that for screen printing.

  The fabric used in the present invention may be pretreated if necessary. In the ink jet textile printing method, the treatment may be performed before or after the paste is attached to the fabric. Moreover, you may add and use a pre-processing agent to the paste solution adhering before dyeing | staining. Specifically, JP-A-2002-339268, JP-A-2000-54277, JP-A-7-150482, JP-A-2008-174865, JP-A-2012-154006, JP-A-2012-12730, JP-A-2-68372, JP-B-63. -31594, JP 2002-275769, JP 2001-81680, JP 2004-68208, JP 11-43873, JP 2007-217829, JP 2006-83495, JP 2005-154936, JP 2002-105875. JP-A No. 2002-348786, JP-A No. 11-81163, JP-A No. 2-61183, JP-A No. 2001-295186, JP-A No. 2004-60073, JP-A No. 2003-113583, JP-A No. 8-100399, JP-A No. 2-53976, Open 2000-226781, JP Examples include pretreatment methods described in JP-A-2004-292989, JP-A-2002-249991, JP-A-2002-363872, JP-A-6-341070, JP-A-2004-197237, JP-A-2008-223192, JP-A-2011-179130, and the like. .

The fabric used in the present invention may be fire retardant treatment described in JP-A No. 62-257464, plasma treatment described in JP-A No. 2-47378, JP-A No. 60-94678, JP-A No. 2002, as necessary. -266236, Japanese Patent Application Laid-Open No. 2007-32247, Japanese Patent Application Laid-Open No. 3-287873, Japanese Patent Application Laid-Open No. 2004-131919, etc., may be subjected to fastness improving treatment such as light resistance, wet resistance, and chlorine resistance. These treatments may be performed before dyeing or after dyeing.
The method for inkjet printing of the ink of the present invention is not limited as long as it includes a step of ejecting ink onto a fabric using an inkjet apparatus. For example, Japanese Patent Laid-Open No. 9-2963
79, JP-A-11-43873, JP-A-7-70953, JP-A-7-197384, JP-A-7-70950, JP-A-3-104977, JP-A-2007-303046, JP-A-2007-313717, JP-A-2008-248437, etc. In addition, a method for inkjet printing is known.
Further, as an apparatus used for inkjet printing, any inkjet apparatus can be used. For example, JP-A-3-45774, JP-A-2001-277656, JP-A-2000-290882, JP-A-2001-18390, JP-A-2010-83040, and JP-A-2011-31418 are known.

[Colored compound form and fabric to be dyed]
The compound represented by the general formula (1) is used for the purpose of dyeing or printing a fabric as a dye.
Various types of dyes can be prepared by changing the type of substituent of the compound represented by the general formula (1).
When the compound represented by the general formula (1) contains at least one acidic group such as a sulfo group or a carboxyl group, as an acidic dye, protein fibers such as silk and wool, polyamide fibers such as 6 nylon and 66 nylon Can be dyed.
When the compound represented by the general formula (1) is an oil-soluble compound insoluble in water, it is common to dye hydrophobic fibers such as polyester as disperse dyes, but also dye acrylic fibers and polyamide fibers. be able to.
When the compound represented by the general formula (1) contains at least one basic group such as an amino group, an acrylic fiber can be dyed as a cationic dye.
When the compound represented by the general formula (1) contains at least one group that reacts with a fiber, cellulose fiber such as cotton or polyamide fiber can be dyed as a reactive dye. Specific examples of the group that reacts with the fiber include a chlorotriazinyl group, a chloropyrimidyl group, a vinylsulfonyl group, a chloroethylsulfonyl group, a sulfatoethylsulfonyl group, and a thiosulfatoethylsulfonyl group.
As the fabric, a fabric made of one type of fiber may be used, or a composite fiber made of two or more types of fibers may be used.
The compound represented by the general formula (1) is preferably an acid dye, and particularly has a high dyeing property when dyeing polyamide fiber, and has light resistance, wet fastness and the like. Various performances as a dyed fabric can be improved.
As a preferable polyamide fiber as a fabric to be dyed, a polyamide fiber may be used as long as it contains polyamide fiber, and a fabric made of polyamide alone or a fabric made of composite fiber may be used. Examples of the composite fiber include fibers described in JP-A-2008-202210, JP-A-2006-322131, JP-A-2007-100200, and the like. Among polyamide fibers, fibers containing 6 nylon and 66 nylon are preferable.
The fiber used is preferably a fabric, but the same effect can be obtained even if the yarn is dyed.

  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 “parts” in the examples are% by mass and parts by mass.

[Synthesis Example 1] Synthesis of Exemplified Compound (1-1) (Synthesis of Intermediate (A))

Dichlorosulfophthalein 74.1 g (content 70%, Chugai Kasei DCSF, trade name), 2,4,6-trimethylaniline 80.0 g (Tokyo Kasei) and zinc chloride 28.6 g in 200 g sulfolane The reaction was performed at 3 ° C for 3 hours. The reaction solution was allowed to cool to room temperature, poured into 2 L of dilute hydrochloric acid to precipitate crystals, and the precipitated crystals were filtered off and washed with 1 L of dilute hydrochloric acid and then 1 L of water. The obtained wet cake was dispersed in 1 L of acetonitrile, heated and stirred at 45 ° C. for 30 minutes, the crystals were filtered off and washed with a small amount of acetonitrile, and then the crystals were dried with an air dryer at 60 ° C. to obtain an intermediate. A crude product of A was obtained. Yield 80g. ^{MS (m / z) 602.2 (} M +, 100%), 603.2 ([M + 1] +1).

(Synthesis of Exemplary Compound (1-1))
10 g of intermediate A was added in portions to 100 g of phosphorus oxychloride and reacted at 60 ° C. for 2 hours. The reaction solution was allowed to cool to room temperature and poured into 700 g of ice water to precipitate crystals. The precipitated crystals were filtered off and washed with cold water. Separately, 182.7 g of monosodium aniline-2,5-disulfonate was added to 300 mL of dimethylacetamide and cooled to 5 ° C. or lower. The wet cake filtered earlier was dividedly added so that the internal temperature did not exceed 10 ° C., and after the addition was completed, the reaction solution was returned to room temperature and reacted at room temperature for 6 hours. The obtained reaction solution was concentrated with a rotary evaporator, and the obtained residue was subjected to silica gel chromatography (filler: Wako Gel C200 (trade name, manufactured by Wako Pure Chemical Industries), developing solvent: chloroform / methanol = 20/1, v / v). To obtain crystals of exemplary compound (1-1). Yield 8.2g. MS (m / z, nega) 961 ([M-1] ^- , 100%). The absorption maximum wavelength in the dilute solution in the aqueous solution was 532 nm.

(Synthesis of Exemplary Compound (1-2))

In the same manner as in the synthesis of Exemplified Compound (1-1), except that aniline-2,5-disulfonate monosodium in the synthesis of Exemplified Compound (1-1) was changed to aspartic acid, an intermediate ( 3-2-a) was obtained.
6.9 g of the intermediate (3-2-a) was added in portions to 8.2 g of fuming sulfuric acid and 50 g of sulfuric acid, and then reacted at 24 ° C. for 2 hours. The obtained reaction solution was poured into 250 g of ice water to precipitate crystals, and the obtained crystals were filtered off and washed with ice water. The obtained wet cake was dispersed in 200 mL of water, the pH was adjusted to 9 using 2N sodium hydroxide, and 2N sodium hydroxide was added and stirred until there was no fluctuation at pH 9. The obtained reaction solution was adjusted to pH 8 using dilute hydrochloric acid and desalted using a dialysis tube, followed by gel chromatography (filler: Sephadex LH-20 (trade name, manufactured by Pharmacia), developing solvent: water. / Methanol = 1/1, v / v) to give glossy crystals of exemplary compound (1-2). Yield 5.0 g, MS (m / z, nega) = 915 ([M−1] ⁻ , 100%). The absorption maximum wavelength in the dilute solution in the aqueous solution was 531 nm.

  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.

Composition of ink liquid 1:
Dye (compound (1-1)) 3.50 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 2-8, Comparative Examples 1-3]
Except that the dye was changed as shown in Table 1 below, ink solutions using ink solutions 2 to 8 and comparative compounds 1 to 3 shown below as comparative ink solutions were the same as the preparation of ink solution 1. Was prepared.

(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 Table 1, ozone resistance, light resistance, and moisture resistance are photo glossy paper (manufactured by EPSON Co., Ltd .; PM-700C) and photo glossy paper (manufactured by EPSON Co., Ltd.) using each ink for ink jet recording. Evaluation was performed after recording an image on paper <glossy> (KA420PSK, EPSON)). The print density was evaluated after recording a solid image on plain paper (Canon plain paper (GF500, Canon)) using an inkjet printer (manufactured by EPSON Corporation; PM-700C) using each ink jet recording ink. It is a thing.

<Print density>
The solid image created above is measured using a reflection densitometer (X-Rite 310TR, manufactured by X-Rite Co., Ltd.). The case where the printing density is 2.2 or more is A, and the case where the printing density is 2.0 or more and less than 2.2. The case where B was less than 2.0 was defined as C and evaluated in three stages.

<Light resistance>
After measuring the image density Ci immediately after recording, the image was irradiated with xenon light (100,000 lux) for 7 days using a weather meter (Atlas C.165), and then the image density Cf was measured again. The dye residual ratio (Cf / Ci × 100%) was calculated from the difference in image density before and after irradiation and evaluated. 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 1.0, 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.

<Ozone resistance>
While passing dry air through the double glass tube of the Siemens type ozonizer, 5 kV AC voltage was applied, and using this, the above image was placed 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 dye residual ratio (Cf ₂ / Ci × 100%) was evaluated from the initial image density Ci and the image density Cf ₂ after standing in ozone gas. The image density was measured at three points of 1.0, 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.

<Moisture resistance>
During ink-jet recording, a check pattern (a pattern in which squares having a 1.5 mm square with a density of 100% and 0% were alternately combined) was created to obtain a magenta-white check pattern print with high contrast. . After printing, the check pattern prints that have been dried for 24 hours are allowed to stand for 7 days at 80 ° C. and a relative humidity of 70% RH, and the degree of bleeding from the colored portion to the white portion is visually evaluated, and hardly bleeds. A case was evaluated as A, a case of slightly bleeding as B, and a case of clear bleeding as C.

<Ink storage stability test method>
Regarding the change in pH value, the following levels were used based on the pH value immediately after ink preparation (liquid temperature 25 ° C.) and the pH value (liquid temperature 25 ° C.) after forced thermal aging test (7 days). Set.

A: Difference in pH value before and after forced thermal aging test is less than 0.3 B: Difference in pH value before and after forced thermal aging test is 0.3 or more and less than 0.5 C: pH value before and after forced thermal aging test The difference in pH is 0.5 or more and less than 0.7 D: The difference in pH value before and after the forced thermal aging test is 0.7 or more

  As is apparent from the results in Table 1, the inks of Examples using the compounds of the present invention were excellent in printing density, light resistance and ozone resistance, and were excellent in moisture resistance and ink storage stability. .

Comparative compound 1 (A1 of JP 2013-116956 A, including the following structure)

Comparative compound 2: a mixture of compounds such that the ratio of b and c below is b = 0.5 and c = 1.5 (Exemplary Compound 1 of JP2013-49776A).

Comparative compound 3 (Compound 12 of WO 2000/64988)

[Printing evaluation]
A solid image was printed on the nylon 6 jersey, which was a fabric, using a screen printing machine with the following printing paste.
Printing paste and paste: MEYPRO GUM NP [Mayhall Chemical AG
50g
・ PH adjuster: ammonium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 5g
Colorant: Compound 1-11 2g
・ Water 43g
After the printed fabric was dried, steam treatment was performed with saturated steam at 105 ° C. Thereafter, the fabric was washed with water, and unfixed dye was washed away. The dyed fabric was fixed at 60 ° C. for 5 minutes in a 200 mL bath containing 0.1 g of acetic acid, 0.6 g of ammonium sulfate, and 6 g of Sun Life TN (Nika Group), and dried to obtain a dyed product. The dyed product obtained did not lose its color, and a dyed product with a high density of magenta was obtained.
In the case of Compound 1-13 as well, when printing evaluation was performed in the same manner, a dyed product dyed in a high density magenta color was obtained without fading even after washing with water.

[Inkjet printing evaluation]
Ink jet textile printing was performed according to the method described in JP2013-209786A.

<Pretreatment process>
About the nylon 6 jersey which is a fabric, the component shown below was mixed and the pretreatment agent A was prepared. Using the obtained pretreatment agent A, the fabric was put at a drawing ratio of 90% and naturally dried to obtain a treated fabric.

(Pretreatment agent A)
・ Glue: Guar gum [Nippon Co., Ltd., MEYPRO GUM NP] 2g
・ Hydrotropy: Urea (Wako Pure Chemical Industries) 5g
・ PH adjuster: ammonium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 4g
・ Water 89g

<Printing process>
Next, an ink composition having the following composition was stirred for 1 hour while being heated at 30 to 40 ° C. The obtained liquid was filtered under reduced pressure through a microfilter having an average pore diameter of 0.5 μm to prepare an ink liquid for ink jet printing.
-Compound 1-11 5 mass%
・ Glycerin [Wako Pure Chemical Industries, Ltd.] (aqueous organic solvent) 10% by mass
・ Diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) (aqueous organic solvent) 10% by mass
・ Orphine E1010 [manufactured by Nissin Chemical Co., Ltd.] (acetylene glycol surfactant)
1% by mass
・ 74% by mass of water

  Each ink-jet printing ink solution thus obtained was set in an ink-jet printer (manufactured by Dimatics, Inc., DMP-2381), and a solid image was printed on the resulting pretreated fabric.

<Post-processing process>
After the printed fabric was dried, it was steamed in saturated steam at 100 ° C. for 30 minutes in a steam process to fix the dye to the fabric fibers. Thereafter, the fabric was washed with cold water for 10 minutes and warm water at 60 ° C. for 5 minutes, and then naturally dried. The dyed product obtained did not lose its color, and a dyed product with a high density of magenta was obtained.
In the case of Compound 1-13 as well, when printing evaluation was performed in the same manner, a dyed product dyed in a high density magenta color was obtained without fading even after washing with water.

Claims (11)

A compound represented by the following general formula (1).

In general formula (1), R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, R ² has at least one SO ₃ M or COOM as a substituent. When R ¹ represents a hydrogen atom, R ² represents a substituted or unsubstituted secondary or tertiary alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ¹ and R ² may combine with each other to form a ring.
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a substituted or unsubstituted alkyl group. R ⁷ , R ⁸ and R ⁹ each independently represents a substituent.
M represents a hydrogen atom or a counter cation. M may be the same or different. n1 and n2 each independently represents 0 or 1.
n3 represents the number of 0-4. n4 and n5 each independently represents a number from 0 to 3.
When n3, n4 and n5 each represent a number of 2 or more, the plurality of R ⁷ , R ⁸ and R ⁹ may be the same or different.
However, any one of SO ₃ M or COOM present in the general formula (1) is dissociated to SO ₃ ^- are present as ^- or COO. The compound according to claim 1, wherein R ² has at least one SO ₃ M as a substituent.   The compound according to claim 1 or 2, wherein M represents a lithium ion, a sodium ion, a potassium ion or an ammonium ion.   The coloring composition containing the compound of any one of Claims 1-3.   Ink for inkjet recording containing the compound of any one of Claims 1-3.   An ink jet recording method using the ink for ink jet recording according to claim 5.   An ink jet printer cartridge filled with the ink for ink jet recording according to claim 5.   An ink-jet recorded matter in which a colored image is formed on a recording material using the ink for ink-jet recording according to claim 5. A textile printing method including the following steps (1) to (4).
(1) A step of adding a colored composition according to claim 4 to a liquid containing at least a polymer compound and water to adjust a color paste. (2) Printing the color paste of (1) on a fabric. Step (3) Step of applying to steam printed fabric (4) Step of washing and drying printed fabric A textile printing method comprising the following steps (11) to (14).
(11) A step of applying a paste containing at least a polymer compound and water to the fabric. (12) A step of printing the ink for inkjet recording according to claim 5 on the fabric by an inkjet method. (13) A fabric printed with steam. (14) Washing and drying the printed fabric   The textile printing method according to claim 9 or 10, wherein the fabric contains polyamide.