JP2016138172A - Fiber dyeing coloring composition comprising polyamide, ink composition, printing method, and printed fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber dyeing coloring composition comprising polyamide, a printing method, and a fabric.SOLUTION: A coloring composition comprises a compound comprising two sulfo groups in a molecule, represented by formula (1) (R-Rrepresent a hydrogen atom or a substituent; at least two sulfo groups are present in the molecule).SELECTED DRAWING: None

Description

  The present invention relates to a coloring composition for dyeing fibers containing polyamide, an ink composition, a printing method, and a printed fabric.

  Conventionally, acid dyes, reactive dyes, direct dyes, disperse dyes and the like have been used as dyes for dyeing fabrics. For example, reactive dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes and the like are known as dyes for dyeing cellulose fibers such as cotton and viscose rayon, and dye polyamide fibers such as silk, wool and nylon. Known dyes include acid dyes, metal complex hydrochloric acid dyes, acid mordant dyes, and direct dyes. Ester fibers such as polyester fibers and cellulose ester fibers are known to be dyed with disperse dyes or pigments. Acrylic fibers are generally dyed with a cationic dye, but some fibers are dyed with an acid dye.

In the past, screen printing, roller printing, transfer printing, and the like have been performed as industrial dyeing methods for dyeing fabrics. These methods are dyeing techniques that are completed only after a series of processes such as design pattern planning, engraving or plate making, creation of printing paste, and preparation of fabrics are integrated.
On the other hand, ink jet textile printing using an ink jet method capable of directly supplying a dye to a cloth has been proposed. Unlike conventional textile printing, inkjet textile printing has the advantage that it is not necessary to prepare a plate and can quickly form an image with excellent gradation. It has merits such as no. 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.

  For example, Patent Document 1 describes a composition containing a xanthene dye for dyeing keratin fibers.

US Patent Application Publication No. 2006/0230545

  However, according to the study by the present inventors, the xanthene dye described in Patent Document 1 has insufficient light resistance when dyed with a fiber containing polyamide, and has poor inkjet head ejection in inkjet printing. Furthermore, it has been found that there is a problem that the dyeing speed is slow compared to other color dyes, and that the steam treatment time is required for a long time to obtain a necessary dyeing density.

  In the present invention, when a fiber containing polyamide is dyed, the fiber containing polyamide has high light resistance, ink jet dischargeability is good, and has a high dyeing speed (that is, a high dyeing density). Another object of the present invention is to provide a coloring composition for dyeing fibers containing polyamide. Another object of the present invention is to provide an ink composition containing the colored composition, a printing method using the ink composition, and a printed fabric.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific indolenine-substituted xanthene dye.

  That is, the above problem can be solved by the following means.

一般式（１）中、Ｒ^１０１〜Ｒ^１３５はそれぞれ独立に水素原子又は置換基を表す。ただし、一般式（１）で表される化合物は、分子中にスルホ基を少なくとも２個含む。
［２］
上記一般式（１）で表される化合物が、下記一般式（２）で表される［１］に記載の着色組成物。
一般式（２）：

一般式（２）中、Ｒ^２０１〜Ｒ^２３４はそれぞれ独立に水素原子又は置換基を表す。ただし、一般式（２）で表される化合物は、分子中にスルホ基を少なくとも２個含む。
［３］
上記一般式（１）又は（２）で表される化合物が、下記一般式（３）で表される［１］又は［２］に記載の着色組成物。
一般式（３）：

一般式（３）中、Ｒ^３０１〜Ｒ^３３４はそれぞれ独立に水素原子又は置換基を表す。Ｍはそれぞれ独立に水素原子、又はカウンターカチオンを表す。
［４］
［１］〜［３］のいずれか１項に記載の着色組成物を含むインク組成物。
［５］
［４］に記載のインク組成物を用いる捺染方法。
［６］
［４］に記載のインク組成物を用いてインクジェット法により捺染する捺染方法。
［７］
［５］又は［６］に記載の捺染方法において、シアンインクと、マゼンタインクと、イエローインクの少なくとも３色のインクを含むインクセットを用いる捺染方法であって、上記シアンインクとして、［４］に記載のインク組成物を用いる、捺染方法。
［８］
上記マゼンタインクに、キサンテン酸性染料を含む［７］に記載の捺染方法。
［９］
上記イエローインクに、モノアゾ酸性染料を含む［７］又は［８］に記載の捺染方法。
［１０］
［５］〜［９］のいずれか１項に記載の捺染方法によって捺染された布帛。 [1]
The coloring composition for fiber dyeing containing the polyamide containing the compound represented by following General formula (1).
General formula (1):

In general formula (1), R ^{101 to} R ¹³⁵ each independently represent a hydrogen atom or a substituent. However, the compound represented by the general formula (1) contains at least two sulfo groups in the molecule.
[2]
The colored composition according to [1], wherein the compound represented by the general formula (1) is represented by the following general formula (2).
General formula (2):

In General Formula (2), R ^{201 to} R ²³⁴ each independently represent a hydrogen atom or a substituent. However, the compound represented by the general formula (2) contains at least two sulfo groups in the molecule.
[3]
The colored composition according to [1] or [2], wherein the compound represented by the general formula (1) or (2) is represented by the following general formula (3).
General formula (3):

In general formula (3), R ^{301 to} R ³³⁴ each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation each independently.
[4]
An ink composition comprising the coloring composition according to any one of [1] to [3].
[5]
A textile printing method using the ink composition according to [4].
[6]
A printing method for printing by an ink jet method using the ink composition according to [4].
[7]
In the textile printing method according to [5] or [6], the textile printing method using an ink set including at least three colors of cyan ink, magenta ink, and yellow ink, wherein the cyan ink includes [4] A printing method using the ink composition described in 1.
[8]
The textile printing method according to [7], wherein the magenta ink contains a xanthene acid dye.
[9]
The printing method according to [7] or [8], wherein the yellow ink contains a monoazo acid dye.
[10]
A fabric printed by the printing method according to any one of [5] to [9].

  According to the present invention, when a fiber containing polyamide is dyed, it has high light resistance in the fiber containing polyamide, good ink jet discharge properties, and a high dyeing speed (that is, a high dyeing density). A coloring composition for dyeing fibers containing polyamide. In addition, an ink composition containing the coloring composition, a printing method using the ink composition, and a printed fabric can be provided.

Hereinafter, the present invention will be described in detail.
First, specific examples of the substituent in the present invention are defined as a substituent group A.

(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 a phenylazo group or p-chlorophenylazo group. Group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group 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.

The present invention relates to a coloring composition for dyeing fibers containing polyamide, which contains a compound represented by the general formula (1).
When the compound represented by the general formula (1) is used as a coloring composition for dyeing, a fabric dyed from cyan to blue can be obtained.
The colored portion of the dyed fabric is improved in light resistance, and at the time of coloring, a dyeing speed equivalent to that of other color inks can be realized. In addition, there is no problem with the inkjet head ejection properties during inkjet printing. Although the mechanism of action is unknown, it is considered that having two or more sulfo groups in the general formula (1) is effective for the following reasons.
-Dyeing speed: The hydrophilicity / hydrophobicity of the dye was controlled within a range to achieve the dyeing speed with respect to polyamide.
-Ink jet head discharge property: The dye solubility in the solvent for ink jet ink was improved.

  Below, the compound represented by General formula (1) is demonstrated.

[Compound represented by the general formula (1)]
General formula (1):

In general formula (1), R ^{101 to} R ¹³⁵ each independently represent a hydrogen atom or a substituent. However, the compound represented by the general formula (1) contains at least two sulfo groups in the molecule.

In General Formula (1), R ^{101 to} R ¹⁰⁴ and R ^{111 to} R ¹¹⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent selected from the above substituent group A.
R ^{101 to} R ¹⁰⁴ and R ^{111 to} R ¹¹⁴ are each independently preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and more preferably a hydrogen atom, an alkyl group, or an aryl group. And particularly preferably a hydrogen atom or an alkyl group. R ¹⁰¹ and R ¹⁰⁴ , R ¹¹¹ and R ¹¹⁴ may be connected to each other to form a ring.
R ^{101 to} R ¹⁰⁴ and R ^{111 to} R ¹¹⁴ may further have a substituent, and the substituent in the case of further having a substituent includes a substituent selected from the above substituent group A. An alkyl group, an aryl group, a halogen atom, an amino group, an alkoxy group, a nitro group, and an ionic hydrophilic group are preferable, and an alkyl group, a halogen atom, and an ionic hydrophilic group are particularly preferable.

In general formula (1), R < ¹⁰⁵ > -R < ¹⁰⁸ > and R < ¹¹⁵ > -R < ¹¹⁸ > represent a hydrogen atom or a substituent each independently. Examples of the substituent include a substituent selected from the above substituent group A.
R ^{105 to} R ¹⁰⁸ and R ^{115 to} R ¹¹⁸ are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a sulfamoyl group, an arylcarbonylamino group, or an ionic hydrophilic group, and a hydrogen atom , A sulfamoyl group, a halogen atom, or an ionic hydrophilic group is more preferable, and a hydrogen atom or an ionic hydrophilic group is particularly preferable. The ionic hydrophilic group is preferably a sulfo group.
R ^{105 to} R ¹⁰⁸ , and R ^{115 to} R ¹¹⁸ may further have a substituent, and the substituent in the case of further having a substituent includes a substituent selected from the above substituent group A, An alkyl group, an aryl group, a halogen atom, an amino group, an alkoxy group, a nitro group, and an ionic hydrophilic group are preferable, and an alkyl group, a halogen atom, and an ionic hydrophilic group are particularly preferable.

In General Formula (1), R ^{121 to} R ¹²⁶ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent selected from the above substituent group A.
R ^{121 to} R ¹²⁶ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group, an amino group, an alkoxy group, a sulfamoyl group, or an ionic hydrophilic group, and a hydrogen atom, an alkyl group, an amino group, or an alkoxy group. , A sulfamoyl group, or an ionic hydrophilic group is more preferable. The ionic hydrophilic group is preferably a sulfo group.
R ^{121 to} R ¹²⁶ may further have a substituent, and examples of the substituent in the case of further having a substituent include a substituent selected from the above substituent group A, an alkyl group, an aryl group, a halogen An atom, an amino group, an alkoxy group, a nitro group, and an ionic hydrophilic group are preferable, and an alkyl group, a halogen atom, and an ionic hydrophilic group are particularly preferable.

In General Formula (1), R ^{131 to} R ¹³⁵ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent selected from the above substituent group A.
R ^{131 to} R ¹³⁵ are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a sulfamoyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, or an ionic hydrophilic group, and a hydrogen atom, an ion A hydrophilic hydrophilic group or an alkoxycarbonyl group is more preferable, and a hydrogen atom or an ionic hydrophilic group is particularly preferable. The ionic hydrophilic group is preferably a sulfo group.
R ^{131 to} R ¹³⁵ may further have a substituent, and examples of the substituent in the case of further having a substituent include a substituent selected from the above substituent group A, an alkyl group, an aryl group, a halogen An atom, an amino group, an alkoxy group, a nitro group, and an ionic hydrophilic group are preferable, and an alkyl group, a halogen atom, and an ionic hydrophilic group are particularly preferable.

The compound represented by the general formula (1) contains at least two sulfo groups in the molecule. Here, the form of the sulfo group may be —SO ₃ M or —SO ₃ ^— . M represents a hydrogen atom or a counter cation.
Counter cations represented by M include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidinium ions, tetramethylphosphonium). Alkali metal ions or ammonium ions are preferable, lithium ions, sodium ions, potassium ions, and ammonium ions are more preferable, sodium ions or mixed salts containing sodium ions as main components are more preferable, and sodium ions are most preferable.

  In the compound represented by the general formula (1), 2 to 6 sulfo groups are preferable from the viewpoint of dyeing speed, more preferably 2 to 4, and further preferably 2 to 3 sulfo groups. preferable.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).
General formula (2):

In General Formula (2), R ^{201 to} R ²³⁴ each independently represent a hydrogen atom or a substituent. However, the compound represented by the general formula (2) contains at least two sulfo groups in the molecule.

In General Formula (2), R ^{201 to} R ²⁰⁴ and R ^{211 to} R ²¹⁴ are synonymous with R ^{101 to} R ¹⁰⁴ and R ^{111 to} R ¹¹⁴ in General Formula (1), and preferred examples are also the same. .

In General Formula (2), R ^{205 to} R ²⁰⁸ and R ^{215 to} R ²¹⁸ are synonymous with R ^{105 to} R ¹⁰⁸ and R ^{115 to} R ¹¹⁸ in General Formula (1), and preferred examples are also the same. .

In General Formula (2), R ^{221 to} R ²²⁶ have the same meanings as R ^{121 to} R ¹²⁶ in General Formula (1), and preferred examples are also the same.

In General Formula (2), R ^{231 to} R ²³⁴ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include a substituent selected from the above substituent group A.
R ^{231 to} R ²³⁴ are each independently preferably a hydrogen atom, an alkoxy group, an aryloxy group, a sulfamoyl group, an alkoxycarbonyl group, or an ionic hydrophilic group, more preferably a hydrogen atom or an alkoxycarbonyl group, and particularly preferably a hydrogen atom. preferable. The ionic hydrophilic group is preferably a sulfo group.
R ^{231 to} R ²³⁴ may further have a substituent, and examples of the substituent in the case of further having a substituent include a substituent selected from the above substituent group A.

The compound represented by the general formula (2) contains at least two sulfo groups in the molecule. The form and preferred number of the sulfo group are the same as those in the general formula (1). In the general formula (2), one “—SO ₃ ^— ” which is a sulfo group is described, and at least one sulfo group is included in addition to this.

The compound represented by the general formula (1) or the general formula (2) is more preferably a compound represented by the following general formula (3).
General formula (3):

In general formula (3), R ^{301 to} R ³³⁴ each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation each independently.

In General Formula (3), R ^{301 to} R ³⁰⁴ and R ^{311 to} R ³¹⁴ have the same meanings as R ^{101 to} R ¹⁰⁴ and R ^{111 to} R ¹¹⁴ in General Formula (1), and preferred examples are also the same. .
In General Formula (3), R ^{305 to} R ³⁰⁸ and R ^{315 to} R ³¹⁸ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include a substituent selected from the above substituent group A.
R ^{305 to} R ³⁰⁸ and R ^{315 to} R ³¹⁸ are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a sulfamoyl group, or an ionic hydrophilic group, and the hydrogen atom or sulfamoyl group is preferably More preferred is a hydrogen atom. The ionic hydrophilic group is preferably a sulfo group.
R ^{305 to} R ³⁰⁸ and R ^{315 to} R ³¹⁸ may further have a substituent, and examples of the substituent in the case of further having a substituent include a substituent selected from the above substituent group A.
In the general formula (3), R ^{321 to} R ³²⁶ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include a substituent selected from the above substituent group A.
R ^{321 to} R ³²⁶ are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an amino group, an alkoxy group, a sulfamoyl group, or an ionic hydrophilic group, and a hydrogen atom, an alkyl group, an amino group, or an alkoxy group. Or a sulfamoyl group is more preferred. The ionic hydrophilic group is preferably a sulfo group.
R ^{321 to} R ³²⁶ may further have a substituent, and examples of the substituent in the case of further having a substituent include a substituent selected from the above substituent group A.
In the general formula ^(3), R 331 ^{to R 334} are the same as ^R 231 ^{to R 234} in formula (2), and preferred examples are also the same.

  In General Formula (3), M has the same meaning as M in the sulfo group described in General Formula (1), and preferred examples are also the same.

  Specific examples of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to these specific examples.

(Synthesis method)
As a method for synthesizing the compound represented by the general formula (1), it can be synthesized according to a synthesis method described in US Published Patent US4267251A, US Published Patent US4258118A, US Published Patent US4258119A, US Published Patent US4416971A, and the like.

(Coloring composition)
The coloring composition for fiber dyeing containing the polyamide of the present invention contains a compound represented by the general formula (1).
The fiber containing polyamide may be a single fiber of polyamide, or a blend of polyamide and other materials. It is preferred that the polyamide comprises nylon.
In the colored composition of the present invention, only one type of the compound represented by the general formula (1) may be used, or two or more types may be used in combination.
The coloring composition of the present invention may contain only the compound represented by the general formula (1) as a coloring agent. However, other coloring agents may be used 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.
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 colored composition is 20% by mass or less, the discharge property of the colored composition can be improved when used in an inkjet method, In addition, it is possible to obtain an effect such that the inkjet nozzle is not easily clogged.

The colored composition in the present invention generally contains a solvent in addition to the compound represented by the general formula (1). The type and amount of the solvent vary depending on the type of the compound represented by the general formula (1), the dyeing concentration, and the dyeing method, but the solvent is preferably contained in an amount of 40% by mass or more based on 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.
The recording medium for printing the colored composition of the present invention includes various fabrics, paper, coated paper coated with an ink receiving layer, a plastic film, and the like. Development of ink suitable for ink jet recording has also been performed.
The colored composition of the present invention can be used for a colored composition for dyeing on a fabric, an inkjet recording ink for printing on paper, a color toner, a resist for a color filter, and the like. Suitable as a coloring composition.
The colored composition of the present invention can be used as an ink composition, and can be preferably used as an ink for ink jet recording. In particular, it is used as an ink for ink jet textile printing in a textile printing method (ink jet textile printing) using an ink jet method. be able to. The ink composition of the present invention can be suitably used as a cyan hue ink.

[Coloring composition for dyeing and dyeing method]
The usage form of the coloring composition for dyeing of the present invention is not limited as long as it is a coloring composition for dyeing fibers containing polyamide. 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 dipped in a dye solution in which a dye is dissolved or dispersed in a solvent, adsorbed uniformly on the fiber surface, diffused into the fiber, and 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 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 colorable composition of the present invention is used for dip dyeing, the colorable composition is used as a dyeing solution capable of dipping a fabric or yarn. 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 described on pages 285 to 286, and migration inhibitors described on pages 279 to 284. Dye fixing agents described in dyeing notes on pages 304 to 321; dyeing fastness improvers; and pH adjusting agents described in dyeing notes on pages 322 to 334. In order to dye the dye uniformly at a high concentration, it can be adjusted by controlling the dye concentration, dye bath pH, salt concentration, dyeing temperature, dyeing time, pressure, and liquid flow, in addition to using the additive.
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, transfer printing, and printing method using the same]]
When the ink composition of the present invention is used for screen printing, roller printing, or transfer printing, the coloring composition is used as a color paste for printing on a fabric via a plate or transfer paper.
The textile printing method of the present invention is not particularly limited, but a method including at least the following steps (1) to (4) is preferable.
(1) A step of adding a coloring composition of the present invention to a liquid containing at least a polymer compound and water and adjusting a color paste (2) A step of printing the color paste of (1) on a fabric (3) Process of applying steam to the printed fabric (4) Process of washing and drying the printed fabric Coloring paste is suitable for printing on the plate and dyeing, washing, etc. It is required to satisfy the textile printing requirements.
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 paste for printing described in pages 349 to 361 of dyeing notes 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 a solvent containing at least water is most preferably used.
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 steam to the printed fabric is performed. In the process of applying steam to the printed fabric, the temperature and time for treatment with steam vary depending on the type of the colored composition and the type of the fabric, but the temperature is preferably 90 ° C to 140 ° C, more preferably 100 ° C to 108 ° C. preferable. The time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes. After the process of applying steam to the printed fabric, a printed product is obtained through a washing process and a drying process similar to the dip dyeing.

The ink composition of the present invention is preferably used as a cyan ink, but it can be preferably used not only for forming a single color image but also for forming a full color image in combination with other color inks.
In order to form a full-color image, it is preferable to use an ink set using a magenta hue ink and a yellow hue ink in addition to the ink composition (cyan ink) of the present invention. Further, in order to adjust the hue, other cyan hue ink and black hue ink may be used.

<Ink set>
The ink set is preferably a three-color ink set having at least magenta ink and yellow ink in addition to the cyan ink described above. Furthermore, a four-color ink set to which black ink is added is also preferable. In addition, 5 to 15 colors with inks commonly called “special colors” such as light yellow, light magenta, light cyan, light black, blue, violet, red, orange, green, golden yellow, brown, etc. are added as necessary. It is also possible to achieve printing with richer hues.
The colorant contained in each ink may be a known one and is not particularly limited, but is preferably a dye rather than a pigment. In particular, an acid dye is preferably used. Examples of the colorant contained in the ink used in the ink set of the present invention include acid dyes described in JP-A No. 2004-292522.

<Magenta ink>
The colorant contained in the magenta ink that can be used in the ink set is not particularly limited, but a dye is preferable, and an acid dye is particularly preferable. Specific examples of acidic dyes that can be used in the present invention include C.I. I. Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97: 1, 106, 111, 114, 118, 119, 127, 131 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415.
Of these, xanthene acid dyes are more preferably used. I. Acid Red 289 is preferred.
The content of the colorant in the total mass of the magenta ink is usually 0.5 to 20% by mass, preferably 7 to 15% by mass.
The additive that may be added to the magenta ink is preferably the same as the cyan ink described above.

<Yellow ink>
The colorant contained in the yellow ink that can be used in the ink set is not particularly limited, but a dye is preferable, and an acid dye is particularly preferable. Specific examples of acidic dyes that can be used in the present invention include C.I. I. Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 67, 72, 73, 79 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219: 1, 220, 230, 232, 235, 241, 242, 246.
Among these, monoazo acid dyes are more preferably used. I. Acid Yellow 110 is preferred.
Further, the content of the colorant in the total mass of the yellow ink is usually 0.5 to 20% by mass, preferably 7 to 15% by mass.
Additives that may be added to the yellow ink are the same as those of the cyan ink described above.

  In addition, this invention relates also to the fabric which printed the ink composition of this invention by said method.

[[Coloring composition for inkjet printing and printing method using the same]]
When the ink composition of the present invention is used for textile printing by the ink jet method, the ink composition is used as an ink for ink jet textile 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 impart ink suitability such as ink storage stability and ejection stability, image quality such as light resistance, water resistance, and chlorine resistance, printing suitability such as bleeding prevention and contamination prevention, and the like.
Although there is no restriction | limiting in particular in the inkjet textile printing method, The method containing the process of following (11)-(14) is mentioned preferably.
(11) A step of applying a paste containing at least a polymer compound and water to the fabric (12) A step of printing an ink for inkjet printing on the fabric by an inkjet method (13) A step of applying steam to the printed fabric (14) The process of washing and drying the printed fabric Inkjet printing methods may cause clogging of the nozzles when the color paste used in the conventional printing method is used. It is preferable to perform a pretreatment step (step of applying a paste containing at least a polymer compound and water to the fabric). 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 printing can be prepared by dissolving and / or dispersing the compound represented by the general formula (1) of the present invention (may be a mixture) in a lipophilic medium or an aqueous medium. . Preferably, the ink uses an aqueous medium.
Therefore, for the purpose of imparting appropriate ink, proper printing, and image fastness, the ink-jet printing ink can contain a solvent and a surfactant in addition to the dye.
The solvent is determined by the type of the substituent in the general formula (1) to be used, the type of the solvent component used for producing the colored composition, the type of fabric to be dyed, and the like, but preferably an aqueous medium, Preferably, water or a water-soluble organic solvent is used. The solvent can be prepared by dissolving and / or dispersing the compound represented by the general formula (1) in a lipophilic solvent or a water-soluble solvent.
The organic solvent that can be contained in the ink composition of the present invention is preferably an aqueous organic solvent. For example, in addition to polyhydric alcohols such as diethylene glycol and glycerin, amines, monohydric alcohols, polyhydric alcohol alkyls, and the like. And ethers. 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 is preferably 10% by mass or more and 60% by mass or less with respect to the total mass of the ink for inkjet 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 can contain another additive as needed in the range which does not impair the effect of this invention. Other additives include, for example, drying inhibitors (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, infrared absorbers, antiseptics, antifungal agents, pH adjusters, surface tension. Known additives such as a regulator, an antifoaming agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, a chelating agent, a reducing agent, an antioxidant, an antistatic agent, and a fluorescent brightening agent are included. . 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. 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 dispersant.
As the anti-drying agent, anti-fading agent, ultraviolet absorber, anti-mold agent, pH adjuster, surface tension adjuster, antifoaming agent and chelating agent, those described in JP-A-2014-5462 [0224] to [0231] are applied. it can. Further, a wet fastness improving agent described in JP-A-6-166969 and a light fastness improving agent 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 represented by the general formula (1) is dispersed in an aqueous medium, it can be dispersed by the method described in JP 2014-5462 A [0232] to [0233].
The ink for inkjet textile printing 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.
Ink for inkjet textile printing has a dyeing speed equivalent to that of other colors, so that it can be preferably used not only for the formation of single-color images but also for the formation of full-color images in combination with other color inks.
In order to form a full-color image, it is preferable to use an ink set containing at least a magenta hue ink and a yellow hue ink in addition to the ink composition of the present invention. Further, in order to adjust the hue, other cyan hue ink and black hue ink may be used.

  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.

A fabric that has been treated in advance may be used as 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 004-292989, JP 2002-249991, JP 2002-363872, JP-A 6-341070, JP 2004-197237, JP 2008-223192, and the like pre-treatment method of JP 2011-179130 publication.

  If necessary, the dyed fabric may be subjected to flame retardant treatment described in JP-A No. 62-257464, plasma treatment described in JP-A No. 2-47378, etc., JP-A No. 60-94678, and JP-A No. 2002-266236. In addition, fastness improving treatment such as light resistance, wet resistance, and chlorine resistance described in JP-A-2007-32247, JP-A-3-287873, JP-A-2004-131919, and the like may be performed. 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, JP-A-9-296379, 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, Japanese Laid-Open Patent Publication No. 2008-248437 and the like disclose an ink jet printing method.
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.

  In addition, this invention relates also to the fabric which carried out the inkjet printing of the ink composition of this invention by said method.

[Colored compound form and fabric to be dyed]
The compound represented by the general formula (1) is used for the purpose of dyeing 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).
The compound represented by the general formula (1) can dye protein fibers such as silk and wool, polyamide fibers such as nylon 6 and nylon 66 as acidic dyes, and is particularly preferable when dyeing fibers containing polyamide. Used.
When the compound represented by the general formula (1) is an oil-soluble compound, hydrophobic fibers such as polyester are generally dyed as disperse dyes, but acrylic fibers and polyamide fibers can also be dyed.
When the compound represented by the general formula (1) contains at least one cationic group such as a quaternary ammonium group, 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 chlorotriazinyl group, fluorotriazinyl group, chloropyrimidyl group, vinylsulfonyl group, chloroethylsulfonyl group, sulfatoethylsulfonyl group, and thiosulfatoethylsulfonyl group. Can be mentioned.

  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) has remarkably high dyeing properties especially when dyeing polyamide fibers, and is used as a dyeing fabric such as light resistance, water resistance, and chlorine resistance. Various performances 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.

<Examples 1-2 and Comparative Examples 1-4>
[Screen printing]
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 / glue: MEYPRO GUM NP [manufactured by MAYHALL CHEMICAL AG]
50g
・ PH adjuster: ammonium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 5g
Colorant: 2g of the dyes listed in Table 1
・ Water 43g
After the printed fabric was dried, steam treatment was performed with saturated steam at 105 ° C. for 20 minutes. Thereafter, the fabric was washed with water, and unfixed dye was washed away. The dyed cloth 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. The dyed fabric was dyed in a high density cyan to blue without fading. Table 1 shows the results of evaluating the dyed product according to the following evaluation method.

<Examples 11-12, Comparative Examples 11-14>
[Inkjet printing]
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.
(Composition of ink composition)
-5% by mass of the dyes shown in Table 2
・ 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 thus obtained was set in an ink-jet printer (manufactured by Dimatics Co., Ltd., DMP-2381), and an A4-sized solid image was printed on the resulting pretreated fabric.
<Post-processing process>
After the printed fabric was dried, steam was applied in saturated steam at 100 ° C. for 20 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.
Table 2 shows the results of evaluating the dyed product according to the following evaluation method.

[Performance evaluation]
1. Dischargeability In the printing process of inkjet printing, the presence or absence of streaks or blurs in the solid image was confirmed.
Evaluation criteria:
A: No streaking / scratching is observed B: Streaking / scratching is observed C: Ink is not ejected at all

2. Dyeing Concentration For each solid image formed on each fabric, the OD value was measured with a spectral densitometer (“X-rite 938” manufactured by Xrite).
Measurement condition:
Filter: Red (1SO status I density, defined in ISO standard “ANSI / ISO 5-3-1995”)
Light source: D50
Viewing angle: 2 degrees Evaluation criteria:
A: OD value ≧ 1.5
B: 1.5> OD value ≧ 1.0
C: 1.0> OD value

3. Light Resistance Using a xenon fade meter, a xenon light was irradiated for 6 hours to a stained sample prepared according to ISO 105-B02.
Before and after the irradiation with xenon light, each sample was measured with a spectral densitometer (“X-rite 938” manufactured by Xrite) to obtain ΔEab. The smaller the value, the smaller and better the behavior before and after light irradiation.
^{△ Eab = (△ L 2 +} △ a 2 + △ b 2) 0.5
Colorimetric conditions:
Light source: D50
Viewing angle: 2 degrees Evaluation criteria:
A: ΔEab ≧ 30
B: 30> ΔEab ≧ 10
C: ΔEab> 10

  Separately, the fabric was changed from nylon 6 jersey to silk fabric, wool fabric, and nylon 66 jersey, and ink jet printing was similarly applied to each fabric according to the method described in JP2013-209786A. As a result, a high light fastness and a dyeing density equivalent to that of magenta ink or yellow ink were obtained.

  As shown in the results of Tables 1 and 2, by using the colored composition of the present invention, there is no problem in inkjet discharge, excellent light resistance, and a polyamide capable of realizing a dyeing speed equivalent to magenta ink or yellow ink. An ink composition for dyeing fibers could be provided.

Claims (10)

The coloring composition for fiber dyeing containing the polyamide containing the compound represented by following General formula (1).
General formula (1):

In general formula (1), R ^{101 to} R ¹³⁵ each independently represent a hydrogen atom or a substituent. However, the compound represented by the general formula (1) contains at least two sulfo groups in the molecule. The coloring composition according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (2).
General formula (2):

In General Formula (2), R ^{201 to} R ²³⁴ each independently represent a hydrogen atom or a substituent. However, the compound represented by the general formula (2) contains at least two sulfo groups in the molecule. The colored composition according to claim 1 or 2, wherein the compound represented by the general formula (1) or (2) is represented by the following general formula (3).
General formula (3):

In general formula (3), R ^{301 to} R ³³⁴ each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation each independently.   The ink composition containing the coloring composition of any one of Claims 1-3.   A textile printing method using the ink composition according to claim 4.   A printing method for printing by an ink jet method using the ink composition according to claim 4.   7. The textile printing method according to claim 5, wherein the ink set includes at least three colors of cyan ink, magenta ink, and yellow ink. The cyan ink according to claim 4. A printing method using the ink composition.   The textile printing method according to claim 7, wherein the magenta ink contains a xanthene acid dye.   The textile printing method according to claim 7 or 8, wherein the yellow ink contains a monoazo acid dye.   A fabric printed by the printing method according to any one of claims 5 to 9.