JP2019019423A - Inkjet textile printing method, inkjet ink for textile printing, and colored textile production method - Google Patents

Abstract

To provide an inkjet textile printing method, a colored textile production method, and an inkjet ink for textile printing, which are capable of providing a colored textile excellent in image clarity, texture, wet rubbing fastness, and washing resistance.SOLUTION: An inkjet textile printing method comprises: directly printing a textile by inkjet printing with an inkjet ink containing a water dispersion of a polymer which has a structure derived from a dye and a carboxyl group, where the carboxyl group forms a salt with an organic amine; and performing heat treatment. Also provided are a colored textile production method, and an inkjet ink for textile printing that contains a water dispersion of the polymer.SELECTED DRAWING: None

Description

  The present invention relates to an inkjet printing method, an inkjet ink for printing, and a method for producing a colored fabric.

  Ink-jet printing does not require the production of a plate, can quickly form an image with excellent gradation, and uses only a necessary amount of ink as a formed image, so it has environmental advantages such as less waste liquid. It can be said that this is an excellent printing method.

Patent Document 1 describes sublimation transfer printing using ink containing resin particles containing a disperse dye.
Patent Document 2 describes an inkjet printing method using an inkjet ink containing a pigment. In this method, a pigment and a surfactant as a dispersant are mixed in water and then finely dispersed with an attritor or a mill machine together with glass beads, zirconia beads, titania beads, or stainless steel balls, etc., are used as a colorant. It has been. Then, this colorant is diluted with a reducer containing an emulsion resin for fixing the pigment, a pigment ink is prepared, adhered to the fiber by an ink jet method, and the resin is fused by a heating roller to fix the pigment. .

Patent Documents 3 and 4 describe inks containing an aqueous dispersion of polyurethane combined with a colorant.
Patent Document 5 describes an ink-jet ink containing an aqueous dispersion of an acrylic polymer to which an azomethine dye, an indoaniline dye or an azo dye is bonded.

JP-A-10-58638 JP 2010-37700 A Special table 2002-509957 gazette Special table 2004-534143 gazette Special table 2004-534106 gazette

However, the sublimation transfer printing described in Patent Document 1 cannot form a clear image on a cloth other than a polyester cloth. That is, a property capable of forming a clear image on various types of fabrics (also called “image sharpness”) is required. In addition, the ink-jet textile printing using the ink-jet ink containing the pigment described in Patent Document 2 cannot be said to have an excellent texture of the resulting colored cloth, and has poor wet friction fastness. Furthermore, there is room for improvement in the washing resistance of the colored fabric.
Note that Patent Documents 3 to 5 do not specifically disclose textile printing.

  An object of the present invention is to provide an inkjet printing method, an inkjet ink for printing, and a method for producing a colored fabric, which can provide a colored fabric excellent in all of image clarity, texture, fastness to wet friction, and washing resistance. It is to provide.

  The inventors of the present invention have made extensive studies and found that the above problems can be solved by the following means.

[1]
A step of directly printing an ink-jet ink having a structure derived from a dye and a carboxyl group, and an aqueous dispersion of a polymer in which the carboxyl group forms a salt with an organic amine, on a fabric by an inkjet method; and a heat treatment step. An ink-jet printing method comprising:
[2]
The inkjet printing method according to [1], wherein the organic amine has a boiling point of 250 ° C. or lower.
[3]
The inkjet printing method according to [1] or [2], wherein the organic amine is a tertiary amine.
[4]
The inkjet printing method according to any one of [1] to [3], wherein the organic amine is a compound represented by any one of the following general formulas (N-1) to (N-3).

In General Formula (N-1), R _{N1 to} R _N3 each independently represents an organic group. Two or more selected from R _{N1 to} R _N3 may be bonded to each other to form a ring.
In general formula (N-2), R _{N4 to} R _N7 each independently represents an organic group. Two or more selected from R _{N4 to} R _N7 may be bonded to each other to form a ring. L _N1 represents a linking group.
In General Formula (N-3), R _{N8 to} R _N12 each independently represents an organic group. Two or more selected from R _{N8 to} R _N12 may be bonded to each other to form a ring. L _N2 and L _N3 each independently represent a linking group.
[5]
The above dyes are azo dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine dyes, azomethine dyes, indoaniline dyes, indophenol dyes, nigrosine dyes, oxazine dyes, thiazine dyes. An anthraquinone dye, an indigo dye, a quinophthalone dye, a porphyrin dye, a cyanine dye, and at least one dye selected from the group consisting of a phthalocyanine dye [1] to [4] .
[6]
The inkjet printing method according to any one of [1] to [5], wherein the polymer is an acrylic polymer or a urethane polymer.
[7]
The inkjet printing method according to any one of [1] to [6], wherein the average particle size of the polymer in the aqueous dispersion is 50 to 500 nm.
[8]
An inkjet ink for textile printing comprising an aqueous dispersion of a polymer having a structure derived from a dye and a carboxyl group, wherein the carboxyl group forms a salt with an organic amine.
[9]
A step of directly printing an ink-jet ink having a structure derived from a dye and a carboxyl group, and an aqueous dispersion of a polymer in which the carboxyl group forms a salt with an organic amine, on a fabric by an inkjet method; and a heat treatment step. The manufacturing method of the colored cloth containing this.

  According to the present invention, there are provided an inkjet printing method, an inkjet ink for printing, and a method for producing a colored fabric, which can provide a colored fabric excellent in all of image clarity, texture, fastness to wet friction, and washing resistance. Can be provided.

Hereinafter, the present invention will be described in detail.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, “(meth) acrylic acid” represents at least one of acrylic acid and methacrylic acid, and “(meth) acrylic ester” represents at least one of acrylic acid ester and methacrylic acid ester.

In the present specification, the “substituent selected from substituent group A” refers to the substituents described in [0012] to [0051] of International Publication No. 2015/199135.
In the present specification, the substituent group A1 includes the following substituents.

(Substituent group A1)
A halogen atom, an alkyl group (preferably 1 to 30 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms), a heterocyclic group (preferably 3 to 3 carbon atoms) 30), acyl groups (preferably having 2 to 30 carbon atoms), hydroxyl groups, carboxyl groups, sulfo groups, cyano groups, nitro groups, alkoxy groups (preferably having 1 to 30 carbon atoms), aryloxy groups (preferably having carbon numbers) 6-30), an acyloxy group (preferably having 2 to 30 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms), a carbamoyl group, a sulfamoyl group, An alkylsulfonyl group (preferably having 1 to 30 carbon atoms), an arylsulfonyl group (preferably having 6 to 30 carbon atoms), an amino group, an A substituent comprising a ruamino group (preferably having 1 to 30 carbon atoms), an alkylsulfonylamino group (preferably having 1 to 30 carbon atoms), an arylsulfonylamino group (preferably having 6 to 30 carbon atoms), or a combination of two or more thereof. Group.

<Polymer having structure derived from dye>
In the present invention, an aqueous dispersion of a polymer having a structure derived from a dye and a carboxyl group and the carboxyl group forming a salt with an organic amine is used. First, a polymer having a structure derived from a dye will be described. To do.
In the polymer having a structure derived from a dye (hereinafter, also referred to as “dye polymer”) used in the present invention, the structure derived from a dye means one or more arbitrary hydrogen atoms from an organic compound used as a dye. A group formed by removing (dye residue), preferably a group formed by removing one or two arbitrary hydrogen atoms from an organic compound used as a dye.
The dye polymer is a pigment multimer including a structure derived from a dye, and may be a linear polymer or a network polymer. In the case of a linear polymer, the structure derived from the dye may be included in the main chain of the polymer, or may be included in the side chain.
The dye polymer may be a polymer having a repeating unit including a structure derived from a dye.

As the dye polymer, a polymer obtained by polymerizing a monomer having an ethylenically unsaturated group (for example, an acrylic polymer, a vinyl polymer, a styrene polymer) or a urethane polymer is preferable, and an acrylic polymer or a urethane polymer is more preferable.
The acrylic polymer in the present invention is a polymer having at least one repeating unit out of the group consisting of repeating units derived from (meth) acrylic acid and repeating units derived from (meth) acrylic acid esters. The urethane polymer (also referred to as “polyurethane”) in the present invention is a polymer having a urethane bond, and is formed by a polymerization reaction between a compound having two or more hydroxyl groups and a compound having two or more isocyanate groups. The Moreover, the styrene polymer in this invention means the polymer which has a repeating unit derived from styrene.
The method for obtaining the dye polymer is arbitrary, but a monomer containing a structure derived from a dye (also referred to as “dye monomer”) is polymerized or copolymerized with other monomers to form a dye polymer. Examples thereof include a method of obtaining a dye polymer by preparing a polymer not having a structure derived from a dye in advance and then introducing a structure derived from the dye by a polymer reaction or the like. The method for producing the dye polymer or the polymer having no structure derived from the dye is not particularly limited, but those synthesized by radical polymerization, addition polymerization or condensation polymerization are preferably used.

As a structure derived from a dye, a structure derived from a dye as classified by a color index (abbreviation “CI”), or an arbitrary substituent within the scope of the effect of the present invention in the structure A structure in which is substituted, or a structure in which an arbitrary substituent is removed from the structure within a range where the effects of the present invention are obtained is preferable.
Examples of the dye include an azo dye (monoazo dye, disazo dye, trisazo dye, polyazo dye), stilbene dye, carotenoid dye, diarylmethane dye, triarylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye (monomethine). Dyes, polymethine dyes), azomethine dyes, aniline dyes, indoaniline dyes, indamine dyes, indophenol dyes, azine dyes, oxazine dyes, thiazine dyes, anthraquinone dyes, indigo dyes, quinophthalone dyes, digrosine dyes, porphyrin dyes, cyanine dyes And phthalocyanine dyes.
Dyes are azo dye, stilbene dye, diarylmethane dye, triarylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye, azomethine dye, indoaniline dye, indophenol dye, nigrosine dye, oxazine dye, thiazine dye, It is preferably at least one dye selected from the group consisting of anthraquinone dyes, indigo dyes, quinophthalone dyes, porphyrin dyes, cyanine dyes and phthalocyanine dyes.
More preferably, from the viewpoint of coloring power, it consists of an azo dye, a stilbene dye, a diarylmethane dye, a triarylmethane dye, a xanthene dye, an indoaniline dye, an indophenol dye, a nigrosine dye, an anthraquinone dye, a quinophthalone dye, and a phthalocyanine dye. At least one dye selected from the group, more preferably an azo dye, a stilbene dye, a triarylmethane dye, a xanthene dye, an indoaniline dye, an indophenol dye, a nigrosine dye, an anthraquinone dye, a quinophthalone dye, and a phthalocyanine At least one dye selected from the group consisting of dyes, particularly preferably an azo dye, a triarylmethane dye, a xanthene dye, an anthraquinone dye, a quinophthalone dye, and a phthalocyanine At least one dye selected from the group consisting of charge, the dye represented by any one of the later-described general formulas (M1) ~ (M8) is most preferred.

  The dye may be a water-soluble dye or a water-insoluble dye, but it may be a water-insoluble dye from the viewpoint of water resistance and washing resistance of the dye polymer. preferable. Moreover, it is preferable that it is a dye which does not have ionic groups, such as a carboxyl group, a sulfo group, a phosphoric acid group, these salts, and an ammonium group. Such a dye is not particularly limited, and for example, a water-insoluble dye such as a disperse dye may be used, or a water-soluble dye obtained by removing an ionic group may be used.

As the dye polymer, a polymer containing at least one of a structure represented by the following general formula (1) and a structure represented by the following general formula (2), or a structure represented by the following general formula (3): It is preferable that it is a polymer containing.
As a polymer containing at least one of the structure represented by the following general formula (1) and the structure represented by the following general formula (2), one or two of the structures represented by the following general formula (1) may be used. A polymer containing the above, a polymer containing one or more structures represented by the following general formula (2), one or more structures represented by the following general formula (1), and the following general formula (2) Examples thereof include a polymer containing one or more types of structures represented, a structure represented by the following general formula (1), a polymer containing at least one kind of the structure represented by the following general formula (2) and other structures.
As a polymer including a structure represented by the following general formula (3), a polymer including one or more structures represented by the following general formula (3), a structure represented by the following general formula (3), and Examples thereof include polymers containing other structures.

In General Formula (1), X ¹ and X ² each independently represent —O—, —NH—, or —NR ¹ —, R ¹ represents a substituent, L ¹ represents a trivalent linking group, L ² represents a divalent linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye. When ^one of X ¹ and X ² represents —NR ¹ — and the other represents —NH— or —NR ¹ —, X ¹ and X ² may be bonded.

In general formula (2), X ³ and X ⁴ each independently represent —O—, —NH— or —NR ¹ —, R ¹ represents a substituent, and L ³ and L ⁴ each independently represent a single bond. Alternatively, it represents a divalent linking group, L ⁵ represents a divalent linking group, and D ² represents a dye residue obtained by removing two arbitrary hydrogen atoms from a dye. When one of X ³ and X ⁴ represents —NR ¹ — and the other represents —NH— or —NR ¹ —, X ³ and X ⁴ may be bonded.

In general formula (3), R ^{2 to} R ⁴ each independently represent a hydrogen atom or a substituent, and L ⁶ is a single bond or a divalent group represented by the following formula (L6-1) or (L6-2). Represents a linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye.

In Formula (L6-1), L ⁷ represents a single bond or a divalent linking group, * 4 represents a position bonded to the carbon atom in General Formula (3), and * 5 represents General Formula (3 ) represents a position bonded with D ¹ of the in.
Wherein (L6-2), ^{L 8} represents a single bond or a divalent linking group, * 6 represents the general formula (3) position and a carbon atom in the, * 7, the general formula (3 ) represents a position bonded with D ¹ of the in.

[Structure represented by formula (1)]
The structure represented by the general formula (1) will be described.
In General Formula (1), X ¹ and X ² each independently represent —O—, —NH—, or —NR ¹ —, and R ¹ represents a substituent. R ¹ is preferably an alkyl group, a cycloalkyl group or an aryl group. X ¹ and X ² preferably represent —O— or —NH—, and more preferably —O—.
It is preferable that at least one of X ¹ and X ² represents —O—.

In General Formula (1), L ¹ represents a trivalent linking group. The trivalent linking group represented by L ¹ is not particularly limited as long as the effects of the present invention can be achieved, but it is a substituted or unsubstituted linear, branched or cyclic aliphatic hydrocarbon having 1 to 30 carbon atoms. A group (may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group), a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms (even an aromatic hydrocarbon group) May be an aromatic heterocyclic group), a linking group represented by the following general formula (L-1), a linking group represented by the following general formula (L-2), and two or more of these. Are preferably formed. Examples of the substituent in the case where these have a substituent include a substituent selected from the above substituent group A (preferably a substituent selected from the above substituent group A1). In the linking group, -O-, -S-, -NR- (R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), -C (= O). -, - SO -, - SO 2 - may have the like.

In General Formulas (L-1) and (L-2), L ¹¹ and L ¹² each independently represent a single bond or a divalent linking group. * 1 and * 2 represent positions that bind to X ¹ and X ² in the general formula (1), respectively. * 3 represents positions that bind to D ¹ in the general formula (1).

In General Formulas (L-1) and (L-2), L ¹¹ and L ¹² each independently represent a single bond or a divalent linking group. The divalent linking group in the case where L ¹¹ and L ¹² represent a divalent linking group is not limited as long as the effects of the present invention can be obtained, but a substituted or unsubstituted alkylene group (linear Or may be branched, and preferably has 1 to 30 carbon atoms.), Substituted or unsubstituted cycloalkylene group (preferably 3 to 30 carbon atoms), substituted Or an unsubstituted arylene group (having preferably 6 to 30 carbon atoms), a substituted or unsubstituted heterocyclic group (preferably having 2 to 30 carbon atoms), -CH = CH-, —O—, —S—, —NR— (R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C (═O) —, —SO—, —SO ₂ —, Or, a linking group formed by linking two or more of these is preferable. . Examples of the substituent in the case where these have a substituent include a substituent selected from the above substituent group A (preferably a substituent selected from the above substituent group A1).

In general formula (1), L ² represents a divalent linking group. The divalent linking group represented by L ² is a divalent linking group in the case where L ¹¹ and L ^{12 in} the general formulas (L-1) and (L-2) represent a divalent linking group. This is the same as described in the description.

In the general formula (1), D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye. D ¹ is not limited as long as it exhibits the effects of the present invention, but represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye represented by any one of the following general formulas (M1) to (M8). It is preferable. In addition, general formula (M2) and (M3) shall also include each resonance structure.

In General Formula (M1), R ^{101 to} R ¹¹⁰ each independently represent a hydrogen atom or a substituent.
In General Formula (M2), R ^{201 to} R ²¹⁵ each independently represent a hydrogen atom or a substituent, X ²⁰¹ represents a monovalent anion, and n ²⁰¹ represents 0 or 1.
In General Formula (M3), R ^{301 to} R ³¹⁷ each independently represent a hydrogen atom or a substituent, X ³⁰¹ represents a monovalent anion, and n301 represents 0 or 1.
In General Formula (M4), R ^{402 to} R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent, Ar ⁴⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In General Formula (M5), R ^{501 to} R ⁵⁰⁸ each independently represent a hydrogen atom or a substituent.
In General Formula (M6), R ^{601 to} R ⁶⁰² each independently represent a hydrogen atom or a substituent, R ⁶⁰³ represents a hydrogen atom or a substituent, and Ar ⁶⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group. And the phenyl group, the naphthyl group, or the heterocyclic group may further have a substituent.
In general formula (M7), R ^{701 to} R ⁷⁰⁶ each independently represent a hydrogen atom or a substituent.
In General Formula (M8), R ^{811 to} R ⁸¹⁸ and R ^{821 to} R ⁸²⁸ each independently represent a hydrogen atom or a substituent.

R ^{101 to} R ¹¹⁰ in general formula (M1), R ^{201 to} R ²¹⁵ in general formula (M2), R ^{301 to} R ³¹⁷ in general formula (M3), R ^{402 to} R in general formula (M4) ⁴⁰⁷ , R ^{501 to} R ⁵⁰⁸ in general formula (M5), R ^{601 to} R ⁶⁰³ in general formula (M6), R ^{701 to} R ⁷⁰⁶ in general formula (M7), and R in general formula (M8) Examples of the substituent when ^{811 to} R ⁸¹⁸ and R ^{821 to} R ⁸²⁸ represent a substituent include a substituent selected from the substituent group A (preferably a substituent selected from the substituent group A1).

R ^{101 to} R ¹¹⁰ in general formula (M1), R ^{201 to} R ²¹⁵ in general formula (M2), R ^{301 to} R ³¹⁷ in general formula (M3), R ^{402 to} R in general formula (M4) ⁴⁰⁷ , when R ^{501 to} R ⁵⁰⁸ in the general formula (M5) and R ^{601 to} R ⁶⁰² in the general formula (M6) represent a substituent, at least two of the substituents are bonded to each other, and It may form a 6-membered, 6-membered, or 7-membered saturated or unsaturated ring. When the formed 5-membered, 6-membered, and 7-membered rings are further substitutable groups, they may further have a substituent, and the substituent is selected from the above substituent group A. (Preferably a substituent selected from the above substituent group A1).

The substituent in the case where Ar ⁴⁰¹ in the general formula (M4) further has a substituent and the substituent in the case where Ar ⁶⁰¹ in the general formula (M6) further has a substituent are selected from the above substituent group A. And a substituent (preferably a substituent selected from the substituent group A1).

X ²⁰¹ in the general formula (M2) and X ³⁰¹ in the general formula (M3) are preferably chlorine ion, acetate ion, triflate ion, tetrafluoroborate ion, tetrakis (pentafluorophenyl) borate ion, perchlorate ion, or Bis (trifluoromethanesulfonyl) imide anion is preferred.

  Some of the dyes represented by the general formulas (M1) to (M8) are classified by color index, and can be synthesized by a conventionally known method (for example, Japanese Patent Publication No. 7-49583, patent) No. 5715380, International Publication No. 2010/110199, Japanese Translation of PCT International Publication No. 2002-509957, etc.).

  Specific examples of the dyes represented by the general formulas (M1) to (M8) are those described in [0126] to [0132] of PCT / JP2017 / 002788, and [0092] to [0092] of Japanese Patent Application No. 2017-034066. Reference can be made to those described in [0100] and those described in [0068] of JP 2013-535558.

[Structure represented by formula (2)]
Next, the structure represented by the general formula (2) will be described.
X ³ and X ⁴ in the general formula (2) have the same meanings as X ¹ and X ² in the general formula (1), and preferred ranges are also the same.
In General Formula (2), L ³ and L ⁴ each independently represent a single bond or a divalent linking group, and L ⁵ represents a divalent linking group. Examples of the divalent linking group when L ³ and L ⁴ represent a divalent linking group, and the divalent linking group represented by L ⁵ include those in the general formulas (L-1) and (L-2) described above. Are the same as those described in the description of the divalent linking group in the case where L ¹¹ and L ¹² in the formula represent a divalent linking group.
L ³ and L ⁴ preferably represent a single bond.

In the general formula (2), D ² represents a dye residue obtained by removing two arbitrary hydrogen atoms from a dye. D ² is not limited as long as it has the effect of the present invention, but D ² is a dye residue obtained by removing two arbitrary hydrogen atoms from the dye represented by any one of the general formulas (M1) to (M8). More preferably, it represents.
Also in D ² of the general formula (2), preferable ranges and examples of the general formula (M1) ~ (M8) are the same as those described above.

When the dye polymer in the present invention is a polymer containing at least one of the structure represented by the general formula (1) and the structure represented by the general formula (2) (a polyurethane having a structure derived from a dye) Typically, polymerization of a compound having two or more hydroxyl groups such as diol or triol which is a monomer and a compound (polyisocyanate compound) having two or more isocyanate groups such as diisocyanate which is a monomer Although it is synthesized by reaction, as can be seen from the structure represented by the general formula (1) or (2), it is not limited to this and is selected from the group consisting of a hydroxyl group, a primary amino group, and a secondary amino group It can have a structure obtained by a polymerization reaction of a monomer having 2 or more groups in total and a monomer having 2 or more isocyanate groups
When the dye polymer in the present invention is a polyurethane, the dye polymer has a structure derived from a dye and has a total of two or more groups selected from the group consisting of a hydroxyl group, a primary amino group, and a secondary amino group. It preferably has a structure obtained by polymerizing a monomer (dye monomer) and a monomer having two or more isocyanate groups.
The number of groups selected from the group consisting of the hydroxyl group, primary amino group, and secondary amino group is the number of groups that can react with an isocyanate group in consideration of steric hindrance and the like.
The aforementioned dye (preferably a dye represented by any one of the general formulas (M1) to (M8)) is composed of 2 groups selected from the group consisting of a hydroxyl group, a primary amino group, and a secondary amino group in total. When it has more than one, it can be used as a dye monomer.
In addition, when the above-described dye (preferably a dye represented by any one of the general formulas (M1) to (M8)) does not have a hydroxyl group, a primary amino group, or a secondary amino group, A dye monomer can be obtained by introducing a group, a primary amino group or a secondary amino group by a chemical reaction.

(Polyisocyanate compound)
The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule, and in the present invention, a compound having two isocyanate groups in one molecule is preferable.
Polyisocyanate compounds include phenylene diisocyanate, cyclohexane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, bis (isocyanatomethyl) cyclohexane, Norbornene diisocyanate, lysine diisocyanate, a multimer of the above diisocyanate, and a reaction product of 1 mol of diol and 2 mol of diisocyanate can be used. These may be used alone or in combination.

  A catalyst can be used in the reaction between the dye monomer and the polyisocyanate compound. As the catalyst, a tin compound, a titanium compound, a bismuth compound, a zinc compound, an organic base (such as a tertiary amine compound or diazabicycloundecene (DBU)), or the like can be preferably used.

(Other monomers)
When the dye polymer in the present invention is polyurethane, it may be a polymer obtained by further reacting other monomers in addition to the dye monomer and the polyisocyanate compound.
As other monomers, diol, triol or diamine is preferable. A diol having a carboxyl group or a triol having a carboxyl group is also preferred.

When the dye polymer in the present invention is polyurethane, it may be a polymer having a urea bond. A polymer having a urethane bond and a urea bond is also referred to as “polyurethane / urea”.
As one type of preferred form of the dye polymer in the present invention, there is a polyurethane / urea in which a structure derived from a dye and a first partial structure including a urethane bond and a second partial structure including a urethane bond are bonded by a urea bond. Can be mentioned.

[Structure represented by formula (3)]
Next, the structure represented by the general formula (3) will be described.
The polymer including the structure represented by the general formula (3) is preferably a vinyl polymer, an acrylic polymer, or a styrene polymer.
R ² and R ³ in the general formula (3) each independently represent a hydrogen atom or a substituent, and the substituent in the case of representing the substituent is a substituent selected from the substituent group A (preferably the above-mentioned Substituents selected from substituent group A1). R ² and R ³ preferably represent a hydrogen atom.
R ⁴ in the general formula (3) represents a hydrogen atom or a substituent, and the substituent in the case of representing the substituent is a substituent selected from the above substituent group A (preferably selected from the above substituent group A1). Substituents). R ⁴ preferably represents a hydrogen atom or a methyl group.
L ^{7 in the} above formula (L6-1) and L ⁸ in the above formula (L6-2) each independently represent a single bond or a divalent linking group and represent a divalent linking group. The linking group is the same as that described in the description of the divalent linking group in the case where L ¹¹ and L ^{12 in} the general formulas (L-1) and (L-2) represent a divalent linking group. It is.
L ⁶ in the general formula (3) preferably represents a divalent linking group represented by the above formula (L6-1).
In General Formula (3), D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye. D ¹ is not limited as long as it exhibits the effects of the present invention, but D ¹ is a dye residue obtained by removing one hydrogen atom from the dye represented by any one of the general formulas (M1) to (M8). More preferably, it represents.
Also in D ¹ of the general formula (3), preferable ranges and examples of the general formula (M1) ~ (M8) are the same as those described above.

When the dye polymer in the present invention is a polymer obtained by polymerizing a monomer having an ethylenically unsaturated group (preferably an acryloyl group or a methacryloyl group), the dye polymer has a structure derived from a dye and has an ethylenically unsaturated group. A polymer obtained by polymerizing a compound having a saturated group (dye monomer) is preferred.
When the above-mentioned dye (preferably a dye represented by any one of the general formulas (M1) to (M8)) has an ethylenically unsaturated group, it can be used as a dye monomer.
Moreover, when the above-mentioned dye (preferably the dye represented by any one of the general formulas (M1) to (M8)) does not have an ethylenically unsaturated group, the dye is chemically reacted with the ethylenically unsaturated group. It can be set as a dye monomer.

(Other monomers)
When the dye polymer in the present invention is a polymer obtained by polymerizing a monomer having an ethylenically unsaturated group, it was obtained by copolymerizing other monomers in addition to the dye monomer. It may be a polymer.

[Organic amine]
The dye polymer used in the present invention is a polymer having a carboxyl group in addition to a structure derived from a dye. In the aqueous dispersion of the dye polymer in the present invention, the carboxyl group of the dye polymer forms a salt with the organic amine.
“The carboxyl group forms a salt with the organic amine” means that the carboxyl group interacts with the organic amine. Hereinafter, “the carboxyl group forms a salt with an organic amine” may be expressed as “has an organic amine salt of a carboxyl group”. In the present invention, it is sufficient that at least the carboxyl group of the dye polymer forms a salt with an organic amine. When the dye polymer further has an ionic group other than the carboxyl group, An ionic group other than the carboxyl group may form a salt with the organic amine.
In the present invention, since the dye polymer has an organic amine salt of a carboxyl group in the aqueous dispersion of the dye polymer, it is considered that the particles are close to each other due to charge repulsion and excellent in dispersion stability. On the other hand, when an ink jet ink containing an aqueous dispersion of a dye polymer is deposited on a fabric by the ink jet method and then subjected to a heat treatment, the organic amine that forms a carboxyl group and a salt is volatilized to form a carboxyl group. It is presumed that the hydrophobicity of the polymer is increased and the washing resistance of the obtained colored fabric is improved.

  Examples of the organic amine include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tris (2-ethylhexyl) amine, N, N-dimethylethylamine, N, N-dimethyln-propylamine, N , N-dimethylisopropylamine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethyldodecylamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N , N-dimethyl-N ′, N′-dimethyl-1,3-propanediamine, triethylenediamine, N, N-dimethylethanolamine, N, N-dibutylethanolamine, N, N′-dimethylpiperazine, bis (2- Dimethylaminoethyl) ether, pentamethyldi Chirentoriamin, N, N, N ', N'-tetramethyl-1,6-hexanediamine, N- methylpiperidine, etc. N- ethylpiperidine and the like.

  The organic amine is preferably a compound represented by any one of the following general formulas (N-1) to (N-3).

In General Formula (N-1), R _{N1 to} R _N3 each independently represents an organic group. Two or more selected from R _{N1 to} R _N3 may be bonded to each other to form a ring.
In general formula (N-2), R _{N4 to} R _N7 each independently represents an organic group. Two or more selected from R _{N4 to} R _N7 may be bonded to each other to form a ring. L _N1 represents a linking group.
In General Formula (N-3), R _{N8 to} R _N12 each independently represents an organic group. Two or more selected from R _{N8 to} R _N12 may be bonded to each other to form a ring. L _N2 and L _N3 each independently represent a linking group.

In the general formulas (N-1) to (N-3), the organic group represented by R _{N1 to} R _N12 is preferably an organic group having 1 to 12 carbon atoms. As the organic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group is preferable, and a substituted or unsubstituted alkyl group is more preferable. When these have a substituent, the substituent is preferably a hydroxyl group.
In the general formulas (N-2) and (N-3), the linking group represented by L _{N1 to} L _N3 is preferably a substituted or unsubstituted alkylene group that may contain an oxygen atom in the chain. When these have a substituent, the substituent is preferably a hydroxyl group.

From the viewpoint of dispersion stability in the aqueous dispersion of the dye polymer and the water resistance and washing resistance of the resulting colored fabric, the boiling point of the organic amine is preferably 250 ° C. or less, more preferably 200 ° C. or less, More preferably, it is 150 ° C. or lower. The boiling point is the boiling point at 101325 Pa.
Further, from the viewpoint of dispersion stability in the aqueous dispersion of the dye polymer, the organic amine is preferably a tertiary amine.
Specific examples of the organic amine include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, N, N-dimethylethylamine, N, N-dimethyln-propylamine, N, N- Dimethylisopropylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N-dimethyl-N ′, N′-dimethyl-1,3-propanediamine, Triethylenediamine is preferred, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, N, N-dimethyl-N ′, N′-dimethyl-1,3-propanediamine, and triethylenediamine are more preferred, and triethylamine Is particularly preferred.

As a method for introducing an organic amine salt of a carboxyl group into a dye polymer, a method in which a dye polymer is synthesized using a monomer having a carboxyl group and then neutralized with an organic amine can be mentioned.
The monomer having a carboxyl group may be a dye monomer or other monomer.
When the monomer having a carboxyl group is another monomer, when the dye polymer is an acrylic polymer, acrylic acid, methacrylic acid, succinic acid mono (2-acryloyloxyethyl), succinic acid mono ( 2-methacryloyloxyethyl), 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, ω-carboxy Polycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, reaction product of 2-hydroxyethyl acrylate and acid anhydride, reaction product of 2-hydroxyethyl methacrylate and acid anhydride, etc. Acid mono (2-acryloyloxyethyl) Succinic acid mono (2-methacryloyloxyethyl), ω-carboxypolycaprolactone monoacrylate, and ω-carboxypolycaprolactone monomethacrylate are preferably used.
When the dye polymer is a urethane polymer, one-to-one reaction product of dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpropionic acid and acid anhydride, one pair of dimethylolbutanoic acid and acid anhydride 1 reaction product etc. are mentioned, dimethylol propionic acid and dimethylol butanoic acid are used preferably.

(Ionicity of dye polymer)
Since the dye polymer is used in a state dispersed in water, the dye polymer itself preferably has charge repulsion. When the dye polymer itself has charge repulsion, it is excellent in dispersion stability required for ink jet ejection. In the present invention, the dye polymer has an organic amine salt of a carboxyl group as an ionic group.
On the other hand, when there are too many ionic groups of a dye polymer, a dye polymer will melt | dissolve in water and it will become difficult to obtain the aqueous dispersion of a dye polymer. In addition, the amount of ionic groups in the dye polymer has an optimum range from the viewpoint of water resistance (color fading during washing, etc.) of the resulting colored fabric. The amount of the ionic group (ionic group amount) of the dye polymer is preferably 0.1 to 1.8 mmol / g, more preferably 0.2 to 1.3 mmol / g.

(Structure of dye polymer)
The dye polymer may have a structure derived from a dye and an organic amine salt of a carboxyl group as an essential structure, but may further have an ionic or nonionic dispersing group. The molecular structure of the dye polymer may be linear or branched.

<Aqueous dispersion of dye polymer>
The aqueous dispersion of the dye polymer (dye polymer aqueous dispersion) contains at least water and the dye polymer, and the dye polymer is dispersed in water. The dye polymer aqueous dispersion may contain an aqueous organic solvent. Further, depending on the method for producing the aqueous dispersion of the dye polymer, either a low molecular surfactant or a high molecular dispersant may be used together or not (so-called self-dispersing).
Only one dye polymer can be used, or two or more dye polymers can be mixed and used in an arbitrary ratio.

In the present invention, the above dye polymer is used in a state of being dispersed in water, not in a state of being dissolved in water.
In the state where the dye polymer is dispersed in water, unlike the state in which the dye polymer is dissolved in water, the polymer is substantially insoluble in water, and thus is excellent in terms of water resistance such as washing resistance and sweat resistance. In the ink-jet printing method of the present invention, a step of washing with water after printing is unnecessary, and therefore the dye polymer is a polymer that is substantially insoluble in water. In the aqueous dispersion of the dye polymer, the dye polymer that is not soluble in water is dispersed as particles, and the average particle diameter is preferably 50 to 500 nm. When the dye polymer is dissolved in water, the dye polymer is not present as particles in water.
It is preferable to use ultrapure water as water.

  When dispersed in water, the dye polymer is easily compatible with water (easy to get wet) and electrostatic repulsion (repulsive force) as a property of the dye polymer itself or by adsorption with the low molecular surfactant or polymer dispersant used in combination. ) Or steric repulsion prevents re-aggregation of the fine particles of the dye polymer, and has a function of suppressing sedimentation.

The dye polymer is in the form of particles in the aqueous dispersion. The average particle diameter of the particulate dye polymer in the aqueous dispersion of the dye polymer is preferably 50 to 500 nm, more preferably 50 to 300 nm, and particularly preferably 50 to 200 nm. Within this range, the fabric can be printed by the ink jet method.
The value measured using the particle size distribution measuring apparatus (Nanotrack UPA EX150, the Nikkiso Co., Ltd. make, brand name) was used for the average particle diameter in this specification.

The content of the dye polymer in the dye polymer aqueous dispersion is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass. Within this range, a high-density colored cloth can be obtained in printing while ensuring storage stability as an inkjet ink.
The content of water in the dye polymer aqueous dispersion is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and particularly preferably 60 to 90% by mass. This range is preferable because the stability of the dye polymer aqueous dispersion and the ejection stability as an inkjet ink can be imparted. In addition, the stability of the dye polymer aqueous dispersion indicates that precipitation or the like hardly occurs.

(Aqueous organic solvent)
The aqueous organic solvent preferably has a water solubility at 25 ° C. of 10 g / 100 g-H ₂ O or more, more preferably 20 g / 100 g-H ₂ O or more, and is miscible with water at an arbitrary ratio. Is particularly preferred. Examples of the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents.
The content of the aqueous organic solvent in the dye polymer aqueous dispersion is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. This range is preferable because the stability of the dye polymer aqueous dispersion and the ejection stability as an inkjet ink can be imparted.

(Low molecular surfactant or polymer dispersant)
The low molecular surfactant or the high molecular dispersant is preferably a low molecular surfactant or a high molecular dispersant having a hydrophobic group and an ionic group, and is added when the dye polymer is dispersed. The low molecular surfactant or polymer dispersant adsorbs to the surface of the dye polymer and blends (wet) it with water, and the dye polymer fine particles ground by mechanical action are electrostatically repulsive (repulsive) or steric repulsive. This prevents the re-aggregation of fine particles and has a function of suppressing sedimentation.

  The content of the low molecular surfactant is preferably in the range of 0.001 to 5.0% by mass with respect to the total mass of the dye polymer aqueous dispersion, and the surface tension of the aqueous dispersion can be arbitrarily set within this range. It is preferable to adjust to.

  The content of the polymeric dispersant is preferably in the range of 0.001 to 50% by mass with respect to the total mass of the dye polymer aqueous dispersion, and the surface tension of the aqueous dispersion is arbitrarily adjusted within this range. It is preferable to do.

(Method for producing aqueous dispersion of dye polymer)
Although the manufacturing method of the aqueous dispersion of dye polymer is not specifically limited, For example, the method shown to the following (i)-(v) is mentioned.
(I) a method in which a dye polymer powder or paste is mixed in water and then finely dispersed in an attritor or a mill with glass beads, zirconia beads, titania beads, or stainless steel balls,
(Ii) A method of obtaining an aqueous dispersion of a dye polymer by mixing water and a dye monomer to polymerize the dye monomer to obtain a dye polymer,
(Iii) The dye polymer is synthesized in an organic solvent, or the dye polymer taken out in a solid state after being synthesized in an organic solvent is dissolved in the organic solvent, water and a neutralizing agent are added, and the organic solvent is not removed. Or a method of obtaining an aqueous dispersion of a dye polymer by removing an organic solvent,
(Iv) Mixing an organic solvent and a dye monomer, polymerizing the dye monomer to obtain an organic solvent solution of the dye polymer, and adding water and a neutralizing agent to the organic solvent solution of the dye polymer And emulsifying to obtain an aqueous dispersion of the dye polymer,
(V) an organic solvent solution of a first prepolymer having a structure derived from a dye and having an isocyanate group at the terminal, and an organic solvent of a second prepolymer having a dispersible structure and having an isocyanate group at the terminal A method of mixing a solvent solution, adding water and emulsifying to obtain an aqueous dispersion of a dye polymer

(I) is prepared by mixing an aqueous organic solvent, a low molecular surfactant or a high molecular dispersant in water, if necessary, in addition to the dye polymer powder or paste, in glass, glass beads, zirconia beads, It may be a method of fine dispersion with an attritor or a mill machine together with titania beads or stainless steel balls.
(Ii) is a dye prepared by mixing water and an aqueous organic solvent, a dye monomer, and, if necessary, other monomers, a polymerization initiator, an organic solvent, a neutralizing agent and an emulsifier (surfactant). A method of obtaining a dye polymer by polymerizing the monomer and other monomers as required, and obtaining an aqueous dispersion of the dye polymer by appropriately removing the organic solvent when an organic solvent is added, It may be.
(Iii) is a method of synthesizing a dye polymer in an organic solvent, or dissolving a dye polymer taken out in a solid state after synthesizing in an organic solvent in an organic solvent, water, a neutralizing agent, and optionally an emulsifier (surfactant). ) And an organic solvent, and an organic solvent is appropriately removed to obtain an aqueous dispersion of a dye polymer.
(Iv) is a method of mixing an organic solvent, a dye monomer, and other monomers and a polymerization initiator as necessary, and adding a dye monomer and other monomers as necessary. Polymerization is carried out to obtain an organic solvent solution of the dye polymer. The organic solvent solution of the dye polymer is emulsified by adding water and a neutralizing agent, optionally an emulsifier (surfactant) and a chain extender, and the dye polymer is chained. After extension, a method of removing an organic solvent as appropriate to obtain an aqueous dispersion of a dye polymer may be used.
(V) is an organic solvent solution of a first prepolymer having an isocyanate group at the terminal, having a structure derived from a dye, and a second prepolymer having a dispersible structure and having an isocyanate group at the terminal The organic solvent solution is optionally mixed with an emulsifier (surfactant) and an organic solvent, and further emulsified by adding water and optionally an emulsifier (surfactant), and the organic solvent is appropriately removed to obtain a dye polymer. The method of obtaining the water dispersion of this may be sufficient.

The organic solvent may be an aqueous organic solvent or a non-aqueous organic solvent.
The non-aqueous organic solvent is an organic solvent that is not an aqueous organic solvent, and preferably has a water solubility at 25 ° C. of less than 10 g / 100 g-H ₂ O.
In addition, glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, polyethylene glycol, etc., and urea, hyaluronic acid, sucrose, etc., are added to the aqueous dispersions of these dye polymers as necessary. can do. In addition, a nonionic surfactant or an anionic surfactant can be added as a dispersion aid, but these surfactants are blended in a small amount so as not to lower the performance as dispersion stability. It is preferable.

The dye polymer aqueous dispersion is used for the above reason because there are few precipitates, dispersion stability is good, streaks and unevenness are less likely to occur when droplets are ejected by the ink jet method, and a clear print can be obtained. A method of preparing an inkjet ink using the dye polymer aqueous dispersion manufactured by the method iv) or (v) and using these methods is preferable.
As the organic solvent in the methods (iv) and (v), ethyl acetate, methyl ethyl ketone, tetrahydrofuran and the like are preferable.

<Inkjet ink for textile printing>
The inkjet ink for textile printing of the present invention contains at least an aqueous dispersion of a dye polymer. That is, the inkjet ink for textile printing of the present invention is a dispersion liquid in which a dye polymer is dispersed in a liquid containing water. The dye polymer is in the form of particles in the inkjet ink for textile printing, and the preferred average particle diameter of the particulate dye polymer is the same as that described above.

(Crosslinking agent)
For the purpose of improving the friction resistance or the fastness to washing of the colored fabric, the inkjet ink for printing may contain a crosslinking agent. Examples of the crosslinking agent include blocked isocyanate crosslinking agents (for example, Meikanate CX, TP-10, DM-35HC, SU-268A, etc., all manufactured by Meisei Kogyo Co., Ltd., trade names) and polyfunctional epoxy crosslinking agents (for example, , Denacor EX-313, 314, 322, 411, etc., all manufactured by Nagase ChemteX Corporation, trade names).

(Other ingredients)
The inkjet ink for textile printing of the present invention may contain other components other than those described above. Other components include, for example, colorants other than the above dye polymers, organic solvents, surfactants, pH adjusters, fluorescent brighteners, surface tension adjusters, antifoaming agents, anti-drying agents, lubricants, and thickeners. Agents, ultraviolet absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, resistivity regulators, rust inhibitors, inorganic pigments, anti-reducing agents, antiseptics, antifungal agents, chelating agents, etc. It is done.

The content of the dye polymer in the inkjet ink for textile printing is preferably 0.1 to 20% by mass, and more preferably 1 to 15% by mass.
The water content in the inkjet ink for textile printing is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and still more preferably 50 to 80% by mass.

  The method for preparing the inkjet ink for textile printing is not particularly limited. For example, it can be prepared by mixing an aqueous dispersion of a dye polymer with water or other components as necessary.

[Inkjet printing method]
The ink jet textile printing method of the present invention is an ink jet textile printing method having a step of printing on a fabric by an ink jet method using the ink jet ink of the present invention, and there are the following two preferred embodiments.
1st aspect: The inkjet printing method which has the process of printing directly on a fabric by the inkjet system using the inkjet ink of this invention.
Second aspect: Applying an aqueous pretreatment liquid containing a flocculant to a fabric to obtain a pretreated fabric, and marking the fabric pretreated by the inkjet method using the inkjet ink of the present invention. An inkjet printing method having a printing process.
In the present invention, “direct printing” on a fabric by an ink jet method does not require a transfer step, and does not require a step of printing ink jet ink directly on a fabric and a step of applying printing paste. Both ink jet inks are printed directly on the fabric.
The ink jet textile printing method of the present invention produces an effect of being excellent in the quality (texture), image sharpness and fastness to wet friction of a colored cloth with simple workability without producing waste materials such as waste water and transfer paper.

(Pretreatment process)
The pretreatment step in the second aspect is a step of obtaining a pretreated fabric by applying an aqueous pretreatment liquid containing a flocculant to the fabric. The method for applying the aqueous pretreatment liquid to the fabric is not particularly limited, and examples thereof include a coating method, a padding method, an ink jet method, a spray method, and a screen printing method.
The flocculant contained in the aqueous pretreatment liquid is not particularly limited as long as it has an action of aggregating the dye polymer, but is at least one selected from organic acids, polyvalent metal salts, and cationic compounds. It is preferable.

  The ink-jet printing method of the present invention is further integrated with the fiber by fusing the dye polymer to the fiber of the fabric by adding a heating step, and further improving the friction resistance without impairing the texture. There is an advantage that it can be granted.

(Heat treatment process)
The ink jet textile printing method of the present invention preferably further includes a heat treatment step. In particular, by performing a heat treatment step after printing on the fabric, the dye polymer particles can be melted (or softened) and the adhesion to the fibers can be improved (that is, heat-treated for melt dyeing). Is possible). The colored fabric is preferably dried and then subjected to heat treatment for the purpose of melting and dyeing, usually at 100 to 250 ° C., more preferably 100 to 200 ° C., particularly preferably 120 to 200 ° C. The heat treatment time is preferably 30 seconds to 3 minutes. In addition, when a reactive group (for example, a blocked isocyanate group) is introduced into the dye polymer, or when a crosslinking agent (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent) is used as an additive, From the viewpoint of friction resistance, it is possible to cause a crosslinking reaction using a reactive group introduced into the polymer (for example, a blocked isocyanate group) or a crosslinking agent used in combination as an additive (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent). preferable.
Since it is preferable to perform the heat treatment step at the above temperature, the dye polymer is preferably melted at 200 ° C. or lower, more preferably 180 ° C. or lower.
Whether the dye polymer melts at a specific temperature can be confirmed by raising the temperature of the dye polymer to a specific temperature at 10 ° C./min with a melting point measuring instrument and visually checking the state of the dye polymer.

(Post-processing)
The fabric colored by the inkjet printing method of the present invention (colored fabric) is excellent in the flexibility and fastness (friction resistance) of the texture, but if necessary, the entire surface is padded with a post-treatment agent. Thus, it is possible to obtain a colored fabric with improved texture flexibility and fastness (particularly friction resistance).

(Fabric)
Examples of fabrics to which the inkjet printing method of the present invention can be applied include the following. Fabrics (fiber types) include synthetic fibers such as nylon, polyester and acrylonitrile, semi-synthetic fibers such as acetate and rayon, natural fibers such as cotton, silk and wool, and mixed fibers, woven fabrics, knitted fabrics, non-woven fabrics, etc. Is mentioned.
As the fabric, a pretreated fabric can also be used. The pretreatment liquid can be applied by a coating method, a padding method, an ink jet method, a spray method, a screen printing method, or the like. The pretreatment liquid contains an aggregating agent that aggregates the dye polymer, and is preferably an aqueous solution. Examples of the flocculant include organic acids, polyvalent metal salts, and cationic compounds.
Apparel includes T-shirts, trainers, jerseys, pants, sweatsuits, dresses, blouses and the like. It is also suitable for bedding, handkerchiefs, cushion covers, curtains and the like.

[Ink cartridge and inkjet printer]
The present invention also relates to an ink cartridge having the inkjet ink of the present invention and an inkjet printer having the inkjet ink of the present invention.

[Method for producing colored fabric]
The present invention relates to a method for producing a colored fabric comprising a step of directly printing an ink-jet ink containing an aqueous dispersion of a polymer having a structure derived from a dye and an organic amine salt of a carboxyl group on a fabric by an inkjet method, and a heat treatment step. Also related. The inkjet ink and each step in the method for producing a colored cloth are as described above.

  Hereinafter, the present invention will be described in more detail based on examples. However, the scope of the present invention is not limited to the examples shown below.

(Synthesis of dye monomer YM-1)
The dye monomer YM-1 was synthesized according to the following scheme.

  In a three-necked flask, 333 g of Q-1 and 1 L of nitrobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 20 ° C. Further, 130 mL of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was washed with 300 mL of nitrobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 90 ° C. for 10 hours. The mixture was cooled to 20 ° C., and further 1.3 L of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred, and the precipitate was collected by filtration to obtain Q-2. Q-2 was used as it was in the next step. In a three-necked flask, 141 g of iminodiacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 420 mL of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), 1.8 L of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) are placed under ice cooling. Stir with. Further, Q-2 was added thereto, stirred for 30 minutes after the addition, and further stirred at 20 ° C. for 30 minutes. After stirring, 1.8 L of water was added, and the precipitate was collected by filtration to obtain Q-3. To a three-necked flask, 273 g of Q-3, 1.3 L of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) and 52 g of tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and maintained at 110 ° C. . Further, 283 mL of 2-ethylhexyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 110 ° C. for 5 hours. After cooling this mixture to 20 ° C., 3.6 L of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added, 1160 mL of 0.1 mol / L sodium hydroxide aqueous solution was added, and the organic phase was separated. The organic phase was washed with 1450 mL of 0.05 mol / L aqueous hydrochloric acid, the organic phase was separated and dehydrated with magnesium sulfate, and then the solvent was removed with an evaporator to obtain 350 g of YM-1.

(Preparation of prepolymer 1 in ethyl acetate solution)
In a three-necked flask, 38.9 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 95.7 parts by mass of YM-1, 135 parts by mass of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.), Neostan U 0.4 part by mass of −600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) was added and stirred at 75 ° C. for 4 hours. Ethyl acetate was added so that the final solid content concentration was 50% by mass, and an ethyl acetate solution of Prepolymer 1 was obtained. The prepolymer 1 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the terminal.

(Preparation of prepolymer 2 in ethyl acetate)
In a three-necked flask, 38.0 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.7 parts by mass of dimethylolbutanoic acid (manufactured by Wako Pure Chemical Industries, Ltd.), polycaprolactone diol (manufactured by Aldrich, average molecular weight) 530) 24.0 parts by mass, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 75 parts by mass, Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) 0.2 parts by mass, 75 ° C. For 4 hours. Ethyl acetate was added so that the final solid content concentration was 50% by mass, and the mixture was filtered to obtain a prepolymer 2 ethyl acetate solution. The prepolymer 2 is a polyurethane having a carboxyl group and a urethane bond and having an isocyanate group at the terminal.

(Preparation of aqueous dye polymer dispersion (ULx-1))
In a container, 15.8 parts by mass of the ethyl acetate solution of prepolymer 1 obtained above, 2.9 parts by mass of the ethyl acetate solution of prepolymer 2 obtained above, ethyl acetate (Wako Pure Chemical Industries, Ltd.) 12.5 parts by mass, and 0.3 parts by mass of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) as a neutralizing agent. Furthermore, a mixed solution of 35.6 parts by mass of pure water and 11.7 parts by mass of a 4% by mass aqueous sodium dodecyl sulfate solution was added, stirred for 12 minutes at 16000 rpm, and emulsified to obtain an emulsion. Thereafter, the emulsion was removed under reduced pressure to remove ethyl acetate. 2.8 parts by mass of a 10% by mass aqueous solution of UCAT SA102 (trade name, manufactured by San Apro Co., Ltd.) was added, water was added so that the solid content concentration was 18% by mass, and the mixture was held at 50 ° C. for 2 days. Thereafter, coarse particles were removed by filtration to obtain 45 parts by mass of a dye polymer aqueous dispersion (ULx-1). The final solid content concentration of the dye polymer aqueous dispersion (ULx-1) was 18.1% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-1) was polyurethane / urea having a triethylamine salt of a carboxyl group, and the average particle size thereof was 142 nm.

[Preparation of aqueous dye polymer dispersion (ULx-2)]
A dye polymer aqueous dispersion (ULx-2) was obtained in the same manner as the dye polymer aqueous dispersion (ULx-1) except that the neutralizing agent was changed to tributylamine. The final solid content concentration of the dye polymer aqueous dispersion (ULx-2) was 18% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-2) was polyurethane / urea having a tributylamine salt of a carboxyl group, and the average particle size thereof was 175 nm.

(Preparation of prepolymer 3 in tetrahydrofuran)
In a three-necked flask, 4.5 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.3 parts by mass of Disperse Brown 4, 25.3 parts by mass of tetrahydrofuran (THF), Neostan U-600 (Nitto Kasei) 0.03 part by mass of Kogyo Co., Ltd., trade name) was added and stirred at 65 ° C. for 4 hours. THF was added so that the final solid content concentration was 30% by mass, and a THF solution of prepolymer 3 was obtained. The prepolymer 3 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the terminal.

(Preparation of aqueous dye polymer dispersion (ULx-3))
In a container, 17.6 parts by mass of the THF solution of prepolymer 3 obtained above, 2.9 parts by mass of the ethyl acetate solution of prepolymer 2 obtained above, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) ) 10.4 parts by mass, 0.8 parts by mass of tetrahydrofuran (THF), and 0.3 parts by mass of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) as a neutralizing agent were added. Furthermore, a mixed liquid of 35.6 parts by mass of pure water and 11.7 parts by mass of a 4% by mass sodium dodecyl sulfate aqueous solution was added, and thereafter the dye polymer aqueous dispersion was treated in the same manner as the dye polymer aqueous dispersion (ULx-1). (ULx-3) was obtained. The final solid content concentration of the dye polymer aqueous dispersion (ULx-3) was 18.3% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-3) was polyurethane / urea having a triethylamine salt of a carboxyl group, and the average particle size thereof was 135 nm.

(Preparation of Prepolymer 4 in THF)
A THF solution of prepolymer 4 was obtained in the same manner as the THF solution of prepolymer 3, except that Disperse Brown 4 was replaced with the following phthalocyanine dye D-3. The following phthalocyanine dyes were synthesized according to JP 2013-535558 A. From elemental analysis, it was m + n = 2 and p + q = 2. The prepolymer 4 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the terminal.

(Preparation of aqueous dye polymer dispersion (ULx-4))
A dye polymer aqueous dispersion (ULx-4) was obtained in the same manner as the dye polymer aqueous dispersion (ULx-3) except that the THF solution of prepolymer 3 was replaced with the THF solution of prepolymer 4. The final solid content concentration of the dye polymer aqueous dispersion (ULx-4) was 18% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-4) was polyurethane / urea having a triethylamine salt of a carboxyl group, and the average particle size thereof was 160 nm.

(Synthesis of dye monomer YM-2)
The dye monomer YM-2 was synthesized according to the following scheme.

In a three-necked flask, 66.7 g of Q-1 and 400 mL of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) and 8.4 g of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed at 110 ° C. Stir. Further, 46 mL of 2-ethylhexyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 110 ° C. for 2.5 hours. Further, 4 L of water was added thereto, and the precipitate was filtered. The precipitate was reslurried with 400 mL of acetonitrile, filtered and dried to obtain Q-4.
In a three-necked flask, 100 g of Q-4 and 1 L of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved, and then kept at 0 ° C. Further, 133 g of 2-methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester HO-MS) is added, and further 110 g of tosyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) is added. -After adding 94.9 g of methylimidazole (Tokyo Chemical Industry Co., Ltd.), it stirred at 25 degreeC for 1 hour. The obtained mixture was separated with ethyl acetate / saturated aqueous sodium chloride solution, and the organic phase was washed with sodium hydrogen carbonate, washed with pure water, and dehydrated with magnesium sulfate. 0.234 g of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the organic phase after washing and dehydration, and the solvent was removed by an evaporator to obtain 113 g of YM-2.

(Preparation of aqueous dye polymer dispersion (ALx-1))
15.0 parts by mass of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a three-necked flask, stirred under nitrogen, and maintained at 65 ° C. Thereto, 4 parts by mass of YM-2, 1.0 part by mass of mono (2-acryloyloxyethyl) succinate (manufactured by Tokyo Chemical Industry Co., Ltd.), n-butyl acrylate (Wako Pure Chemical Industries, Ltd.) 4 parts by mass, 22.5 parts by mass of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.), and 0.3 parts by mass of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) The solution was added dropwise over 2 hours, followed by further stirring for 2 hours. Furthermore, after adding 0.03 mass part of V-65 (made by Wako Pure Chemical Industries Ltd.) and stirring for 2 hours, V-65 (made by Wako Pure Chemical Industries, Ltd.) 0.03 mass further. A polymer solution was obtained by stirring at 75 ° C. for 2 hours. 12 parts by mass of polymer solution, 6.0 parts by mass of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.), 0.6 parts by mass of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) as a neutralizing agent, 29.9 parts by mass of pure water The parts were mixed, stirred at 14000 rpm for 12 minutes and emulsified to obtain an emulsion. The organic solvent was removed from the emulsion under reduced pressure at 50 ° C., and coarse particles were removed by filtration to obtain a dye polymer aqueous dispersion (ALx-1). The dye polymer contained in the dye polymer aqueous dispersion (ALx-1) was an acrylic polymer having a triethylamine salt of a carboxyl group, and the average particle size was 57 nm. The final solid content concentration of the dye polymer aqueous dispersion (ALx-1) was 13% by mass.

(Preparation of aqueous dye polymer dispersion (RLx-1))
In the preparation of the dye polymer aqueous dispersion (ULx-1), the dye polymer aqueous dispersion (ULx-) was used except that triethylamine as a neutralizing agent was changed to a 10% by mass sodium hydroxide aqueous solution containing equimolar sodium hydroxide. A dye polymer aqueous dispersion (RLx-1) was prepared in the same manner as in 1). The dye polymer contained in the dye polymer aqueous dispersion (RLx-1) was a polyurethane / urea having a sodium salt of a carboxyl group, and the average particle size was 188 nm.

Example 1
[Preparation of inkjet ink (A1) for textile printing]
The following components were mixed at room temperature (20 ° C.), stirred for 15 minutes, and then filtered through a membrane filter (average pore size 0.8 μm) to prepare a printing inkjet ink (A1).
Dye polymer aqueous dispersion (ULx-1) 3.0g
Trimethylolpropane 0.056g
0.913g of ultrapure water
1,12-hexanediol 0.112g
Glycerin 0.560g
Triethylene glycol monobutyl ether 0.112 g
2-pyrrolidone 0.168g
Propylene glycol 0.028g
Surfynol 465 (trade name, manufactured by Nissin Chemical Industry) 0.056g

[Inkjet printing method]
Ink-jet ink (A1) for textile printing is loaded into an ink cartridge, and polyester fabric (polyester tropical (manufactured by Teijin Limited), Color Co., Ltd.) using an ink-jet printer (Calario PX-045A, product name) manufactured by Seiko Epson Corporation. Manufactured by Dyeing Co., Ltd., product code A02-01019), cotton fabric (with cotton broad sill, manufactured by Color Dyeing Co., Ltd., product code A02-01002), and polyester 65% cotton 35% blend (blended polyester 65 / cotton 35 broad, Each image was printed on a product code A02-01030) manufactured by Color Dye Co., Ltd. and dried at room temperature for 12 hours. After drying, heat treatment is performed using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type) at a temperature of 200 ° C., a pressure of 0.20 N / cm ² , and a time of 60 seconds. As a result, a clear image without blurring was obtained.

(Examples 2 to 5)
Except for changing the dye polymer aqueous dispersion (ULx-1) to dye polymer aqueous dispersions (ULx-2) to (ULx-4) and (ALx-1), respectively, the same as the inkjet ink (A1) for textile printing Inkjet inks (A2) to (A5) for textile printing were prepared.
In Examples 2 to 5, inkjet printing was performed in the same manner as in Example 1 except that the printing inkjet ink used was changed to the inkjet printing inks (A2) to (A5), respectively.

(Comparative Example 1) Sublimation transfer printing After printing an image on transfer paper using a sublimation transfer printing printer SureColor F6000 (trade name, manufactured by Seiko Epson Corporation), polyester fabric (polyester tropical (made by Teijin Limited), stock Company Color Dyeing Co., Ltd., product code A02-01019), cotton fabric (with cotton broad sill, product made by Color Dyeing Co., Ltd., product code A02-01002), and 65% polyester 35% cotton blend (blend polyester 65 / cotton 35) Each of the images was printed on Broad, manufactured by Color Dyeing Co., Ltd., product code A02-01030), and dried at room temperature for 12 hours. After drying, heat treatment is performed using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type) at a temperature of 200 ° C., a pressure of 0.20 N / cm ² , and a time of 60 seconds. Thus, a transferred image was obtained. A clear image was obtained for the polyester fabric, but a 35% polyester 65% cotton blend produced a clear but low dyeing density image, and a cotton fabric gave a very blurred image. It was.

(Comparative Example 2) Coloring by inkjet method using pigment (Preparation of pigment dispersion)
3 g of a styrene-acrylic acid copolymer (Johncrill 678, manufactured by BASF, trade name), 1.3 g of dimethylaminoethanol, and 80.7 g of ion-exchanged water were stirred and mixed at 70 ° C. Next, C.I. I. Pigment Blue 15: 3 (15 g, zirconia beads having a particle size of 0.5 mm) was filled in 50% by volume and dispersed using a sand grinder mill to obtain a pigment dispersion having a cyan pigment content of 15% by mass. .

(Preparation of aqueous binder)
50 g of 2-butanone was placed in a three-necked flask and the internal temperature was heated to 75 ° C., and a mixture of 80 g of n-butyl methacrylate, 20 g of acrylic acid, 50 g of 2-butanone and 0.5 g of azoisobutyronitrile was added for 3 hours. It was dripped over. After dropping, the mixture was heated to reflux for 5 hours, cooled to room temperature, and heated under reduced pressure to obtain a polymer residue. To this, 350 mL of ion-exchanged water and 1.05 times moles of sodium hydroxide of acrylic acid added as a monomer were added and dissolved. It diluted with ion-exchange water so that the whole quantity might be 500g, and obtained 20 mass% aqueous solution of the aqueous | water-based binder.

(Preparation of pigment ink and coloring by inkjet method)
46.6 g of the pigment dispersion, 15 g of a 20% by weight aqueous solution of the aqueous binder, 2.9 g of PDX-7664A (trade name, manufactured by BASF), 10 g of triethylene glycol monobutyl ether, 5 g of 1,2-hexanediol, diethylene glycol 11 .2g, Olfin 465 (manufactured by Nissin Chemical Industry Co., Ltd., 0.6g) is mixed, and ion-exchanged water is added thereto to prepare a total amount of 100g, followed by filtration with a 0.8µm filter for comparison pigment Ink was obtained.
The obtained pigment ink is loaded into an ink cartridge, and a polyester fabric (polyester tropical (manufactured by Teijin Ltd.), Color Dyeing Co., Ltd.) is used with an ink jet printer (Calario PX-045A, product name manufactured by Seiko Epson Corporation). Product code A02-01019), cotton fabric (with cotton broad sill, color dye, product code A02-01002), and 65% polyester 35% cotton blend (blend polyester 65 / cotton 35 broad, Co., Ltd.) An image was printed on each of product codes A02-01030) manufactured by Color Dyeing Co., Ltd. and dried at room temperature for 12 hours. After drying, heat treatment is performed using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type) at a temperature of 100 ° C., a pressure of 0.20 N / cm ² , and a time of 60 seconds. Thus, a colored cloth printed with the pigment ink was obtained.

(Comparative Example 3)
A printing inkjet ink (R1) was prepared in the same manner as the printing inkjet ink (A1) except that the dye polymer aqueous dispersion (ULx-1) was changed to the dye polymer aqueous dispersion (RLx-1).
In Comparative Example 3, inkjet printing was performed in the same manner as in Example 1 except that the printing inkjet ink used was changed from the printing inkjet ink (A1) to the printing inkjet ink (R1).

The evaluation results of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1. The evaluation of the colored fabric is the result of the following method. Of the three types of fabrics, cotton fabric was used for evaluation of texture, fastness to wet friction, and washing resistance. The fastness to wet friction and the washing resistance were evaluated according to “JIS Handbook 31 Fiber” edited by Japanese Standards Association, published in 2015.
-Image clarity: The sensory evaluation was performed visually. The three types of fabrics were evaluated in four stages: A for the case of clearness, B for the case of clearness with two types, C for the case of only one type, and D for no clear image.
-Texture: The untreated cloth before dyeing and the colored cloth after dyeing were touched by hand, and the texture of the colored cloth was subjected to sensory evaluation. 10 points were assigned to the fabrics with the texture of the colored fabric that was close to that of the untreated fabrics, and 0 points were assigned to the other. The total score was shown in Table 1 below. A larger numerical value indicates an excellent texture close to the untreated cloth (100 (points)).
-Wet friction fastness: JIS (Japanese Industrial Standard) L-0849 It evaluated based on the Gakushin type | mold friction test.
The evaluation result of wet friction fastness shows that the larger the value, the better the fastness.
Washing resistance: Evaluated based on JIS L-0844 A-2.
The evaluation result of washing resistance indicates that the larger the value, the better the washing resistance.

  As is clear from the above results, the examples of the present invention can form clear images (excellent image clarity) on various types of fabrics, and have good texture, fastness to wet friction, and washing resistance. It can be seen that a colored fabric having properties is provided.

Claims (9)

  A step of directly printing an ink-jet ink having a structure derived from a dye and a carboxyl group, and an aqueous dispersion of a polymer in which the carboxyl group forms a salt with an organic amine, on a fabric by an inkjet method; and a heat treatment step. An ink-jet printing method comprising:   The inkjet printing method according to claim 1, wherein the boiling point of the organic amine is 250 ° C. or less.   The inkjet printing method according to claim 1, wherein the organic amine is a tertiary amine. The inkjet printing method according to any one of claims 1 to 3, wherein the organic amine is a compound represented by any one of the following general formulas (N-1) to (N-3).

In General Formula (N-1), R _{N1 to} R _N3 each independently represents an organic group. Two or more selected from R _{N1 to} R _N3 may be bonded to each other to form a ring.
In general formula (N-2), R _{N4 to} R _N7 each independently represents an organic group. Two or more selected from R _{N4 to} R _N7 may be bonded to each other to form a ring. L _N1 represents a linking group.
In General Formula (N-3), R _{N8 to} R _N12 each independently represents an organic group. Two or more selected from R _{N8 to} R _N12 may be bonded to each other to form a ring. L _N2 and L _N3 each independently represent a linking group.   The dye is an azo dye, stilbene dye, diarylmethane dye, triarylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye, azomethine dye, indoaniline dye, indophenol dye, nigrosine dye, oxazine dye, thiazine dye The inkjet printing method according to any one of claims 1 to 4, which is at least one dye selected from the group consisting of an anthraquinone dye, an indigo dye, a quinophthalone dye, a porphyrin dye, a cyanine dye and a phthalocyanine dye.   The inkjet printing method according to claim 1, wherein the polymer is an acrylic polymer or a urethane polymer.   The inkjet printing method according to any one of claims 1 to 6, wherein an average particle diameter of the polymer in the aqueous dispersion is 50 to 500 nm.   An inkjet ink for textile printing comprising an aqueous dispersion of a polymer having a structure derived from a dye and a carboxyl group, wherein the carboxyl group forms a salt with an organic amine. A step of directly printing an ink-jet ink having a structure derived from a dye and a carboxyl group, and an aqueous dispersion of a polymer in which the carboxyl group forms a salt with an organic amine, on a fabric by an inkjet method; and a heat treatment step. The manufacturing method of the colored cloth containing this.