WO2019013265A1 - Inkjet ink, inkjet printing method, and colored fabric - Google Patents

Abstract

The present invention provides: an inkjet ink containing an aqueous dispersion of a polymer having a dye-derived structure and a crosslinked structure, an inkjet printing method comprising a step for directly printing on a fabric by an inkjet system using the inkjet ink; and a colored fabric containing a fabric and a polymer that has a dye-derived structure and has a crosslinked structure.

Description

Ink jet ink, ink jet printing method, and colored cloth

The present invention relates to an inkjet ink, an inkjet printing method, and a colored cloth.

An inkjet ink is an ink applicable to the inkjet method, and is widely used in various applications.
Ink-jet textile printing does not have to make a plate, can quickly form an image with excellent gradation, and uses only the amount of ink necessary for forming an image, so it has environmental advantages such as little waste liquid. It can be said that it is an excellent textile printing method.

Patent Document 1 describes sublimation transfer printing using an ink containing resin particles containing a disperse dye.
Patent Document 2 describes an ink jet printing method using an ink jet ink containing a pigment. In this method, a pigment and a surfactant as a dispersant are mixed in water, and then finely dispersed together with glass beads, zirconia beads, titania beads, or stainless steel balls by an attritor or milling machine, etc. It is done. Then, the colorant is diluted by a reducer blended with an emulsion resin for pigment fixation to prepare a pigment ink, and the pigment ink is adhered to a fiber by an ink jet system, and the pigment is adhered by fusing a resin by a heating roller. .

Patent Document 3 describes an inkjet ink containing a polymer having a specific structure in which a specific dye is linked to a polymer backbone. Patent Documents 4 and 5 describe an ink containing an aqueous dispersion of polyurethane to which a colorant is bound.

Japanese Patent Application Laid-Open No. 10-58638 Japanese Patent Laid-Open Publication No. 2010-37700 Japanese Patent Publication No. 2004-534106 Japanese Patent Publication No. 2002-509957 Japanese Patent Publication No. 2004-534143

However, the sublimation transfer printing described in Patent Document 1 can not form a clear image on fabrics other than polyester fabrics. That is, a property capable of forming a clear image (also referred to as "image clearness") is required for various types of fabrics. Moreover, the inkjet textile printing by the inkjet ink containing the pigment described in patent document 2 can not be said that the feel of the colored cloth obtained is excellent, and the wet rub fastness is also inferior.
Patent Documents 3 to 5 have no specific disclosure on crosslinking and printing, and neither describes the problems of image clarity, texture and wet rub fastness.

An object of the present invention is to provide an inkjet ink capable of providing an image excellent in image sharpness, texture and wet rub fastness, an inkjet printing method using the above ink, and a colored cloth.

The inventors of the present invention have conducted intensive studies to solve the above problems, and an image clearness, feeling and wet friction are obtained by an inkjet ink containing an aqueous dispersion of a polymer having a structure derived from a dye and having a crosslinked structure. It has been found that it is possible to provide an image with excellent fastness.
In addition, image sharpness, texture and texture are obtained by a method including the step of printing directly on a fabric by an inkjet method using an inkjet ink containing an aqueous dispersion of a polymer having a structure derived from a dye and having a crosslinked structure. It was found that an image with excellent wet rub fastness was obtained.
Although the detail is unknown as a mechanism which can solve the above-mentioned subject by the above-mentioned method, the present inventors presume as follows.
The polymer having a structure derived from the dye contained in the inkjet ink is capable of coloring various types of fabrics. When the dye polymer contained in the ink-jet ink has a crosslinked structure, the strength of the film formed by fusing the dye polymer is improved, and a colored cloth having excellent durability can be obtained. From this, it is considered that an image having excellent image clarity and texture and excellent in wet rub fastness can be provided.
The object of the present invention was specifically achieved by the following means.

[1]
An inkjet ink comprising an aqueous dispersion of a polymer having a structure derived from a dye and having a crosslinked structure.
[2]
The 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) as a structure derived from the above dye, or a polymer represented by the following general formula (3 The inkjet ink according to [1], which is a polymer containing a structure represented by

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 any one hydrogen atom from the 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 combined.

In 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 Or 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 the 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 to each other.

In the 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 represented by the following formula (L6-1) or (L6-2) D ¹ represents a linking group, and D ¹ represents a dye residue obtained by removing one hydrogen atom from the dye.

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

[3]
^{D 1} of the above general formula (1), the general formula (2) Medium ^{D 2,} or ^{D 1} of the above general formula (3) is selected from the group of the following formula (M1) ~ (M8) The inkjet ink according to [2], which represents a dye residue obtained by removing one or two arbitrary hydrogen atoms from the dye represented by at least one.

In formula (M1), R ¹⁰¹ to R ¹¹⁰ each independently represent a hydrogen atom or a substituent.
In 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 formula (M3), R ³⁰¹ to R ³¹⁷ each independently represent a hydrogen atom or a substituent, X ³⁰¹ represents a monovalent anion, and n ³⁰¹ represents 0 or 1.
In formula (M4), R ⁴⁰² to R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent, and Ar ⁴⁰¹ represents a phenyl group, a naphthyl group or a heterocyclic group, and the above phenyl group, the above naphthyl group or The above-mentioned heterocyclic group may further have a substituent.
In Formula (M5), R ⁵⁰¹ to R ⁵⁰⁸ each independently represent a hydrogen atom or a substituent.
In 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 formula (M7), R ⁷⁰¹ to R ⁷⁰⁶ each independently represent a hydrogen atom or a substituent.
In formula (M8), R ⁸¹¹ to R ⁸¹⁸ and R ⁸²¹ to R ⁸²⁸ each independently represent a hydrogen atom or a substituent.

[4]
The inkjet ink according to any one of [1] to [3], wherein the average particle size of the polymer is 50 to 500 nm.
[5]
The inkjet ink according to any one of [1] to [4], wherein the polymer is a urethane polymer.
[6]
The inkjet ink according to any one of [1] to [4], wherein the polymer is an acrylic polymer.
[7]
The inkjet ink according to any one of [1] to [6], which has a viscosity of 40 mPa · s or less at 25 ° C.

[8]
The inkjet ink according to any one of [1] to [7], which is for textile printing. [9]
An ink jet printing method comprising the step of printing directly on a fabric by an ink jet method using the ink jet ink according to any one of [1] to [8].
[10]
The inkjet textile printing method according to [9], further comprising a heat treatment step.
[11]
A colored cloth comprising a cloth and a polymer having a structure derived from a dye and having a crosslinked structure.

According to the present invention, it is an object of the present invention to provide an ink jet ink capable of providing an image excellent in image sharpness, texture and wet rub fastness, an ink jet printing method using the ink, and a colored cloth.

Hereinafter, the present invention will be described in detail.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
In the present specification, “(meth) acrylate” represents at least one of acrylate and methacrylate, “(meth) acrylic” represents at least one of acrylic and methacrylic, and “(meth) acryloyl” represents at least one of acryloyl and methacryloyl. Represents a kind.

In the present specification, the “substituent selected from Substituent Group A” refers to the substituents described in [0012] to [0051] of WO 2015/199135.
Further, in the present specification, the substituent group A1 includes the following substituents.

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

In the present invention, an ionic group such as a sulfo group or a carboxyl group may be in a state including a cation or an anion (also referred to as a “salt state”). For example, a carboxyl group, a phosphate group, and a sulfo group may be in a state including a cation, and examples of the cation forming a salt state include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion) Potassium ion) and organic cations (eg, tetramethyl ammonium ion, tetramethyl guanidinium ion, tetramethyl phosphonium).

<A polymer having a structure derived from a dye and having a crosslinked structure>
In a polymer having a structure derived from a dye and having a cross-linked structure (hereinafter also referred to as "dye polymer") used in the present invention, the structure derived from a dye means any organic compound used as a dye. It is a group (dye residue) formed by removing one or more hydrogen atoms, and 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 dye multimer containing a structure derived from a dye, and is a reticulated polymer.

The method for obtaining the dye polymer is optional, but the monomer containing the structure derived from the dye (also referred to as "dye monomer") is polymerized or copolymerized with other monomers to obtain the dye polymer. Alternatively, after preparing a polymer not having a structure derived from a dye in advance, there is a method of introducing a structure derived from a dye by a polymer reaction or the like to obtain a dye polymer. 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.

The structure derived from the dye may be any structure derived from the dye as classified by the color index (abbreviated as "CI"), or any substituent within the range that exerts the effect of the present invention on the structure. It is preferable that it is the structure which substituted, or the structure which remove | eliminated the arbitrary substituent in the range from which the effect of this invention is show | played from the structure.

Examples of dyes include azo dyes (monoazo dyes, disazo dyes, trisazo dyes, polyazo dyes), stilbene dyes, carotenoid dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine dyes (monomethine) Dyes, polymethine dyes), azomethine dyes, aniline dyes, indoaniline dyes, indamine dyes, indophenol dyes, indophenol dyes, azine dyes, oxazine dyes, thiazine dyes, anthraquinone dyes, indigo dyes, quinophthalone dyes, diglossin dyes, porphyrin dyes, dicyanostyryl dyes And dyes, cyanine dyes, and phthalocyanine dyes.

Preferably, from the viewpoint of colorability, the dye is an azo dye, stilbene dye, diarylmethane dye, triarylmethane dye, xanthene dye, acridine dye, quinoline dye, polymethine dye, monomethine dye, azomethine dye, indoaniline dye, indoline dye At least one dye selected from the group consisting of phenol dyes, nigrosine dyes, oxazine dyes, thiazine dyes, anthraquinone dyes, indigo dyes, quinophthalone dyes, porphyrin dyes, cyanine dyes and phthalocyanine dyes, more preferably azo dyes, Stilbene dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, indoaniline dyes, indophenol dyes, nigrosine dyes, anthraquinone dyes, quinophthalone dyes, and phthalocyani At least one dye selected from the group consisting of dyes, the dye represented by any one of the later-described general formulas (M1) ~ (M8) is particularly preferred.

The dye may be a dye that is soluble in water or a dye that is insoluble in water, but is a dye that is insoluble in water from the viewpoint of the water resistance and the wash 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. For example, a dye insoluble in water such as a disperse dye may be used, or a dye structure in which an ionic group is removed from a water-soluble dye may be used.

As the dye polymer, a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond, or a urethane polymer is preferably used.

As a polymer obtained by polymerizing the monomer which has an ethylenically unsaturated bond, an acrylic polymer, a vinyl polymer, or a styrene polymer is mentioned, for example.

The acrylic polymer in the present invention is a polymer having at least one repeating unit from the group consisting of repeating units derived from (meth) acrylic acid and repeating units derived from (meth) acrylic acid ester.
Further, the styrene polymer in the present invention refers to a polymer having a repeating unit derived from styrene.
The urethane polymer (also referred to as "polyurethane") in the present invention is a polymer having a urethane bond, and is formed by the polymerization reaction of a compound having two or more hydroxyl groups and a compound having two or more isocyanate groups. Ru.

As a dye polymer, an acrylic polymer or a urethane polymer is preferable.

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 a structure represented by the following general formula (1) and a structure represented by the following general formula (2), one or two of the structures represented by the following general formula (1) Polymers Containing Above, Polymers Containing One or Two or More Structures Represented by the Following General Formula (2), One or More Structures Contained by the Following General Formula (1), and the Following General Formula (2) Examples thereof include a polymer containing one or more of the structures represented, a polymer containing a structure represented by the following general formula (1) and at least one structure represented by the following general formula (2), and other structures.
As a polymer containing a structure represented by the following general formula (3), a polymer containing one or two or more types of a structure represented by the following general formula (3), a structure represented by the following general formula (3) Examples 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 any one hydrogen atom from the 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 combined.

In 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 Or 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 the 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 to each other.

In the 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 represented by the following formula (L6-1) or (L6-2) D ¹ represents a linking group, and D ¹ represents a dye residue obtained by removing one hydrogen atom from the dye.

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

[Structure Represented by General Formula (1)]
The structure represented by the general formula (1) will be described.
In the 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-, more preferably -O-.
Preferably, 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 exhibited. However, substituted or unsubstituted linear, branched or cyclic aliphatic hydrocarbon having 1 to 30 carbon atoms Group (which 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) , 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 linking The linking group formed is preferred. As a substituent in case these have a substituent, the substituent (The substituent selected preferably from said substituent group A1) chosen from said substituent group A is mentioned. Further, in the above linking group, further, -O-, -S-, -NR- (wherein R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), -C (= O) -, -SO-, -SO _2- and the like may be included.

In 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 each represent a position to be bonded to X ¹ and X ² in the general formula (1), and * 3 represents a position to be bonded to D ¹ in the general formula (1).

In 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 particularly limited as long as the effects of the present invention can be exhibited, but substituted or unsubstituted alkylene groups (linear May be branched or branched, and preferably has 1 to 30 carbon atoms), a substituted or unsubstituted cycloalkylene group (preferably having 3 to 30 carbon atoms), and substitution Or an unsubstituted arylene group (preferably having a carbon number of 6 to 30), a substituted or unsubstituted heterocyclic group (preferably having a carbon number of 2 to 30), -CH = CH-, -O-, -S-, -NR- (wherein 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 preferred . As a substituent in case these have a substituent, the substituent (The substituent selected preferably from said substituent group A1) chosen from said substituent group A is mentioned.

In general formula (1), L ² represents a divalent linking group. Examples of the divalent linking group represented by L ² include divalent linking groups 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 similar to that described in the description.

In general formula (1), D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from the dye. Although D ¹ is not limited as long as the effects of the present invention can be exhibited, it represents a dye residue obtained by removing one arbitrary hydrogen atom from the dye represented by any one of the following formulas (M1) to (M8) Is preferred. In addition, General formula (M2) and (M3) shall also contain each resonance structure.

In formula (M1), R ¹⁰¹ to R ¹¹⁰ each independently represent a hydrogen atom or a substituent.
In 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 formula (M3), R ³⁰¹ to R ³¹⁷ each independently represent a hydrogen atom or a substituent, X ³⁰¹ represents a monovalent anion, and n ³⁰¹ represents 0 or 1.
In formula (M4), R ⁴⁰² to R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent, and Ar ⁴⁰¹ represents a phenyl group, a naphthyl group or a heterocyclic group, and the above phenyl group, the above naphthyl group or The above-mentioned heterocyclic group may further have a substituent.
In Formula (M5), R ⁵⁰¹ to R ⁵⁰⁸ each independently represent a hydrogen atom or a substituent.
In 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 formula (M7), R ⁷⁰¹ to R ⁷⁰⁶ each independently represent a hydrogen atom or a substituent.
In formula (M8), R ⁸¹¹ to R ⁸¹⁸ and R ⁸²¹ to R ⁸²⁸ each independently represent a hydrogen atom or a substituent.
In addition, General formula (M2) and (M3) shall also contain each resonance structure.

R ¹⁰¹ to R ^{110 in} the general formula (M1), R ²⁰¹ to R ^{215 in} the general formula (M2), R ³⁰¹ to R ³¹⁷ in the general formula (M3), R ⁴⁰² to R in the general formula (M4) ⁴⁰⁷ , R ⁵⁰¹ to R ⁵⁰⁸ in the general formula (M5), R ⁶⁰¹ to R ⁶⁰³ in the general formula (M6), R ⁷⁰¹ to R ⁷⁰⁶ in the general formula (M7), and R in the 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 above-mentioned Substituent Group A (preferably, a substituent selected from the above Substituent Group A1).

R ¹⁰¹ to R ^{110 in} the general formula (M1), R ²⁰¹ to R ^{215 in} the general formula (M2), R ³⁰¹ to R ³¹⁷ in the general formula (M3), R ⁴⁰² to R in the general formula (M4) ^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 preferably bonded to each other 6-membered or 7-membered saturated ring or unsaturated ring may be formed. When the formed 5-, 6-, and 7-membered rings are further substitutable groups, they may further have a substituent, and the substituent is selected from Substituent Group A above. Included (preferably, a substituent selected from the above-mentioned Substituent Group A1).

The substituent when Ar ⁴⁰¹ in General Formula (M4) further has a substituent and the substituent when Ar ⁶⁰¹ in General Formula (M6) further has a substituent is selected from Substituent Group A above The substituent (preferably, a substituent selected from the above-mentioned substituent group A1) can be mentioned.

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

The dyes represented by the above general formulas (M1) to (M8) may be classified by color index and may be synthesized by a conventionally known method (for example, Japanese Patent Publication No. 7-49583, Patent Patent Publication No. 5715380, International Publication No. WO 2010/110199, Japanese Patent Publication No. 2002-509957, etc.).

Specific examples of the dyes represented by the above general formulas (M1) to (M8) are those described in [0126] to [0132] of PCT / JP 2017/002788, [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-A-2013-535558.

[Structure Represented by General 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 the preferred range is 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 the groups represented by general formulas (L-1) and (L-2) described above. Are the same as described in the description of the divalent linking group when L ¹¹ and L ^{12 in the above} each represent a divalent linking group.
L ³ and L ⁴ preferably represent a single bond.

In formula (2), D ² represents a dye residue obtained by removing two arbitrary hydrogen atoms from the dye. D ² is not limited as long as the effects of the present invention can be obtained, but a dye residue obtained by removing two arbitrary hydrogen atoms from the dye represented by any one of the general formulas (M1) to (M8) is It is further preferable to represent.
Also in D ² of the general formula (2), preferred ranges and specific examples of the general formulas (M1) to (M8) are the same as those described above.

When the dye polymer in the present invention is a polyurethane having a structure derived from a dye, typically, a compound having two or more hydroxyl groups such as diol or triol which is a monomer, and diisocyanate which is a monomer Etc. is synthesized by polymerization reaction with a compound (polyisocyanate compound) having two or more isocyanate groups such as, but as is also apparent from the structure represented by the above general formula (1) or (2), it is not limited thereto. Obtained by the polymerization reaction of a monomer having 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, and a monomer having two or more isocyanate groups. It can have a structure.
When the dye polymer in the present invention is a polyurethane, it has a structure derived from the dye and is a single substance having 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 is preferable to have a structure formed by polymerizing a monomer (dye monomer) and a monomer having two or more isocyanate groups.
The number of the groups selected from the group consisting of the hydroxyl group, the primary amino group and the secondary amino group is the number of those which can react with the 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)) comprises a total of 2 groups selected from the group consisting of a hydroxyl group, a primary amino group and a secondary amino group. When it has one or more, it can be used as a dye monomer.
Moreover, when the above-mentioned dye (preferably a dye represented by any of the general formulas (M1) to (M8)) does not have a hydroxyl group, a primary amino group or a secondary amino group, hydroxyl is used as the dye. A dye monomer can be obtained by introducing a group, a primary amino group or a secondary amino group by a chemical reaction.

[Structure Represented by General Formula (3)]
Next, the structure represented by the general formula (3) will be described.
The polymer containing 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 as a substituent when representing a substituent, a substituent selected from the above-mentioned Substituent Group A (preferably the above-mentioned Substituents selected from Substituent Group A1) can be mentioned. 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 a substituent selected from the above-mentioned Substituent group A (preferably selected from the above-mentioned Substituent group A1) as a substituent when representing a substituent Substituent)). R ⁴ preferably represents a hydrogen atom or a methyl group.
Each of L ^{7 in the} above formula (L 6-1) and L ⁸ in the above formula (L 6-2) independently represents a single bond or a divalent linking group, and in the case of 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) above represent a divalent linking group. It is.
It is preferable that L ⁶ in the general formula (3) represents a divalent linking group represented by the above formula (L6-1).
In the general formula (3), D ¹ represents a dye residue obtained by removing an arbitrary hydrogen atom from the dye. D ¹ is not limited as long as the effects of the present invention can be exhibited, but a dye residue obtained by removing one arbitrary hydrogen atom from the dye represented by any one of the general formulas (M1) to (M8) is It is further preferable to represent.
Also in D ¹ of the general formula (3), preferred ranges and specific examples of the general formulas (M1) to (M8) are the same as described above.

(Structure of dye polymer)
The dye polymer is a polymer having a structure derived from a dye and having a crosslinked structure.
In the case of a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond, the crosslinked structure refers to a compound having two or more ethylenically unsaturated bonds in the molecule as at least one monomer in the case of a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond. It represents a structure obtained by polymerization.
Moreover, in the case of a urethane polymer, a crosslinked structure represents the structure obtained by using the compound which has a hydroxyl group and an isocyanate group three or more in total in a molecule | numerator as at least one monomer.

Examples of compounds having two or more ethylenically unsaturated bonds in the molecule include divinylbenzene, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol (meth) acrylate Etc.

Examples of compounds having a total of three or more hydroxyl groups and isocyanate groups in the molecule include compounds having a total of three or more hydroxyl groups in the molecule or compounds having a total of three or more isocyanate groups in the molecule. .
Examples of the compounds having a total of three or more hydroxyl groups in the above molecule include glycerin, polyglycerin, trimethylolpropane, pentaerythritol and the like.
Examples of the compound having a total of three or more isocyanate groups in the molecule described above include polymeric MDI, duranate (manufactured by Asahi Kasei Corp., trade name), and the like.

As a compound which has a hydroxyl group and an isocyanate group in total 3 or more in a molecule | numerator, the compound which has 3 or more hydroxyl groups in a molecule | numerator is preferable.

The presence or absence of the crosslinked structure of the dye polymer can be judged by the solubility of the dye polymer. An aqueous dispersion containing the dye polymer of the present invention or an inkjet ink is mixed with various solvents such as dimethyl sulfoxide (DMSO), N-methyl pyrrolidone (NMP), tetrahydrofuran and the like, and in any case it has a crosslinked structure It can be judged to be a gel. If it can not be determined visually, it is filtered through a filter of the average particle size of the aqueous dispersion, or if the particle size can be observed by particle size measurement, it is judged to be a gel having a crosslinked structure. it can. Alternatively, it can be determined by measuring the gel fraction in accordance with JIS Standard 6769.

In the case of a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond, the dye polymer in the present invention has a structure derived from the dye and a compound having one or more ethylenically unsaturated bonds (dye It is preferable that it is a polymer obtained by polymerizing a monomer).
When the aforementioned dye (preferably a dye represented by any of the general formulas (M1) to (M8)) has an ethylenically unsaturated bond, it can be used as a dye monomer.
When the aforementioned dye (preferably a dye represented by any of the general formulas (M1) to (M8)) does not have an ethylenically unsaturated bond, the dye chemically reacts with the ethylenically unsaturated bond. The dye monomer can be obtained by introducing

(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.
Examples of 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, It is possible to use norbornene diisocyanate, lysine diisocyanate, an oligomer of the above diisocyanate, and a reaction product of 1 mole of diol and 2 moles of diisocyanate. These may be used alone or in combination of two or more.

A catalyst can be used in the reaction of the dye monomer and the polyisocyanate compound. As the catalyst, tin compounds, titanium compounds, bismuth compounds, zinc compounds, organic bases (tertiary amine compounds, or diazabicycloundecene (DBU) and the like) can be suitably used.

The dye polymer may have a structure other than the structure derived from the dye.
When the dye polymer is a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond, a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond as another monomer It may be.
When the dye polymer in the present invention is a polyurethane, it may be a polymer obtained by reacting the above-mentioned dye monomer and another monomer other than the polyisocyanate compound.
As another monomer, a diol is preferable. Further, diols having a carboxyl group are also preferred.

The dye polymer in the present invention may have a soft segment to improve the quality (feel) and the fastness of the colored cloth. The soft segment can be introduced into the dye polymer by copolymerizing the corresponding diol compound or diamine compound. These may be used alone or in combination of two or more.
Diol compounds which can be used for the introduction of the soft segment include polyethylene glycol diol, polypropylene glycol diol, polytetramethylene oxide, polyester diol, polycaprolactone diol, polycarbonate diol, polybutadiene diol, polyisoprene diol, hydrogenated polybutadiene diol, Hydrogenated polyisoprene diol and polydimethylsiloxane diol can be preferably used. The polyester diol is preferably a compound obtained by condensing a dibasic acid such as adipic acid or isophthalic acid with an alcohol such as ethylene glycol, diethylene glycol, 1,4-butanediol or 1,6-hexanediol. The polycaprolactone diol is preferably a compound obtained by ring-opening polymerization of caprolactone from ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol or the like.
As a diol compound that can be used for soft segment introduction, polyethylene glycol diol, polypropylene glycol diol, polytetramethylene oxide, polyester diol, polycaprolactone diol, and polycarbonate diol are more preferable.
The diamine compound that can be used for the introduction of the soft segment is preferably polyethylene glycol diamine or polypropylene glycol diamine.

When the dye polymer in the present invention is a polyurethane, it may further have a urea bond. A polymer having a urethane bond and a urea bond is also called "polyurethane / urea".
In a preferred embodiment of the dye polymer according to the present invention, a polyurethane / urea in which a structure derived from a dye and a first partial structure containing a urethane bond and a second partial structure containing a urethane bond are linked by a urea bond. It can be mentioned.

<Water dispersion of dye polymer>
The aqueous dispersion of dye polymer (dye polymer aqueous dispersion) contains at least water and dye polymer, and the dye polymer is dispersed in water. The dye polymer water dispersion may contain an aqueous organic solvent. Further, depending on the method for producing the aqueous dispersion of the dye polymer, the low molecular weight surfactant or the high molecular weight dispersant may be used in combination or may not be used in combination (so-called self-dispersion).
The dye polymer may be used alone or in combination of two or more at any ratio.

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

The dye polymer, when dispersed in water, is easy to be compatible with water (wettable) or electrostatic repulsion (repulsive force) as a property of the dye polymer itself or by adsorption with a low molecular type surfactant or a polymer type dispersant used in combination. Or steric repulsion to prevent reaggregation of the fine particles of the dye polymer, and has the function of suppressing sedimentation.

The dye polymer is in the form of particles in the aqueous dispersion. The average particle size 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 inkjet method.
The average particle diameter in this specification used the value measured using the particle size distribution measuring apparatus (Nanotrac UPA EX150, the Nikkiso Co., Ltd. make, brand name).

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. If it is in this range, it is possible to obtain a colored cloth with high density in printing while securing the 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. Within this range, the stability of the dye-polymer water dispersion and the ejection stability as an inkjet ink can be imparted, which is preferable. The stability of the dye-polymer water dispersion indicates that sedimentation and the like hardly occur.

(Aqueous organic solvent)
The aqueous organic solvent is preferably 10 g / 100 g-H ₂ O or more as water solubility at 25 ° C., more preferably 20 g / 100 g-H ₂ O or more, and 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. Within this range, the stability of the dye-polymer water dispersion and the ejection stability as an inkjet ink can be imparted, which is preferable.

(Low-molecular-weight surfactant or polymeric dispersant)
The low molecular weight surfactant or the high molecular weight dispersant is preferably a low molecular weight surfactant or a high molecular weight dispersant having a hydrophobic group and an ionic group, and is added when the dye polymer is dispersed. Low-molecular-weight surfactant or high-molecular-weight dispersant adsorbs to the surface of the dye polymer and makes it wet (is wet) with water, and electrostatic repulsion (repulsion) or steric repulsion of dye polymer fine particles milled by mechanical action It prevents the reaggregation of fine particles and has the function of suppressing the formation of sedimentation.

The content of the low molecular weight 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 is arbitrarily selected in this range It is preferable to adjust to

The content of the polymer-type dispersant is preferably in the range of 0.001 to 50% by mass with respect to the total mass of the dye polymer water dispersion, and the surface tension of the water dispersion is arbitrarily adjusted in such a range It is preferable to do.

(Method for producing aqueous dispersion of dye polymer)
The method for producing the aqueous dispersion of the dye polymer is not particularly limited, and examples thereof include the methods shown in (i) to (v) below.
(I) A method of mixing the powder or paste of the crosslinked dye polymer in water and then finely dispersing it with an attritor or mill together with glass beads, zirconia beads, titania beads or stainless steel balls, etc.
(Ii) A method of obtaining an aqueous dispersion of a dye polymer by polymerizing water, a dye monomer and, if necessary, another monomer to obtain a dye polymer,
(Iii) Synthesize a dye polymer in an organic solvent or synthesize it in an organic solvent, dissolve the dye polymer taken out in solid state in an organic solvent, add water and a neutralizing agent, and do not remove the organic solvent Or removing the organic solvent to obtain an aqueous dispersion of the dye polymer,
(Iv) The organic solvent, the dye monomer, and, if necessary, other monomers are polymerized to obtain an organic solvent solution of the dye polymer, and water and neutralization of the organic solvent solution of the dye polymer A method of obtaining an aqueous dispersion of a dye polymer by adding an agent and emulsifying it,
(V) An organic solvent solution of a first prepolymer having a structure derived from a dye and having an isocyanate group at the end, and an organic solvent solution of a second prepolymer having a dispersible structure and having an isocyanate group at the end A method of mixing with a solvent solution and further adding water for emulsification to obtain an aqueous dispersion of dye polymer.
When the dye polymer is a polymer obtained by polymerizing a compound having an ethylenically unsaturated bond, a compound having two or more ethylenically unsaturated bonds in at least one of the monomers is a method of introducing a crosslinked structure into the dye polymer In the case where the dye polymer is a polyurethane, it may be produced by using a trifunctional or higher functional polyisocyanate and / or a polyol and / or a polyamine for at least one of the monomers. Moreover, the method manufactured using the prepolymer of 3 or more functional groups in at least one of the prepolymer which has an isocyanate group at the terminal is mentioned. Moreover, after producing the water dispersion of the dye polymer which has a functional group (for example, a carboxyl group and an epoxy group) which can be post-reacted, the method of making the said functional group react and forming a crosslinked structure is mentioned.

The non-aqueous organic solvent is not an aqueous organic solvent among organic solvents, and preferably less than 10 g / 100 g-H ₂ O as water solubility at 25 ° C.
If necessary, 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 dispersion of these dye polymers as required. can do. In addition, nonionic surfactants or anionic surfactants can be added as dispersion aids, but these surfactants should be added in a small amount so as not to degrade the performance as dispersion stability. Is preferred.

The dye polymer water dispersion is used in the above-mentioned manner (a) because the amount of the precipitate is small, the dispersion stability is good, streaks and unevenness are less likely to occur when deposited by the ink jet method, and clear printed matter can be obtained. Preferred is a method of preparing an inkjet ink using the dye polymer water dispersion produced by the method iv) or (v) and produced by these methods.
Ethyl acetate, methyl ethyl ketone, tetrahydrofuran and the like are preferable as the organic solvent in the above methods (iv) and (v).

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

(Crosslinking agent)
The ink jet ink may contain a crosslinking agent in order to improve the abrasion resistance or the washing fastness of the colored cloth. Examples of the crosslinking agent include blocked isocyanate crosslinking agents (for example, Maycanate CX, TP-10, DM-35 HC, SU-268A, etc., all manufactured by Meisei Kogyo Co., Ltd., trade names) and polyfunctional epoxy crosslinking agents (for example, And Denacol EX-313, 314, 322, 411, etc., all of which are manufactured by Nagase ChemteX Co., Ltd. (trade names).

(Other ingredients)
The inkjet ink of the present invention may contain other components other than those described above. As other components, for example, colorants other than the above dye polymers, organic solvents, surfactants, pH adjusters, fluorescent brighteners, surface tension adjusters, antifoamers, anti-drying agents, lubricants, thickening agents Agents, UV absorbers, antifading agents, antistatic agents, matting agents, antioxidants, specific resistance regulators, rust inhibitors, inorganic pigments, reduction inhibitors, preservatives, fungicides, chelating agents, etc. Be

The content of the dye polymer in the inkjet ink is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 12% by mass.
The content of water in the inkjet ink is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and still more preferably 50 to 80% by mass.

(Viscosity of inkjet ink)
The viscosity at 25 ° C. of the inkjet ink of the present invention is preferably 40 mPa · s or less, more preferably 1 to 30 mPa · s, and more preferably 2 to 20 mPa · s.
When the viscosity at 25 ° C. of the inkjet ink is 40 mPa · s or less, the ink is excellent in the dischargeability.
The viscosity at 25 ° C. of the inkjet ink can be measured, for example, by a commercially available vibration viscometer.

Although the preparation method of an inkjet ink is not specifically limited, For example, it can prepare by mixing the water dispersion liquid of a dye polymer, and water or other components as needed.

The inkjet ink of the present invention is preferably for printing.

[Ink jet 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 embodiments as preferable embodiments.
First aspect: An ink jet printing method comprising the step of printing directly on a fabric by an ink jet method using the ink jet ink of the present invention.
Second aspect: A pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to a fabric to obtain a pretreatment fabric, and directly using the inkjet ink of the present invention on a fabric pretreatment with an inkjet method An ink jet printing method comprising the step of printing.
In the present invention, “directly printing on a fabric” by the inkjet method does not require a transfer step, and the inkjet ink can be printed directly on the fabric, and a step of applying a printing paste is unnecessary. It refers to both that the inkjet ink is directly printed on the fabric.
The ink jet textile printing method of the present invention does not produce waste materials such as waste water and transfer paper, and has an effect of being excellent in the quality (texture) of the colored cloth, the image sharpness and the wet rub fastness with simple workability.

(Pretreatment process)
The pretreatment step in the second aspect is a step of applying an aqueous pretreatment liquid containing a coagulant to the fabric to obtain a pretreated 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 inkjet method, a spray method, a screen printing method, and the like.
The aggregating agent contained in the aqueous pretreatment solution is not particularly limited as long as it has an effect of aggregating the dye polymer, and is at least one selected from organic acids, polyvalent metal salts, and cationic compounds. Is preferred.

In the ink jet printing method of the present invention, the dye polymer is further fused to the fibers of the fabric by adding the heating step, whereby the fibers are more integrated with the fibers and the texture is not impaired, and the abrasion resistance and the like are further reduced. It has the advantage of being able to be granted.

(Heat treatment process)
The ink jet printing method of the present invention preferably further includes a heat treatment step. In particular, after printing on the fabric, the dye polymer particles can be melted (or softened) by the heat treatment step to improve the adhesion with the fibers (that is, melt dyeing by heat treatment) Can) After drying, the colored cloth is preferably subjected to a heat treatment for the purpose of causing the above-mentioned melt dyeing to be performed, and usually it is preferably carried out at 100 to 250 ° C, more preferably 100 to 200 ° C, particularly preferably 120 to It is 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 together as an additive, The crosslinking reaction is carried out using a reactive group (for example, a blocked isocyanate group) introduced into the polymer, or a crosslinking agent (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent) used in combination as an additive preferable.
Since the heat treatment step is preferably performed at the above temperature, the dye polymer is preferably melted at 200 ° C. or less, more preferably 180 ° C. or less.
Whether the dye polymer melts at a specific temperature can be confirmed by heating the dye polymer at a temperature of 10 ° C./min to a specific temperature by a melting point meter and visually observing the state of the dye polymer.

(Post-processing)
The cloth (colored cloth) colored by the inkjet textile printing method of the present invention is excellent in the softness and fastness (abrasion resistance) of the texture, but if necessary, the colored cloth may be subjected to a padding treatment over the entire surface. Thus, it is possible to obtain a colored cloth with further improved texture softness and fastness (especially abrasion resistance).

(Fabric)
Examples of the fabric 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 hair, and mixed fibers thereof, woven fabrics, knitted fabrics, non-woven fabrics, etc. Can be mentioned.
A pretreated fabric can also be used as the fabric. The pretreatment liquid can be applied by a coating method, a padding method, an inkjet method, a spray method, a screen printing method or the like. The pretreatment liquid contains an aggregating agent for aggregating the dye polymer, and is preferably an aqueous solution. Examples of the aggregating agent include organic acids, polyvalent metal salts, and cationic compounds.
Clothing items include T-shirts, trainers, jerseys, pants, sweat suits, 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 comprising the inventive inkjet ink, and to an inkjet printer comprising the inventive inkjet ink.

[Colored cloth]
The present invention is a colored cloth comprising a fabric and a polymer having a structure derived from a dye and having a crosslinked structure (dye polymer).
The fabric and the dye polymer are as described above.
The colored cloth of the present invention can be obtained by printing a cloth by the above-mentioned ink jet printing method of the present invention.

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the scope of the present invention is not limitedly interpreted by the examples shown below.

(Synthesis of Dye Monomer YM-1)
YM-1 was synthesized by 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 the mixture was stirred at 20 ° C. Into a flask, 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., 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 is 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.) and 1.8 L of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) are added. Stir. Q-2 was added to the flask and stirred for 30 minutes after 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. 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 to a three-necked flask and maintained at 110 ° C. . 283 mL of 2-ethylhexyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 110 ° C. for 5 hours. After cooling to 20 ° C., 3.6 L of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added, 1160 mL of a 0.1 mol / L aqueous solution of sodium hydroxide was added, and the organic layer was separated. The organic layer was washed with 1450 mL of 0.05 mol / L aqueous hydrochloric acid, and the organic layer was separated and dried over magnesium sulfate, and then the solvent was removed by an evaporator to obtain 350 g of YM-1.

Preparation of Ethyl Acetate Solution of Prepolymer 1
In a three-necked flask, 6.9 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 17.0 parts by mass of YM-1, and 24.0 parts by mass of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) Then, 0.07 parts by mass of Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) was added and stirred at 75 ° C. for 4 hours. Ethyl acetate was added to a final solid concentration of 50% by mass to obtain an ethyl acetate solution of Prepolymer 1. Prepolymer 1 is a polyurethane having a structure derived from a dye and a urethane bond, and having an isocyanate group at the end.

(Preparation of ethyl acetate solution of prepolymer 2)
In a three-necked flask, 24.5 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.5 parts by mass of dimethylolbutanoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) (equivalent to an acid value of 15 mg KOH / g), poly 11.9 parts by mass of caprolactone diol (manufactured by Aldrich, average molecular weight 530), 1.0 parts by mass of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 105.0 ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) A mass part, 0.14 mass parts of Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) was added, and the mixture was stirred at 75 ° C. for 4 hours. Ethyl acetate was added to a final solid content concentration of 50% by mass, followed by filter filtration to obtain an ethyl acetate solution of Prepolymer 2. The prepolymer 2 is a polyurethane containing a carboxyl group and a urethane bond and having an isocyanate group at the end.

(Preparation of Dye-Polymer Water Dispersion (ULx-1))
In a container, 15.8 parts by mass of an ethyl acetate solution of prepolymer 1 obtained above, 4.9 parts by mass of an ethyl acetate solution of prepolymer 2 obtained above, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 10.6 parts by mass, 0.3 parts by mass of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) as a neutralizing agent were added. 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 solution of sodium dodecyl sulfate was added, and the mixture was stirred for 12 minutes at 16000 rpm and emulsified to obtain an emulsion. Thereafter, the obtained emulsion was distilled off under reduced pressure to remove the organic solvent. Thereafter, 2.8 parts by mass of a 10% by mass aqueous solution of UCAT SA102 (San Apro Co., Ltd., trade name) is added to the emulsion, and pure water is added so that the solid concentration becomes 18% by mass. Kept for 2 days. Thereafter, coarse particles were removed by filter filtration to obtain 42 parts by mass of a dye-polymer aqueous dispersion (ULx-1). The final solid content concentration of the dye-polymer water dispersion (ULx-1) was 18% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-1) is polyurethane / urea, and is a gel having a crosslinked structure because it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof Of 184 nm.

Preparation of Ethyl acetate Solution of Prepolymer 1-2
In a three-necked flask, 7.6 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.8 parts by mass of YM-1, 1.1 parts by mass of trimethylolpropane, ethyl acetate (Wako Pure Chemical Industries ( 16.5 parts by mass, and 0.05 parts by mass of Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) were added and stirred at 75 ° C. for 4 hours. Ethyl acetate was added to a final solid concentration of 50% by mass to obtain an ethyl acetate solution of Prepolymer 1-2. Prepolymer 1-2 is a polyurethane having a structure derived from a dye and a urethane bond, and having an isocyanate group at the end.

(Preparation of Dye-Polymer Water Dispersion (ULx-2))
In a container, 15.8 parts by mass of an ethyl acetate solution of prepolymer 1-2 obtained above, 4.9 parts by mass of an ethyl acetate solution of prepolymer 2 obtained above, ethyl acetate (Wako Pure Chemical Industries, Ltd. ) 10.3 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 solution of sodium dodecyl sulfate was added, and the mixture was stirred for 12 minutes at 16000 rpm and emulsified to obtain an emulsion. Thereafter, the obtained emulsion was distilled off under reduced pressure to remove the organic solvent. Thereafter, 2.8 parts by mass of a 10% by mass aqueous solution of UCAT SA102 (San Apro Co., Ltd., trade name) is added to the emulsion, and pure water is added so that the solid concentration becomes 18% by mass. Kept for 2 days. Thereafter, coarse particles were removed by filter filtration to obtain 42 parts by mass of a dye polymer water dispersion (ULx-2). The final solid concentration of the dye-polymer water dispersion (ULx-2) was 18% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-2) is polyurethane / urea, and is a gel having a crosslinked structure because it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof Was 155 nm.

(Preparation of a solution of prepolymer 3 in tetrahydrofuran (THF))
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 Co., Ltd.) 0.03 parts by mass of Kogyo Co., Ltd. (trade name) was added and stirred at 65 ° C. for 4 hours. THF was added to a final solid concentration of 30% by mass to obtain a THF solution of prepolymer 3. Prepolymer 3 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the end.

(Preparation of Dye-Polymer Water Dispersion (ULx-3))
In a container, 16.7 parts by mass of THF solution of prepolymer 3 obtained above, 2.5 parts by mass of 50% by mass ethyl acetate solution of Takenate D-116N, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 11 .3 parts by mass, 0.8 parts by mass of THF were added. 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 solution of sodium dodecyl sulfate was added, and the mixture was stirred for 12 minutes at 16000 rpm and emulsified to obtain an emulsion. Thereafter, the obtained emulsion was distilled off under reduced pressure to remove the organic solvent. Thereafter, 1.8 parts by mass of a 10% by mass aqueous solution of UCAT SA102 (manufactured by San-Apro Co., Ltd., trade name) is added to the emulsion, and pure water is added so that the solid content concentration is 15% by mass. Kept for 2 days. Thereafter, coarse particles were removed by filter filtration to obtain 42 parts by mass of a dye polymer water dispersion (ULx-3). The final solid concentration of the dye-polymer water dispersion (ULx-3) was 15% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-3) is polyurethane / urea and is a gel having a crosslinked structure since it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof Of 105 nm.

(Preparation of THF Solution of Prepolymer 4)
In a three-necked flask, 13.1 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.0 parts by mass of dimethylolbutanoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) (equivalent to an acid value of 64 mg KOH / g), poly 6.4 parts by mass of caprolactone diol (manufactured by Aldrich, average molecular weight 530), 0.5 parts by mass of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 56.0 parts of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 0.7 parts by mass of Neostan U-600 (trade name, manufactured by Nitto Kasei Kogyo Co., Ltd.) was added, and the mixture was stirred at 75 ° C. for 4 hours. Tetrahydrofuran was added to a final solid concentration of 30% by mass, followed by filter filtration to obtain a solution of prepolymer 4 in tetrahydrofuran. The prepolymer 4 is a polyurethane containing a carboxyl group and a urethane bond and having an isocyanate group at the end.

(Preparation of Dye-Polymer Water Dispersion (ULx-4))
In a container, 17.6 parts by mass of THF solution of prepolymer 3 obtained above, 3.2 parts by mass of 30 wt% prepolymer solution in THF, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 10.4 parts 0.23 parts by mass of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added. 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 solution of sodium dodecyl sulfate was added, and the mixture was stirred for 12 minutes at 16000 rpm and emulsified to obtain an emulsion. Thereafter, the obtained emulsion was distilled off under reduced pressure to remove the organic solvent. Thereafter, 1.8 parts by mass of a 10% by mass aqueous solution of UCAT SA102 (manufactured by San-Apro Co., Ltd., trade name) is added to the emulsion, and pure water is added so that the solid content concentration is 15% by mass. Kept for 2 days. Thereafter, coarse particles were removed by filter filtration to obtain 40 parts by mass of a dye-polymer aqueous dispersion (ULx-4). The final solid concentration of the dye-polymer water dispersion (ULx-4) was 15% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-4) is polyurethane / urea and is a gel having a crosslinked structure because it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof Of 109 nm.

(Preparation of THF Solution of Prepolymer 5)
A THF solution of prepolymer 5 was obtained in the same manner as the THF solution of prepolymer 3 except that disperse brown 4 (6.3 parts by mass) was replaced with the following azo dye D-2 (4.7 parts by mass). . The following azo dye D-2 was synthesized according to JP-A-2013-535558. The prepolymer 5 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the end.

(Preparation of Dye-Polymer Water Dispersion (ULx-5))
A dye polymer water dispersion (ULx-5) was obtained in the same manner as the dye polymer water dispersion (ULx-4) except that the THF solution of the prepolymer 3 was replaced with the THF solution of the prepolymer 5. The final solid concentration of the dye-polymer water dispersion (ULx-5) was 14% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-5) is polyurethane / urea and is a gel having a cross-linked structure because it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof Was 140 nm.

(Preparation of THF solution of Prepolymer 6)
A THF solution of prepolymer 6 was obtained in the same manner as the THF solution of prepolymer 3 except that disperse brown 4 (6.3 parts by mass) was replaced with the following phthalocyanine dye D-3 (13.6 parts by mass) . The following phthalocyanine dye D-3 was synthesized according to JP-A-2013-535558. According to elemental analysis, m + n = 2 and p + q = 2. Prepolymer 6 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the end.

(Preparation of Dye-Polymer Water Dispersion (ULx-6))
A dye polymer water dispersion (ULx-6) was obtained in the same manner as the dye polymer water dispersion (ULx-4) except that the THF solution of prepolymer 3 was replaced with the THF solution of prepolymer 6. The final solid content concentration of the dye polymer water dispersion (ULx-6) was 14% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-6) is polyurethane / urea and is a gel having a crosslinked structure since it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof Was 160 nm.

(Synthesis of Dye Monomer YM-2)
YM-2 was synthesized by the following scheme.

66.7 g of Q-1, 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.) were placed in a three-necked flask and stirred at 110 ° C. . 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. 4 L of water was added and the precipitate was filtered. The precipitate was reslurried with 400 mL of acetonitrile, collected by filtration, 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 placed, dissolved, and maintained at 0 ° C. 133 g of 2-methacryloyloxyethylsuccinic acid (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester HO-MS), 110 g of tosyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and N-methylimidazole After 94.9 g of Tokyo Chemical Industry Co., Ltd. was added, the mixture was stirred at 25 ° C. for 1 hour. After partitioning with ethyl acetate / saturated aqueous solution of sodium chloride and washing the organic layer with sodium hydrogen carbonate, the organic layer was washed with pure water and dried over magnesium sulfate. 0.234 g of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the solvent was removed by an evaporator, and 113 g of YM-2 was obtained.

(Preparation of Dye-Polymer Water Dispersion (ALx-1))
In a container, 4.0 parts by mass of YM-2, 1.0 parts by mass of mono (2-acryloyloxyethyl) succinate (manufactured by Tokyo Chemical Industry Co., Ltd.), n-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 4.0 parts by mass, 0.3 parts by mass of divinylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.0 parts by mass of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.), V-65 (Wako Pure Chemical Industries, Ltd. 0.3 parts by mass, manufactured by Co., Ltd., and 0.6 parts by mass of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. A mixed solution of 35 parts by mass of pure water and 12 parts by mass of a 4% aqueous solution of sodium dodecyl sulfate was added, and the mixture was stirred for 12 minutes at 14000 rpm for emulsification to obtain an emulsion. The obtained emulsion is distilled off under reduced pressure to remove the organic solvent, coarse particles are removed by filter filtration, pure water is added so that the solid concentration becomes 13%, and the aqueous dispersion of dye polymer (ALx) 61 parts by mass of -1) was obtained. The final solid concentration of the dye-polymer aqueous dispersion (ALx-1) was 13% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ALx-1) is an acrylic polymer and is a gel having a crosslinked structure since it is insoluble in any solvent of DMSO, NMP, and THF, and the average particle size is It was 140 nm.

Example 1
[Preparation of inkjet ink (1)]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore diameter: 0.8 μm) to prepare an inkjet ink (1).
Dye polymer water dispersion (ULx-1) 3.0 parts by mass Trimethylolpropane 0.060 parts by mass Ultrapure water 0.392 parts by mass 1,2-hexanediol 0.116 parts by mass Glycerin 0.579 parts by mass Triethylene Glycol monobutyl ether 0.119 parts by mass 2-pyrrolidone 0.157 parts by mass Propylene glycol 0.040 parts by mass Surfynol 465 (manufactured by Nisshin Chemical Industry Co., Ltd., trade name) 0.060 parts by mass

[Ink jet printing]
An ink jet ink (1) is loaded into an ink cartridge, and a polyester fabric (Polyester Tropical (manufactured by Teijin Limited), manufactured by Color Dyeing Company, using an ink jet printer (manufactured by Seiko Epson Corp., Carrario PX-045A, trade name) , Product code A02-01019), cotton fabric (with cotton broadsil, product of dyed products, product code A02-01002), and polyester 65% 35% cotton blend (blended polyester 65 / cotton 35 broad, product of dyed products) The image was printed on product code A02-01030) and dried at 20 ° C. for 12 hours. After drying, heat treatment should be performed at a temperature of 160 ° C and a pressure of 0.20 N / cm ² for 60 seconds using a heat press (Asahi Textile Co., Ltd., trade name: desktop automatic flat press AF-54 TEN). Thus, a colored cloth having a clear image with no bleeding was obtained.

(Example 2)
An inkjet ink (2) was prepared in the same manner as in Example 1 except that the dye polymer water dispersion (ULx-1) was changed to the dye polymer water dispersion (ULx-2). In addition, inkjet textile printing was performed in the same manner as in Example 1 except that the inkjet ink (1) was changed to the inkjet ink (2) to obtain a colored cloth.

(Examples 3 to 6)
Ink-jet ink (3) to ink-jet ink (3) to Example 1 in the same manner as in Example 1 except that the dye-polymer aqueous dispersion (ULx-1) was changed from dye-polymer aqueous dispersion (ULx-3) to dye-polymer aqueous dispersion (ULx-6) (6) was prepared. In addition, inkjet textile printing was performed in the same manner as in Example 1 except that the inkjet ink (1) was changed to the inkjet inks (3) to (6), to obtain a colored cloth.

(Example 7)
Dye polymer aqueous dispersion (ULx-1) 3.0 parts by mass, dye polymer aqueous dispersion (ULx-4) 1.5 parts by mass, dye polymer aqueous dispersion (ULx-5) 1.5 parts by mass, and An inkjet ink (7) was prepared in the same manner as in Example 1 except that the dye polymer aqueous dispersion (ULx-6) was changed to 0.2 parts by mass. In addition, inkjet textile printing was performed in the same manner as in Example 1 except that the inkjet ink (1) was changed to the inkjet ink (7) to obtain a colored cloth.

(Example 8)
An inkjet ink (8) was prepared in the same manner as in Example 1 except that the dye polymer water dispersion (ULx-1) was changed to the dye polymer water dispersion (ALx-1). In addition, inkjet textile printing was performed in the same manner as in Example 1 except that the inkjet ink (1) was changed to the inkjet ink (8) to obtain a colored cloth.

(Example 9)
[Preparation of aqueous pretreatment liquid A (1) containing flocculant]
The following components were mixed and stirred to prepare an aqueous pretreatment liquid A (1).
Casio Master PD-7 (Flocculant-containing; made by Yokkaichi Synthetic, solid content 50 mass%)
50g
BYK 348 (made by Big Chemie Japan) 5g
100 g of glycerin
Water 845g

[Pretreatment process]
Polyester fabric (Polyester Tropical (manufactured by Teijin Limited, product name A02-01019) manufactured by Color Dyes Co., Ltd.), cotton fabric (with cotton broadsil, product name A02-01002 manufactured by Color Dyes Co., Ltd.), and polyester The above-prepared aqueous pretreatment solution A (1) is applied to a 65% cotton 35% blend (blended polyester 65 / cotton 35 broad, product name A02-01030, manufactured by Color Dyeing Co., Ltd.) by a padding method, It squeezed by 70% of squeezing rates, and allowed to dry for 24 hours. In addition, a squeeze rate (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid to the fabric after squeezing the fabric containing the aqueous treatment liquid.

[Ink jet printing]
Inkjet printing was performed in the same manner as in Example 4 except that the above-described pretreated fabric was used as the fabric, to obtain a colored fabric.

(Examples 10 to 12)
Inkjet printing was performed in the same manner as in Examples 5 to 7 except that the above-described pretreated fabric was used as the fabric, to obtain a colored fabric.

(Comparative Example 1) Sublimation transfer printing After printing an image on transfer paper using a sublimation transfer printing printer SureColor F 6000 (product name of Seiko Epson Corporation), a polyester fabric (Polyester Tropical (manufactured by Teijin Limited), stock) Co., Ltd. company color dye company, product code A02-01019), cotton fabric (with cotton broadsil, product code A02-01002), and polyester 65% cotton 35% blend (blend polyester 65 / cotton 35) The image was printed on Broad, product name A02-01030), manufactured by Color Dyes Co., Ltd., and dried at room temperature for 12 hours. After drying, heat treatment should be performed at a temperature of 200 ° C and a pressure of 0.20 N / cm ² for 60 seconds using a heat press (Asahi Textile Co., Ltd., trade name: desktop automatic flat press AF-54 TEN). To obtain a transferred image. Although clear images were obtained for the polyester fabric, in the case of the polyester 65% cotton 35% blend, images with sharp but low dyeing density were obtained and in the case of the cotton fabric a very blurred image was obtained. The

Comparative Example 2 Coloring of Ink Jet System Using Pigment (Preparation of Pigment Dispersion)
Three parts by mass of a styrene-acrylic acid copolymer (JONCRYL 678, manufactured by BASF, trade name), 1.3 parts by mass of dimethylaminoethanol, and 80.7 parts by mass of ion exchange water were stirred at 70 ° C. and mixed. Then, C.I. I. 15 parts by mass of pigment blue 15: 3 and 50% by volume of zirconia beads with a particle diameter of 0.5 mm are filled, dispersed using a sand grinder mill, and a pigment dispersion having a content of cyan pigment of 15% by mass Obtained.

(Preparation of aqueous binder)
A three-necked flask was charged with 50 parts by mass of methyl ethyl ketone (MEK) and kept at 75 ° C. under nitrogen. Separately, a mixture of 80 parts by mass of butyl methacrylate, 20 parts by mass of acrylic acid, 50 parts by mass of MEK and 0.5 parts by mass of azoisobutyronitrile was dropped to the flask over 3 hours. After dropping, the mixture was heated under reflux for 5 hours, cooled to 20 ° C., and heated under reduced pressure to obtain a residue of a polymer. Thereto, 350 parts by mass of ion exchanged water and 1.05 moles of sodium hydroxide of acrylic acid added as a monomer were added and dissolved. The whole was diluted with ion exchange water to 500 parts by mass to obtain a 20% by mass aqueous solution of an aqueous binder.

(Preparation of pigment ink and coloring of ink jet system)
46.6 parts by mass of the pigment dispersion, 15 parts by mass of a 20% by mass aqueous solution of the aqueous binder, 2.9 parts by mass of PDX-7664A (manufactured by BASF, trade name), 10 parts by mass of triethylene glycol monobutyl ether, Mix 5 parts by mass of 2-hexanediol, 11.2 parts by mass of diethylene glycol, and 0.6 parts by mass of Orphin 465 (trade name, manufactured by Nisshin Chemical Industry Co., Ltd.), add ion-exchanged water to this to make the total amount 100 parts by mass. The pigment ink was prepared and filtered through a 0.8 μm filter to obtain a pigment ink (R2) for comparison.
The obtained pigment ink (R2) is loaded into an ink cartridge, and a polyester fabric (polyester tropical (made by Teijin Ltd.), color, using an ink jet printer (manufactured by Seiko Epson Corp., Carrario PX-045A, trade name) Dyeing company, product code A02-01019), cotton fabric (with cotton broadsil, product of dyed product, product code A02-01002), and polyester 65% cotton 35% blend (blend polyester 65 / cotton 35 broad, color dye The image was printed on a product code A02-01030) and dried at 20 ° C. for 12 hours. After drying, heat treatment should be performed at a temperature of 200 ° C and a pressure of 0.20 N / cm ² for 60 seconds using a heat press (Asahi Textile Co., Ltd., trade name: desktop automatic flat press AF-54 TEN). Thus, a pigmented ink-printed colored cloth was obtained.

The evaluation results of Examples 1 to 12 and Comparative Examples 1 and 2 are shown in Table 1. In addition, evaluation of a colored cloth is the result of implementing with the following method. In the evaluation of texture and wet rub fastness, a cotton fabric was used among the three types of fabrics. The evaluation was made according to the “JIS Handbook 31 Textile” edited by the Japan Standards Association and published in 2015.
Image sharpness: Visual sensory evaluation was performed. All three types of fabrics were evaluated in the following four grades: A, two types, B, one type, C, and no image, D.
-Texture: The untreated cloth before dyeing and the colored cloth after dyeing were touched by hand, and the feeling of the colored cloth was evaluated sensoryally. The evaluation was performed by 10 people, with 10 points being excellent, with the texture of the colored cloth close to the untreated cloth being 0, and the other points being 0, and the numerical values of the total points are shown in Table 1 below. The larger the value, the better the texture close to the untreated cloth (100 (point)).
-Fastness to wet rubbing: It was evaluated based on JIS L-0849 vibration-type friction test. The larger the value, the better the fastness.

As apparent from the above results, it can be seen that the inkjet ink of the example of the present invention gives a colored cloth having good image sharpness, texture and wet rub fastness.

According to the present invention, it is possible to provide an ink jet ink capable of providing an image excellent in image sharpness, texture and wet rub fastness, an ink jet printing method using the above ink, and a colored cloth.

Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application (Japanese Patent Application No. 2017-138198) filed on July 14, 2017, the contents of which are incorporated herein by reference.

Claims (11)

1. An inkjet ink comprising an aqueous dispersion of a polymer having a structure derived from a dye and having a crosslinked structure.
2. A polymer comprising at least one of a structure represented by the following general formula (1) and a structure represented by the following general formula (2) as a structure derived from the dye, or a polymer represented by the following general formula (3 The inkjet ink according to claim 1, which is a polymer containing a structure represented by
   

   

   
   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 any one hydrogen atom from the 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 combined.
   

   

   
   In 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 Or 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 the 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 to each other.
   

   

   
   In the 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 represented by the following formula (L6-1) or (L6-2) D ¹ represents a linking group, and D ¹ represents a dye residue obtained by removing one hydrogen atom from the dye.
   

   

   
   In Formula (L6-1), L ⁷ represents a single bond or a divalent linking group, * 4 represents a position to be bonded to a carbon atom in General Formula (3), and * 5 is a general formula (3) Represents a position to bind to D ^{1 in}
   In formula (L6-2), L ⁸ represents a single bond or a divalent linking group, * 6 represents a position to be bonded to a carbon atom in general formula (3), * 7 represents a general formula (3) Represents a position to bind to D ^{1 in}
3. Wherein ^{D 1} of the general formula (1) in the general formula (2) Medium ^{D 2,} or ^{D 1} of the formula (3) is selected from the group of the following formula (M1) ~ (M8) The inkjet ink according to claim 2, which represents a dye residue obtained by removing one or two optional hydrogen atoms from the dye represented by at least one.
   

   

   
   In formula (M1), R ¹⁰¹ to R ¹¹⁰ each independently represent a hydrogen atom or a substituent.
   In 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 formula (M3), R ³⁰¹ to R ³¹⁷ each independently represent a hydrogen atom or a substituent, X ³⁰¹ represents a monovalent anion, and n ³⁰¹ represents 0 or 1.
   In formula (M4), R ⁴⁰² to R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent, and Ar ⁴⁰¹ represents a phenyl group, a naphthyl group or a heterocyclic group, and the above phenyl group, the above naphthyl group or The above-mentioned heterocyclic group may further have a substituent.
   In Formula (M5), R ⁵⁰¹ to R ⁵⁰⁸ each independently represent a hydrogen atom or a substituent.
   In 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 formula (M7), R ⁷⁰¹ to R ⁷⁰⁶ each independently represent a hydrogen atom or a substituent.
   In formula (M8), R ⁸¹¹ to R ⁸¹⁸ and R ⁸²¹ to R ⁸²⁸ each independently represent a hydrogen atom or a substituent.
4. The inkjet ink according to any one of claims 1 to 3, wherein an average particle size of the polymer is 50 to 500 nm.
5. An ink jet ink according to any of the preceding claims, wherein the polymer is a urethane polymer.
6. An inkjet ink according to any one of the preceding claims, wherein the polymer is an acrylic polymer.
7. The inkjet ink according to any one of claims 1 to 6, which has a viscosity of 40 mPa · s or less at 25 属 C.
8. The inkjet ink according to any one of claims 1 to 7, which is for textile printing.
9. An ink jet printing method comprising the step of printing directly on a fabric by an ink jet method using the ink jet ink according to any one of claims 1 to 8.
10. The inkjet textile printing method according to claim 9, further comprising a heat treatment step.
11. A colored cloth comprising a cloth and a polymer having a structure derived from a dye and having a crosslinked structure.