JP2019194368A - Inkjet printing method, method for producing colored cloth, and colored cloth - Google Patents

Abstract

To provide an inkjet printing method having excellent color development and image fastness, or the like.SOLUTION: An inkjet printing method has a pretreatment step of giving an aqueous pretreatment liquid containing a flocculant to cloth, and a printing step of printing an inkjet ink containing a water dispersion of a dye polymer having a repeating unit containing a dye-derived structure, on the cloth to which the aqueous pretreatment liquid has been given, by inkjet. There are also provided a method for producing colored cloth, and colored cloth.SELECTED DRAWING: None

Description

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

  Conventionally, a colorant used for coloring a fabric is either a dye or a pigment. As a method for industrially coloring a fabric using these colorants, a screen printing method, a roller printing method, a transfer method, An inkjet method has been performed. In particular, the ink jet method does not require a plate to be prepared as compared with other methods, can quickly form an image with excellent gradation, and uses only a necessary amount of ink as a formed image. It can be said that this is an excellent image forming method having environmental advantages such as few.

For example, Patent Document 1 describes ink-jet printing in which a dye is dissolved in water to prepare an ink, and a fabric is dyed by an ink-jet method.
Each dye molecule interacts with the fiber so that the dye penetrates into the inside of the fiber and is integrated with the fiber. Therefore, the fabric dyed with the dye has a soft texture and is preferred as a garment. . On the other hand, ink-jet textile printing using dyes requires a textile paste to be applied to the cloth in advance in order to prevent blurring (improves the sharpness), and in addition, it is a colored cloth to fix the dye after dyeing. It is necessary to wash the excess dye and printing paste by a process such as water washing or soaping. For this reason, a process is complicated and an apparatus and an effort are required, and waste water arises.
Further, in coloring with a dye, it is necessary to appropriately select the type of dye depending on the type of fiber. For example, reactive dyes or direct dyes for cellulose fibers such as cotton and hemp, acid dyes for animal fibers such as wool or silk, acid dyes or disperse dyes for nylon fibers, disperse dyes and acrylics for polyester fibers Cationic dyes are used for the fibers.

An ink-jet sublimation transfer printing method has been widely put into practical use as a dyeing method that has improved the above-described complicated steps in normal ink-jet printing, the problem of time and labor required for the apparatus, and the problem of wastewater (see, for example, Patent Document 2). In the ink-jet sublimation transfer printing method, a pattern to be printed using an ink-jet printer is printed on transfer paper with ink containing resin particles containing a disperse dye, and then the transfer paper and a polyester fabric are superposed and heat-treated. This is a method for transferring the sublimable dye from the resin particles to the polyester fabric.
However, the dyeing mechanism in this system is said to be a phenomenon of thermal diffusion or thermal sublimation of dye molecules, or a mixture of both. In order to use a certain sublimation dye, it mainly corresponds to dyeing | staining of a polyester fabric. In addition, the used transfer paper cannot be recycled and becomes industrial waste.

On the other hand, an ink-jet coloring method using a pigment has also been studied (for example, see Patent Document 3). 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. .
Unlike the coloring method using dyes, the coloring method using pigments does not require the selection of a colorant depending on the fiber type, and does not require a complicated steam heating (steaming) process or water washing process. The pigment can be fixed.
However, the pigment adheres to (is on) the fiber in the form of particles in which the dye molecules are gathered, and maintains fastness such as washing fastness and friction fastness of the colored cloth (colored cloth). A large amount of emulsion resin must be used as a sticking agent, and the texture of the colored cloth becomes stiff. For example, when the colored cloth is a garment, the quality as a garment is inferior to a colored cloth dyed with a dye. Is. In addition, the emulsion resin is dried due to the volatilization of water, the pigment ink is thickened, and a phenomenon such as clogging of the ink jet printer is likely to occur, resulting in poor workability.

Patent Documents 4 and 5 describe a method of applying a pretreatment liquid containing a polyvalent metal ion or an organic acid to a fabric before printing using a pigment or a disperse dye.
Patent Document 6 describes an ink-jet ink containing a polymer having a specific structure in which a specific dye is linked to a polymer skeleton.
Patent Document 7 describes an inkjet ink containing polyurethane having a colorant structure.

JP 2002-348502 A JP-A-10-58638 JP 2010-37700 A Japanese Patent No. 589589 Japanese Patent No. 4655585 Special table 2004-534106 gazette Special table 2002-509957 gazette

As described above, coloring with dyes is excellent in the quality (texture) and fastness of the colored cloth, but it is necessary to select a dye depending on the fiber type, and it is necessary to apply printing paste and wash with water. However, there are problems such as complicated problems, problems that require equipment, and inferior environmental loads such as waste water and waste materials. On the other hand, coloring with pigments does not require the selection of dyes based on the fiber type, and the process is simple, but has problems in workability such as clogging of ink jet printers due to thickening of ink, and coloring cloth There is a problem that many of them are inferior in quality (texture). Furthermore, there is a problem that a colored fabric colored with a pigment is inferior in coloring property, washing resistance, sweat resistance, friction resistance, and dry cleaning resistance.
Further, even when the ink jet textile printing methods described in Patent Documents 4 and 5 are used, the above problem still cannot be solved.

  In view of the above problems, the object of the present invention is to be able to dye various types of fabrics, do not require application of printing paste and washing with water, have a low environmental load, have no problem in workability, and have a good image quality. Ink-jet printing method and coloring fabric with excellent sharpness, color development, and fastness (washing resistance, sweat resistance, friction resistance, and dry cleaning resistance) and excellent quality (texture) of the colored fabric It is in providing a manufacturing method and a colored cloth.

The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and various methods are used for printing on a fabric by an inkjet method using an aqueous dispersion of a dye polymer having a repeating unit containing a structure derived from a dye. It has been found that various types of fabrics can be dyed, application of printing paste and washing with water are unnecessary, there is little environmental load, there is no problem in workability, and an excellent quality colored fabric can be obtained.
Further, by applying an aqueous pretreatment liquid containing an aggregating agent to the fabric before the textile printing step, color development and fastness (washing resistance, sweat resistance, friction resistance, and dry cleaning resistance) It has been found that the property is significantly improved.
Although details are unknown as a mechanism by which the above problem can be solved by the above method, the present inventors presume as follows.
The aqueous dispersion of the dye polymer having a repeating unit containing a structure derived from the dye uses the dye polymer as an aqueous dispersion instead of an aqueous solution, so that bleeding does not occur as in the case of pigment particles, and no printing paste and washing with water are required. In addition, no waste water is generated because no washing process is required. Further, since printing is performed directly on the fabric to which the aqueous pretreatment liquid is applied, waste such as transfer paper is not generated. Since the emulsion resin as the fixing agent is not used unlike the pigment ink, the viscosity of the ink is not increased and the workability is excellent. Furthermore, it is considered that the dye polymer is integrated with the fiber at the molecular level so as to cover the surface of the fiber regardless of the fiber type. For this reason, it is thought that the cloth which consists of various kinds of fibers can be dyed, and the colored cloth of the excellent quality is obtained.
In addition, the aggregating agent suppresses the penetration of the inkjet ink in the depth direction of the fabric by aggregating the dye polymer by charge shielding or forming a complex with the dye polymer on the fabric. It is considered that color development efficiency can be improved and color development can be improved. Further, since the dye polymer becomes a hydrophobic film on the surface of the fabric, it is considered that the washing resistance, sweat resistance, friction resistance, and dry cleaning resistance are improved.
In the present invention, “directly printing” an inkjet ink on a fabric to which an aqueous pretreatment liquid has been applied by an inkjet method does not require a transfer step, and the inkjet ink has been provided with an aqueous pretreatment liquid. It refers to both printing directly on a fabric and printing directly on a fabric to which an aqueous pretreatment liquid is applied without applying printing paste.
Specifically, the object of the present invention has been achieved by the following means.

<1>
The above-mentioned aqueous pretreatment liquid was applied to a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to a fabric, and an ink-jet ink containing an aqueous dispersion of a dye polymer having a repeating unit containing a structure derived from a dye. An ink-jet printing method comprising: a printing step of printing on a fabric by an ink-jet method.
<2>
Furthermore, the inkjet textile printing method as described in <1> including a heat treatment process.
<3>
The ink jet printing method according to <1> or <2>, wherein the pretreatment step is a step of applying the aqueous pretreatment liquid to a fabric by a coating method, a padding method, a spray method, a screen printing method, or an ink jet method.
<4>
The inkjet printing method according to any one of <1> to <3>, wherein the flocculant is at least one selected from organic acids, polyvalent metal salts, and cationic compounds.
<5>
The inkjet printing method according to any one of <1> to <4>, wherein the content of the flocculant is 0.1 to 50% by mass with respect to the total amount of the aqueous pretreatment liquid.
<6>
The inkjet printing method according to any one of <1> to <5>, wherein the aqueous pretreatment liquid further contains a crosslinking agent.
<7>
The inkjet printing method according to any one of <1> to <6>, wherein the inkjet ink containing the aqueous dispersion of the dye polymer further contains a crosslinking agent.
<8>
The inkjet printing method according to <6> or <7>, wherein the crosslinking agent is at least one selected from a blocked isocyanate crosslinking agent, an epoxy crosslinking agent, and a methylol crosslinking agent.
<9>
The above dyes are azo dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, polymethine dyes, monomethine dyes, azomethine dyes, indoaniline dyes, indophenol dyes, nigrosine dyes, oxazine dyes. , Thiazine dye, anthraquinone dye, indigo dye, quinophthalone dye, porphyrin dye, cyanine dye, and at least one dye selected from the group consisting of phthalocyanine dyes according to any one of <1> to <8> Inkjet printing method.
<10>
<1> to <9>, wherein the dye polymer is a dye polymer including a repeating unit represented by the following general formula (1) or (10) as a repeating unit including a structure derived from the dye. The inkjet printing method of any one of Claims.

In General Formula (1), X ¹ represents a linking group, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye.

In general formula (10), X ² and X ³ each independently represent a linking group, and D ² represents a dye residue obtained by removing two arbitrary hydrogen atoms from a dye.
<11>
D ¹ in the general formula (1) or D ² in the general formula (10) is an arbitrary hydrogen atom from the dye represented by any one of the following general formulas (M1) to (M9) or The inkjet printing method according to <10>, which represents a dye residue from which two are removed.

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 ^{401 to} R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent.

In General Formula (M5), R ^{501 to} R ⁵¹¹ each independently represent a hydrogen atom or a substituent.

In General Formula (M6), R ^{601 to} R ⁶⁰⁸ each independently represent a hydrogen atom or a substituent.

In General Formula (M7), R ^{701 to} R ⁷⁰⁸ each independently represent a hydrogen atom or a substituent.

In General Formula (M8), R ^{801 to} R ⁸⁰⁹ each independently represent a hydrogen atom or a substituent.

In General Formula (M9), R ^{901 to} R ⁹¹³ each independently represent a hydrogen atom or a substituent.
<12>
The inkjet printing method according to any one of <1> to <11>, wherein the dye polymer is an acrylic polymer, a urethane polymer, or a styrene polymer.
<13>
The inkjet printing method according to any one of <1> to <12>, wherein the amount of the ionic group in the dye polymer is 0.1 to 1.8 mmol / g.
<14>
The inkjet printing method according to any one of <1> to <13>, wherein the glass transition point of the dye polymer is 200 ° C. or lower.
<15>
The inkjet printing method according to any one of <1> to <14>, wherein the dye polymer melts at 200 ° C. or lower.
<16>
<1> to <15>, wherein the dye polymer in the aqueous dispersion of the dye polymer is a particulate dye polymer, and the average particle diameter of the particulate dye polymer is 50 to 500 nm. Inkjet printing method.
<17>
The ink-jet printing method according to any one of <1> to <16>, wherein the dye polymer has a weight average molecular weight of 3,000 to 2,000,000.
<18>
The above-mentioned aqueous pretreatment liquid was applied to a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to a fabric, and an ink-jet ink containing an aqueous dispersion of a dye polymer having a repeating unit containing a structure derived from a dye. A method for producing a colored fabric, comprising: a printing step of printing on the fabric by an inkjet method.
<19>
A colored cloth having an image including a flocculant and a dye polymer having a repeating unit including a structure derived from a dye on at least a part of the surface of the cloth.

  According to the present invention, it is possible to dye various types of fabrics, there is no need to apply printing paste and washing with water, there is little environmental burden, there is no problem in workability, and the sharpness and color development of the resulting image. Ink-jet printing method, coloring fabric manufacturing method, and coloring, which are excellent in color fastness (washing resistance, sweat resistance, friction resistance, and dry cleaning resistance) and excellent in quality (texture) of colored fabric Cloth can be provided.

Hereinafter, the present invention will be described in detail.
In the present 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 the present specification, “(meth) acrylate” represents at least one of acrylate and methacrylate, “(meth) acryl” represents at least one of acryl and methacryl, and “(meth) acryloyl” represents at least acryloyl and methacryloyl. Represents a kind.

[Inkjet printing method]
In the inkjet printing method of the present invention, an inkjet ink comprising a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to a fabric, and an aqueous dispersion of a dye polymer having a repeating unit containing a structure derived from a dye, And a printing step of printing on the fabric to which the aqueous pretreatment liquid has been applied by an inkjet method.

<Pretreatment process>
The present invention includes a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to a 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.

(Aqueous pretreatment liquid)
The aqueous pretreatment liquid used in the pretreatment step will be described.
The aqueous pretreatment liquid contains at least a flocculant.

(Flocculant)
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.

≪Organic acid≫
Organic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, tricarbaryl Acid, glycolic acid, thioglycolic acid, lactic acid, malic acid, tartaric acid, citric acid, isocitric acid, gluconic acid, pyruvic acid, oxalic acetic acid, diglycolic acid, benzoic acid, phthalic acid, mandelic acid, salicylic acid Of these, at least one selected from tartaric acid, citric acid and lactic acid is more preferable.

≪Polyvalent metal salt≫
The polyvalent metal salt is a compound composed of a divalent or higher valent metal ion and an anion. Examples of divalent or higher metal ions include ions of calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, iron, and the like. Among the metal ions constituting these polyvalent metal salts, at least one of calcium ions and magnesium ions is preferable, and calcium ions are more preferable.

  Examples of the anion constituting the polyvalent metal salt include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, acetate ion, carbonate ion and hydroxide ion. Among the anions constituting these polyvalent metal salts, inorganic ions are preferable from the viewpoint that odor can be suppressed, and chlorine ions are more preferable from the viewpoint that discoloration and the like can be suppressed.

  Polyvalent metal salts include calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium hydroxide, calcium carbonate, magnesium chloride, magnesium acetate, magnesium sulfate, magnesium carbonate, barium sulfate, barium chloride, zinc sulfide, zinc carbonate, Examples thereof include copper nitrate. These polyvalent metal salts may be used alone or in combination of two or more. The polyvalent metal salt is preferably water-soluble (specifically, the solubility in 100 mL of water at 20 ° C. is 10 g or more).

≪Cationic compound≫
The cationic compound is not particularly limited, and may be a low molecular compound or a high molecular compound.

(Low molecular compound)
Examples of the low molecular weight cationic compound include (2-hydroxyethyl) trimethylammonium chloride, benzoylcholine chloride, benzyltriethylammonium chloride, trimethylacetohydrazide ammonium chloride, 1-butyl-1-methylpyrrolidinium chloride, 3- Examples thereof include hydroxy-4- (trimethylammonio) butyrate hydrochloride, glycidyltrimethylammonium chloride, L-carnitine hydrochloride and the like.

(Polymer compound)
Examples of the high molecular weight cationic compound include water-soluble and positively active in water such as polyallylamine or a derivative thereof, an amine-epihalohydrin copolymer, or other quaternary ammonium salt type cationic polymer. Examples include charged cationic polymers. In some cases, a water-dispersible cationic polymer can also be used.

(Aqueous medium)
The aqueous pretreatment liquid used in the present invention may contain an aqueous medium in addition to the aggregating agent. An aqueous medium is a medium that is arbitrarily mixed with water. The aqueous medium contains at least one of water and an aqueous organic solvent, preferably contains water, and more preferably contains 30% by mass or more of water with respect to the total mass (100% by mass) of the aqueous medium. The aqueous pretreatment liquid may contain, for example, a surfactant, a resin and the like in addition to water and an aqueous organic solvent.

≪Water≫
The water is preferably water from which ionic impurities such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water or ultrapure water are removed as much as possible. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, it is preferable because generation of mold and bacteria can be prevented when the pretreatment liquid is stored for a long time.
The content of water contained in the aqueous pretreatment liquid can be, for example, 50% by mass or more, or 60% by mass or more, with respect to the total mass of the aqueous pretreatment liquid.

≪Aqueous organic solvent≫
The aqueous organic solvent is the same as the aqueous organic solvent that can be contained in an aqueous dispersion of a dye polymer described later.

≪Surfactant≫
The surfactant is the same as the surfactant that can be contained in the aqueous dispersion of the dye polymer described later.

≪Crosslinking agent≫
The aqueous pretreatment liquid may further contain a crosslinking agent.
Although it does not specifically limit as a crosslinking agent, It is preferable that it is at least 1 sort (s) chosen from a block isocyanate type crosslinking agent, an epoxy type crosslinking agent, and a methylol type crosslinking agent.

  In addition to the above-described components, the aqueous pretreatment liquid may contain components that may be contained in the inkjet ink used in the present invention described later.

The content of the flocculant is preferably 0.1 to 50% by mass, more preferably 0.1 to 45% by mass, and 0.5 to 40% by mass with respect to the total amount of the aqueous pretreatment liquid. More preferably.
When the content of the flocculant is 50% by mass or more based on the total amount of the aqueous pretreatment liquid, the stability of the treatment liquid may be lowered. In addition, when the content of the flocculant is 0.1% by mass or less with respect to the total amount of the aqueous pretreatment liquid, sufficient effects on color developability and fastness cannot be obtained.

  The content of the aqueous medium is preferably 40 to 99% by mass, more preferably 50 to 97% by mass, and still more preferably 60 to 95% by mass with respect to the total amount of the aqueous pretreatment liquid. .

<Printing process>
The present invention includes a printing process in which an inkjet ink including an aqueous dispersion of a dye polymer having a repeating unit including a structure derived from a dye is printed on a fabric provided with the aqueous pretreatment liquid by an inkjet method.
The printing step in the present invention is a step of directly printing an inkjet ink containing an aqueous dispersion of a dye polymer having a repeating unit containing a structure derived from a dye on a fabric to which an aqueous pretreatment liquid has been applied by an inkjet method. It is preferable.
The dye polymer used in the present invention will be described below.

(Dye polymer having a repeating unit containing a structure derived from a dye)
The dye polymer having a repeating unit including a structure derived from a dye (also simply referred to as “dye polymer”) used in the present invention is a pigment multimer including a structure derived from an arbitrary dye as a repeating unit.
The dye polymer may be a linear polymer or a network polymer. When the dye polymer is 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 structure derived from a dye is a group (dye residue) formed by removing one or more arbitrary hydrogen atoms from an organic compound used as a dye, preferably 1 arbitrary hydrogen atom from an organic compound used as a dye. It is a group formed by removing one or two. 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 structures derived from 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, Examples include methine dyes, aniline dyes, indamine dyes, indophenol dyes, azine dyes, oxazine dyes, thiazine dyes, anthraquinone dyes, indigo dyes, quinophthalone dyes, and phthalocyanine dyes.
Dyes are azo dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, polymethine dyes, monomethine dyes, azomethine dyes, indoaniline dyes, indophenol dyes, nigrosine dyes, oxazine dyes, It is preferably at least one dye selected from the group consisting of thiazine dyes, anthraquinone dyes, indigo dyes, quinophthalone dyes, porphyrin dyes, cyanine dyes and phthalocyanine dyes.
The dye is composed of azo dye, stilbene dye, diarylmethane dye, triarylmethane dye, xanthene dye, indoaniline dye, indophenol dye, digrosine dye, anthraquinone dye, quinophthalone dye, and phthalocyanine dye from the viewpoint of coloring power. More preferably, it is at least one dye selected from the group.

  The structure derived from the dye in the present invention is not limited to the structure that is commercially available as a dye. It is only necessary to have a structure known to be usable as a dye, such as the above azo dye and stilbene dye. For example, the structure which changed these other substituents etc. leaving these structures from the commercially available dye is also contained.

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 ammonium group. Such a dye is not particularly limited. For example, a water-insoluble dye 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 containing a structure derived from a dye in the main chain or side chain is particularly preferably used. The polymer constituting the main chain in the polymer containing a structure derived from a dye in the main chain or side chain is not particularly limited, but an acrylic polymer, a urethane polymer, or a styrene polymer is preferably used, and in particular, an acrylic polymer or a urethane polymer is used. preferable.
The acrylic polymer in the present invention is a polymer having at least one type of repeating unit from 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 a compound having two or more hydroxyl groups (for example, a diol compound) and a compound having two or more isocyanate groups. It is formed by a polymerization reaction of (for example, a diisocyanate compound). Moreover, the styrene polymer in this invention means the polymer which has a repeating unit derived from styrene.

In the dye polymer, a method for introducing a repeating unit including a structure derived from a dye is arbitrary, and a polymer may be obtained by polymerizing or copolymerizing a polymerizable dye monomer. A structure derived from a dye may be introduced by a polymer reaction or the like.
As the dye polymer, a dye polymer comprising a repeating unit represented by the following general formula (1) or (10) is preferable.

In General Formula (1), X ¹ represents a linking group, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye.

In general formula (10), X ² and X ³ each independently represent a linking group, and D ² represents a dye residue obtained by removing two arbitrary hydrogen atoms from a dye.

[Repeating unit represented by general formula (1)]
First, the repeating unit represented by the general formula (1) will be described.
In general formula (1), X ¹ represents a linking group. X ¹ is preferably a linking group formed by polymerization, and preferably a portion corresponding to the main chain formed by the polymerization reaction. That is, X ¹ is preferably a partial structure of the polymer main chain. X ¹ includes a linking group formed by polymerizing a substituted or unsubstituted unsaturated ethylene group, a linking group formed by ring-opening polymerization of a cyclic ether, and a linking group formed by urethane polymerization of a substituted diol. , A linking group formed by urea polymerization of a substituted diamine, a linking group formed by urethane urea polymerization of a substituent having an amino group and a hydroxyl group, and the like. Preferably, an unsaturated ethylene group is polymerized. A linking group formed, a linking group formed by urethane polymerization of a substituted diol, and a linking group formed by urea polymerization of a substituted diamine. Specific examples of X ¹ include the following linking groups, but are not limited thereto. Incidentally, indicating that it is linked to ^{L 1} at a site indicated by * in the following (X-1) ~ (X -15).

  The repeating unit represented by the general formula (1) is preferably a repeating unit represented by any one of the following general formulas (1-1) to (1-7), and the following general formula (1-1) It is more preferable that it is a repeating unit represented by.

In the general formulas (1-1) to (1-7), R _{X1 to} R _X21 each represent a hydrogen atom or a substituent, L ¹ represents a single bond or a divalent linking group, and D ¹ is optional from a dye. Represents a dye residue from which one hydrogen atom is removed.
When R _{X1 to} R _X21 represent a substituent, the substituent is preferably an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, or a group formed by combining these, more preferably an alkyl group. More preferably, it is a methyl group.
R _X1 , R _X6 , R _X13 , R _X16 , and R _X19 preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group, a carboxymethyl group, a hydroxymethyl group, or a methyloxymethyl group, and a hydrogen atom or methyl More preferably it represents a group.
R _X2 , R _X3 , R _X4 , R _X5 , R _X7 , R _X8 , R _X9 , R _X10 , R _X11 , R _X12 , R _X14 , R _X15 , R _X17 , R _X18 , R _X20 , and R _X21 It preferably represents an atom or a carboxyl group, and more preferably represents a hydrogen atom.

In General Formulas (1) and (1-1) to (1-7), L ¹ represents a single bond or a divalent linking group. The divalent linking group in the case where L ¹ represents a divalent linking group is not limited as long as the effect of the present invention can be obtained, but is a substituted or unsubstituted straight chain having 1 to 30 carbon atoms, Branched or cyclic alkylene group (eg, methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthylene group, etc.), substituted Alternatively, an unsubstituted heterocyclic linking group, —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 — and a linking group formed by linking two or more of these are preferably used. In particular, a linking group represented by any of the following general formulas (2) to (7) is preferably used.
When L ¹ represents a divalent linking group, the divalent linking group may have a substituent (for example, an alkyl group, an aryl group, a hydroxyl group, an acyloxy group, etc.).

In the general formula (2) to (7), * 1 and * 2 is, one, ^{X 1} or formula in the formula (1) (1-1) carbon atoms of the polymer backbone in - (1-7) or represents a position bonded with the nitrogen atom and the other, the general formula (1), but is representative of the position which binds to ^{D 1} in (1-1) to (1-7), * 1, the general formula (1) ^{X 1} or the general formula in (1-1) to represent the position at which the group bonds to a carbon atom or nitrogen atom of the polymer backbone in (1-7), * 2, the general formula (1), (1- it is preferred that represents a position bonded with ^{D 1} in 1) to (1-7).
In general formula (2), R ³ represents a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different.
In General Formula (3), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different.
In General Formula (4), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different.
In General Formula (5), R ₅₁ and R ₅₂ each independently represent a hydrogen atom or a substituent. t represents an integer of 1 to 10. The t R ₅₁ and R ₅₂ may be the same or different.
In General Formula (6), R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a substituent. u and v each independently represent an integer of 1 to 10. u R ⁶¹ and R ⁶² may be the same or different. The v R ⁶³ and R ⁶⁴ may be the same or different.
In general formula (7), R ⁷¹ , R ⁷² and R ⁷³ each independently represent a hydrogen atom or a substituent. w represents an integer of 1 to 10. Each of w R ⁷¹ and R ⁷² may be the same or different.

Examples of the alkyl group, aryl group, or heterocyclic group in the case where R ² in the general formula (3) represents an alkyl group, an aryl group, or a heterocyclic group include alkyls described in the substituent group A described later. A group, an aryl group, or a heterocyclic group.
Examples of the substituent represented by R ³ in the general formulas (2) to (4) include a substituent selected from the substituent group A described later.
_Examples of the substituent when R ₅₁ and R ₅₂ in the general formula (5) represent a substituent include a substituent selected from the substituent group A described later. R ₅₁ and R ₅₂ preferably each independently represent a hydrogen atom or a hydroxyl group. t is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
^Examples of the substituent in the case where R ⁶¹ , R ⁶² , R ⁶³ and R ^{64 in the} general formula (6) represent a substituent include a substituent selected from the substituent group A described later. R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently preferably represent a hydrogen atom or a hydroxyl group, more preferably a hydrogen atom. u and v are each independently preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
^Examples of the substituent when R ⁷¹ , R ⁷² and R ^{73 in the} general formula (7) represent a substituent include a substituent selected from the substituent group A described later. R ⁷¹ , R ⁷² and R ⁷³ each independently preferably represent a hydrogen atom or a hydroxyl group, and more preferably represent a hydrogen atom. w is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

In General Formulas (1) and (1-1) to (1-7), 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 (M9). It is more preferable that a dye residue obtained by removing one arbitrary hydrogen atom from the dye represented by any one of the following general formulas (M1) to (M4) is particularly 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 ^{401 to} R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent.

In General Formula (M5), R ^{501 to} R ⁵¹¹ each independently represent a hydrogen atom or a substituent.

In General Formula (M6), R ^{601 to} R ⁶⁰⁸ each independently represent a hydrogen atom or a substituent.

In general formula (M7), R ^{701 to} R ⁷⁰⁸ each independently represent a hydrogen atom or a substituent.

In General Formula (M8), R ^{801 to} R ⁸⁰⁹ each independently represent a hydrogen atom or a substituent.

In General Formula (M9), R ^{901 to} R ⁹¹³ 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 ^{401 to} R in General Formula (M4) ⁴⁰⁷ , R ^{501 to} R ⁵¹¹ in General Formula (M5), R ^{601 to} R ⁶⁰⁸ in General Formula (M6), R ^{701 to} R ⁷⁰⁸ in General Formula (M7), R ⁸⁰¹ in General Formula (M8) to R ^{809, R} 901 ^{to R 913} in formula (M9) is a substituent when it represents a substituent include the substituents for example selected from the following substituent group a.
The substituents included in Substituent Group A are shown below.

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 ^{401 to} R in General Formula (M4) ⁴⁰⁷ , R ^{501 to} R ⁵¹¹ in General Formula (M5), R ^{601 to} R ⁶⁰⁸ in General Formula (M6), R ^{701 to} R ⁷⁰⁸ in General Formula (M7), R ⁸⁰¹ in General Formula (M8) to R ^{809, R} 901 ^{to R 913} in formula (M9) is a substituent when it represents a substituent include the substituents for example selected from the following substituent group a.
The substituents included in Substituent Group A are shown below.

(Substituent group A)
A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, a linear, branched, or cyclic alkyl group; Methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, A cyclohexyl group, a 1-norbornyl group, a 1-adamantyl group), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl group, allyl group, 3-butene- 1-yl group), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, An aryl group, a naphthyl group), a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group such as a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably having 3 to 38 carbon atoms, more preferably carbon number) 3 to 18 silyl groups, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably A linear, branched or cyclic alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methoxy group, Toxyl group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group, cyclopentyloxy group, cyclohexyloxy group), aryloxy group (preferably having 6 to 48 carbon atoms, more preferably An aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group or a 1-naphthoxy group), a heterocyclic oxy group (preferably having a carbon number of 1 to 32, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, For example, a 1-phenyltetrazol-5-oxy group, a 2-tetrahydropyranyloxy group), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, a trimethylsilyloxy group , T-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group ( Preferably, it is an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, pivaloyloxy group, benzoyloxy group, dodecanoyloxy group), an alkoxycarbonyloxy group (preferably having 2 to 2 carbon atoms). 48, more preferably a linear, branched or cyclic alkoxycarbonyloxy group having 2 to 24 carbon atoms, such as ethoxycarbonyloxy group, t-butoxycarbonyloxy group, cyclohexyloxycarbonyloxy group), aryloxycarbonyl An oxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyloxy group), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably Is a C1-C24 carba Yloxy group, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably carbon A sulfamoyloxy group having 1 to 32, more preferably 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group), alkylsulfonyloxy group (preferably Is an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group, or an arylsulfonyloxy group (preferably having a carbon number). 6 to 32, more preferably 6 to 2 carbon atoms An arylsulfonyloxy group of, for example, a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, a linear, branched, or cyclic acyl group, for example, Formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, linear, branched, Or a cyclic alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), an aryloxycarbonyl Group (preferably having 7 to 32 carbon atoms, more preferably Is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a carbamoyl group, N , N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N- Dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group) , 2-ethylhexylamino group, cyclohexylamino group), anilino group (preferably Or an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as an anilino group or an N-methylanilino group, or a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms). A heterocyclic amino group such as a 4-pyridylamino group, a carbonamide group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms such as an acetamido group, a benzamide group, a tetradecanamide group, Pivaloylamide group, cyclohexaneamide group), ureido group (preferably ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, ureido group, N, N-dimethylureido group, N-phenylureido group) ), An imide group (preferably an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, such as N- A succinimide group, N-phthalimido group), an alkoxycarbonylamino group (preferably a linear, branched or cyclic alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonyl Amino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms). An aryloxycarbonylamino group such as a phenoxycarbonylamino group, a sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methanesulfonamide group, butane Sulfonami Group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms, For example, a phenylazo group, a 3-pyrazolylazo group), an alkylthio group (preferably a linear, branched, or cyclic alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylthio group, Ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably having 6 to 48 carbon atoms, more preferred) Is an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzo A thiazolylthio group, a 2-pyridylthio group, a 1-phenyltetrazolylthio group), an alkylsulfinyl group (preferably a C1-C32, more preferably a C1-C24 linear, branched or cyclic alkyl) A sulfinyl group, for example, dodecanesulfinyl group), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably an arylsulfinyl group having 6 to 24 carbon atoms, for example, a phenylsulfinyl group), an alkylsulfonyl group (preferably C1-C48, more preferably C1-C24 linear, branched, or cyclic alkylsulfonyl Group, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably Is an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenylsulfonyl group or 1-naphthylsulfonyl group, a sulfamoyl group (preferably having 32 or less carbon atoms, more preferably 24 carbon atoms). The following sulfamoyl groups include, for example, sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfa Moyl group ), Sulfo group, carboxyl group, phosphate group, phosphonyl group (preferably phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenyl Phosphonyl), phosphinoylamino group (preferably phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as diethoxyphosphinoylamino group, dioctyloxyphosphinoylamino group) Group).

  The ionic group such as a sulfo group, a carboxyl group, or a phosphate group may be in a state containing a cation or an anion (also referred to as a “salt state”). For example, the carboxyl group, the phosphate group, and the sulfo group may be in a state containing a cation. Examples of the cation that forms a salt state include an ammonium ion, an alkali metal ion (eg, lithium ion, sodium ion). Potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidinium ions, tetramethylphosphonium).

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 ^{401 to} R in General Formula (M4) ⁴⁰⁷ , R ^{501 to} R ⁵¹¹ in General Formula (M5), R ^{601 to} R ⁶⁰⁸ in General Formula (M6), R ^{701 to} R ⁷⁰⁸ in General Formula (M7), R ⁸⁰¹ in General Formula (M8) to R ^809, if ^{the R} 901 ^{to R 913} in formula (M9) represents a substituent, the substituent, if it is further displaceable group may further have a substituent, Examples of the substituent include a substituent selected from the above-mentioned substituent group A. When the substituent has two or more substituents, these substituents may be the same or different. 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), and R in the general formula (M4). ^{When 401 to} R ⁴⁰⁷ represent a substituent, at least two of the substituents may be bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated ring, or an 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. When the substituent is substituted with two or more substituents, these substituents may be the same or different.

R ¹⁰¹ in the general formula (M1) is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydroxyl group.
R ¹⁰² in formula (M1) is preferably a hydrogen atom, a halogen atom, a carboxyl group, or an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably a hydrogen atom, a halogen atom, or a carboxyl group, and particularly preferably. Is a hydrogen atom, a bromine atom, or a carboxyl group.
R ¹⁰⁴ in the general formula (M1) is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. And particularly preferably an unsubstituted alkyl group having 1 to 8 carbon atoms.
R ¹⁰⁸ in the general formula (M1) is preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, A substituted or unsubstituted carbamoyl group is represented.
As R ^<103> , R ^<105> , and R ^{<106 >} in general formula (M1), Preferably each independently, a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C10 An aryl group, a halogen atom, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and particularly preferably a hydrogen atom.
As R ^<107> , R ^<109> and R ^{<110 >} in general formula (M1), Preferably each independently, a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C10 An aryl group, a halogen atom, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted carbamoyl group, more preferably a hydrogen atom or a halogen atom, particularly preferably hydrogen. Atom, chlorine atom, bromine atom.

R ²⁰¹ , R ²⁰⁵ , R ²⁰⁶ and R ²¹⁰ in formula (M2) are preferably each independently a hydrogen atom, a halogen atom or a hydroxyl group, more preferably a hydrogen atom.
R ²⁰² and R ²⁰⁹ in the general formula (M2) are preferably each independently a hydrogen atom, a halogen atom, a hydroxyl group, or a sulfo group, more preferably a hydrogen atom or a sulfo group, and particularly preferably hydrogen. Is an atom.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁷ and R ²⁰⁸ in formula (M2) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number of 6 A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and particularly preferably a hydrogen atom. , A substituted or unsubstituted alkyl group having 2 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
R ²¹¹ in the general formula (M2) is preferably a carboxylate group, a sulfonate group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group, more preferably A sulfonate group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, and a substituted or unsubstituted sulfamoyl group, particularly preferably a sulfonate group and an alkoxycarbonyl group.
R ²¹² , R ²¹³ , R ²¹⁴ , and R ²¹⁵ in formula (M2) are preferably each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a carboxyl group, Substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, sulfo group, substituted or unsubstituted sulfamoyl group, substituted or unsubstituted amino group, more preferably each independently a hydrogen atom, halogen atom, A carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a sulfo group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted amino group, particularly preferably each independently a hydrogen atom, Substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted A carbamoyl group, a sulfo group, a substituted or unsubstituted sulfamoyl group, and a substituted or unsubstituted amino group.
R ²¹⁴ and R ²¹⁵ in formula (M2) are also preferably bonded to each other to form a ring.
X ²⁰¹ in the general formula (M2) is preferably a chlorine ion, acetate ion, triflate ion, tetrafluoroborate ion, tetrakis (pentafluorophenyl) borate ion, perchlorate, bis (trifluoromethanesulfonyl) imide anion, and more Tetrakis (pentafluorophenyl) borate ion and bis (trifluoromethanesulfonyl) imide anion are preferable.
N201 in the general formula (M2) is preferably 0 or 1, more preferably 0.

In general formula (M3), R ³⁰¹ , R ³⁰² , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁷ , R ³⁰⁸ , R ³¹¹ , R ³¹² are preferably each independently a hydrogen atom, substituted or unsubstituted C 1-20. An alkyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a halogen atom, and a hydroxyl group, more preferably a hydrogen atom, a halogen atom, and a hydroxyl group, and particularly preferably a hydrogen atom.
R ³⁰³ , R ³⁰⁴ , R ³⁰⁹ and R ³¹⁰ in the general formula (M3) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number 6 to 20 represents an aryl group, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, particularly preferably a hydrogen atom or carbon. These are an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 10 carbon atoms.
R ³¹³ in the general formula (M3) is preferably a carboxylate group (—CO ₂ ^— ), a sulfonate group (—SO ₃ ^— ), a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, substituted or An unsubstituted sulfamoyl group, more preferably a sulfonate group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, particularly preferably a sulfonate group or an alkoxycarbonyl group. It is a group.
R ³¹⁴ in the general formula (M3) is preferably a hydrogen atom, a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a halogen atom. An atom or a hydroxyl group, particularly preferably a hydrogen atom.
R ³¹⁵ in formula (M3) is preferably a hydrogen atom, a substituted or unsubstituted amino group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a sulfo group, substituted or unsubstituted A sulfamoyl group and a hydroxyl group, more preferably a hydrogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, Particularly preferred are a substituted or unsubstituted amino group and a substituted or unsubstituted sulfamoyl group.
R ³¹⁶ and R ³¹⁷ in formula (M3) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, hydroxyl Group, a halogen atom, more preferably a hydrogen atom, a halogen atom, or a hydroxyl group, and particularly preferably a hydrogen atom.
R ³¹⁶ and R ³¹⁷ in formula (M3) are also preferably bonded to each other to form a ring.
X ³⁰¹ in the general formula (M3) is preferably a chlorine ion, an acetate ion, a triflate ion, a tetrafluoroborate ion, a tetrakis (pentafluorophenyl) borate ion, a perchlorate ion, or a bis (trifluoromethanesulfonyl) imide anion. More preferred are tetrakis (pentafluorophenyl) borate ion and bis (trifluoromethanesulfonyl) imide anion.
N301 in the general formula (M3) is preferably 0 or 1, more preferably 0.

R ⁴⁰¹ in the general formula (M4) is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted acyl group. And more preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and particularly preferably a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms.
R ⁴⁰² in formula (M4) is preferably a hydrogen atom, a substituted or unsubstituted amino group, more preferably a substituted or unsubstituted amino group, and particularly preferably a substituted or unsubstituted acylamino group. .
R ⁴⁰³ , R ⁴⁰⁶ and R ⁴⁰⁷ in formula (M4) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted carbon number of 1 -20 alkoxy groups and halogen atoms, more preferably hydrogen atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, and particularly preferably hydrogen atoms.
R ⁴⁰⁴ and R ⁴⁰⁵ in formula (M4) are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and more preferably Is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, particularly preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.

R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ , R ⁵⁰⁶ , R ⁵⁰⁷ , R ⁵⁰⁸ , R ⁵⁰⁹ , and R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R in general formula (M5) ^{604, R 605, R 606,} R 607, R 701 in ^{R 608,} and the general formula ^{(M7), R 702, R} 703, R 704, R 705, R 801 in ^{R 706,} and the general formula (M8), R ⁸⁰² , R ⁸⁰³ , R ⁸⁰⁴ , R ⁸⁰⁵ , R ⁸⁰⁶ , R ⁸⁰⁷ , and R ⁹⁰¹ , R ⁹⁰² , R ⁹⁰³ , R ⁹⁰⁴ , R ⁹⁰⁵ , R ⁹⁰⁶ , R ⁹⁰⁷ , R ⁹⁰⁸ , R ⁹⁰⁹ in general formula (M9) as ^{R 910, R 911,} preferably a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted C 1 20 alkyl groups, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, heterocyclic groups, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted acyl groups, substituted or unsubstituted An amino group, a cyano group, a substituted or unsubstituted sulfamoyl group, a carboxyl group, and a hydroxy group, more preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxyacyl group, a sulfamoyl group, Acylamino group.
R ⁵¹⁰ and R ⁵¹¹ in general formula (M5), R ⁷⁰⁷ and R ⁷⁰⁸ in general formula (M7), and R ⁸⁰⁸ and R ⁸⁰⁹ in general formula (M8), and R ⁹¹² and R ⁹¹³ in general formula (M9) Are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. .

  Specific examples of the dye represented by each of the general formulas (M1) to (M9) are shown below. Me represents a methyl group, Et represents an ethyl group, i-Pr represents an isopropyl group, and Bu represents an n-butyl group.

  Some of the dyes represented by the above general formulas (M1) to (M9) 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, WO 2010/110199, JP 2002-509957, etc.). The synthesis method is specifically illustrated in the examples.

[Repeating unit represented by general formula (10)]
Next, the repeating unit represented by the general formula (10) will be described.

In general formula (10), X ² and X ³ each independently represent a linking group, and D ² represents a dye residue obtained by removing two arbitrary hydrogen atoms from a dye.

In General Formula (10), X ² and X ³ represent a linking group. X ² and X ³ are preferably linking groups formed by polymerization, and are preferably portions corresponding to the main chain formed by the polymerization reaction. X ² and X ^{3 each} represents an alkylene group (a linear, branched, or cyclic alkylene group), an arylene group, a heterocyclic group, —CH═CH—, —O—, —S—, —NR— (R is Represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.), —C (═O) —, —SO—, —SO ₂ —, or a group in which two or more thereof are combined. These groups may have a substituent, and examples of the substituent include a substituent selected from the aforementioned substituent group A.

In the general formula (10), 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 exhibits the effects 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 (M9). It is more preferable to represent the dye residue, and it is particularly preferable to represent a dye residue obtained by removing two arbitrary hydrogen atoms from the dye represented by any one of the general formulas (M1) to (M4).

The repeating unit represented by the general formula (10) is preferably a repeating unit represented by the general formula (10-1) or (10-2).
The dye polymer containing the repeating unit represented by the general formula (10-1) is polyurethane, and the dye polymer containing the repeating unit represented by the general formula (10-2) is polyurea.

In General Formula (10-1) or General Formula (10-2), L ² and L ³ each independently represent a single bond or a linking group, L ⁴ represents a linking group, and D ² represents an arbitrary hydrogen atom from the dye. Represents a dye residue from which 2 are removed.

^{D 2} of the general formula (10-1) or formula (10-2) in is the same as ^{D 2} in the general formula (10).

In the general formula (10-1) or the general formula (10-2), the linking group in the case where L ² , L ³ and L ⁴ represent a linking group is not limited as long as the effects of the present invention can be achieved. Although not substituted, a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, etc.), An unsubstituted arylene group (for example, phenylene group, naphthylene group, etc.), a substituted or unsubstituted heterocyclic group, —CH═CH—, and a linking group formed by linking two or more of these are preferable. In these linking groups, —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.

L ² and L ³ are preferably a single bond or a divalent linking group. When L ² and L ³ are divalent linking groups, an alkylene group or a linking group formed by combining an alkylene group and —O— is preferable. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms.

L ⁴ is preferably a divalent linking group, more preferably an alkylene group, an arylene group, or a linking group formed by combining an alkylene group and an arylene group, and is an alkylene group having 1 to 20 carbon atoms. More preferably.

(Molecular weight of dye polymer)
In the present invention, since the dye polymer is used in a state of being dispersed in water, the dye polymer has an optimum molecular weight range with respect to dispersibility, and re-aggregation of the dispersion hardly occurs if the molecular weight is below the upper limit of the molecular weight range. On the other hand, it is difficult to dissolve in water and an aqueous organic solvent as long as it is at least the lower limit of the optimum molecular weight range. Although it varies depending on the type of dye polymer used, it is generally preferable to use those having a weight average molecular weight of 3,000 to 2,000,000, more preferably 3,000 to 1,000,000. 3,000 to 200,000 are particularly preferred.
The weight average molecular weight of the dye polymer can be calculated from gel permeation chromatography (GPC) measurement. In this specification, unless otherwise specified, GPC is measured using HLC-8220GPC (manufactured by Tosoh Corp.), columns measured with TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corp.), The average molecular weight was calculated by polystyrene conversion. The carrier may be selected as appropriate, but NMP (N-methylpyrrolidone) was used as long as it was soluble.

(Ionicity of dye polymer)
Since the dye polymer in the present invention 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. When the dye polymer has charge repulsion, the dye polymer has an anionic or cationic ionic group. Examples of the anionic group include a carboxyl group, a sulfo group, a phosphoric acid group, and salts thereof, and the cationic group is preferably an ammonium group. In terms of having ink jet suitability, the ionic group of the dye polymer is preferably an anionic group, and most preferably a carboxyl group. Examples of the salt include Li salt, Na salt, K salt, and ammonium salt.
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.

(Dye polymer melting and glass transition point (Tg))
In the inkjet printing method of the present invention, it is preferable to heat-treat after printing the aqueous dispersion of the dye polymer. In the heat treatment step, since the dye polymer is melt-dyed, the dye polymer is preferably melted at a heat treatment temperature or lower. Since it is preferable to perform a heat processing process normally at 100-200 degreeC, it is preferable that a dye polymer melts at 200 degrees C or less, and it is more preferable to melt at 180 degrees C or less.
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.
The Tg of the dye polymer is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 150 ° C. or lower.
The Tg of the dye polymer can be measured by DSC (differential scanning calorimetry).

(Structure of dye polymer)
The dye polymer may have a repeating unit including a structure derived from a dye as an essential structure, but from the viewpoint of dispersibility in water, a hydrophobic group (electrically neutral nonpolar group and water) It is more preferable to introduce a repeating unit containing at least one of an ionic group (a group having a low affinity) and an ionic group (an electrically ionic polar group having a high affinity for water). The molecular structure of the dye polymer may be linear or branched, may be random, alternating, periodic, or block, and may be a graft polymer designed with a trunk and branch structure.
As a method for forming the dye polymer, a method such as so-called copolymerization is preferable from the viewpoint of design flexibility. Examples of the copolymer component include the following hydrophobic group-containing monomers, anionic group-containing monomers, cationic group-containing monomers, and other functional monomers.
The content of the repeating unit having a structure derived from a dye in the dye polymer with respect to all repeating units is preferably 10 to 90% by mass, more preferably 25 to 90% by mass, and particularly preferably 50 to 80% by mass. It is. If the content rate of the repeating unit which has a structure derived from dye is 10 mass% or more, the coloring power per unit mass will improve and the dyeing density to a fabric will become high. Moreover, it is easy to adjust molecular weight to an appropriate range at the time of dye polymer synthesis as it is 90 mass% or less.

(Hydrophobic group-containing monomer)
Examples of the hydrophobic group-containing monomer include vinyl monomers such as styrene monomers, phenyl group-containing (meth) acrylates, (meth) acrylic acid alkyl esters, alkyl vinyl ethers, (meth) acrylonitrile; Urethane group-containing vinyl monomer formed from polyisocyanate and polyol or polyamine; epoxy group-containing vinyl monomer formed from epichlorohydrin and bisphenol; polyvalent carboxylic acid and polyalcohol etc. are formed from monomers Ester group-containing vinyl monomers; silicone group-containing vinyl monomers formed from organopolysiloxanes and the like.
Preferably, styrene, benzyl methacrylate, methyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-isocyanatoethyl methacrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate.

  Next, the ionic group includes an anionic group and a cationic group. Examples of monomers that give these ionic groups include the following.

(Anionic group-containing monomer)
As the anionic group-containing monomer, in the case of radical polymerization, the following unsaturated carboxylic acid monomer, unsaturated sulfonic acid monomer, unsaturated phosphoric acid monomer, or an anhydride or salt thereof: Etc. can be used. Examples of the unsaturated carboxylic acid monomer include (meth) acrylic acid, crotonic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, monoalkyl esters of unsaturated dicarboxylic acid, and anhydrides and salts thereof. Is mentioned. Examples of the salt include Na salt, K salt, Li salt, ammonium salt and the like.
Preferably, acrylic acid, methacrylic acid, acrylic acid dimer, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acrylic acid With leuoxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, acrylamide dodecanoic acid, methacrylamide dodecanoic acid or salts thereof is there.
Examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, sulfuric acid ester of 2-hydroxyalkyl (meth) acrylate, and salts thereof. Methacryloyloxypolypropylene glycol sulfate, alkenyloxypolyalkylene glycol sulfate, allyloxypolytetramethylene glycol / polyethylene glycol sulfate, allyloxypolypropylene glycol sulfate, allyloxypolypropylene glycol / polyethylene glycol sulfate, pentenyloxypolytetramethylene Glycol / polyethylene glycol sulfate, pentenyloxypolypropylene glycol sulfate, pentenyloxypolypropylene glycol / polyethylene glycol Lumpur sulfate, nonyl propenyl phenoxy polyethylene glycol sulfates, and the like. Examples of the salt include Na salt, K salt, Li salt, ammonium salt and the like.
Styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid are preferred.
Examples of the unsaturated phosphoric acid monomer include vinylphosphonic acid, phosphoric acid ester of hydroxyalkyl (meth) acrylate (having 2 to 6 carbon atoms), and (meth) acrylic acid alkylphosphonic acid.

  When the dye polymer is a polyurethane or polyurea having a repeating unit represented by the general formula (10-1) or the general formula (10-2), dimethylolpropionic acid or dimethylol is used as the anionic group-containing monomer. A diol-substituted carboxylic acid monomer such as butyric acid, a diol-substituted sulfonic acid monomer such as bis (2-hydroxyethyl) -5-sulfoisophthalate, or an anhydride or salt thereof can be used. Examples of the salt include Na salt, K salt, Li salt, ammonium salt and the like.

  As the anionic group-containing monomer, it is preferable to use a carboxylic acid monomer or an anhydride or salt thereof from the viewpoint of washing resistance.

(Cationic group-containing monomer)
As the cationic group-containing monomer, the following unsaturated amine-containing monomer, unsaturated ammonium salt-containing monomer, and the like can be used. Examples of the unsaturated amine-containing monomer include vinylamine, allylamine, vinylpyridine, methylvinylpyridine, N, N-dialkylaminostyrene, N, N-dialkylaminoalkyl (meth) acrylate, and dialkylaminoethyl vinyl ether. It is done.
Examples of the unsaturated ammonium salt-containing monomer include those obtained by quaternizing the unsaturated tertiary amine-containing monomer with a quaternizing agent.

[Other functional monomers]
In addition to the above copolymerization method, for example, urethane polymerization of a urethane-forming group-containing monomer into which an ionic group has been introduced in advance, or epoxy polymerization of an epoxy-forming group-containing monomer into which an ionic group has been introduced in advance. This method can also be adopted. In addition, the target polymer can be obtained by introducing a desired ionic group after polymerizing the basic polymer. In addition, other components may be contained, for example, polyethylene oxide having a hydroxyl group or an amide group without ionicity, a polyol or a hydroxyalkyl ester-containing monomer, acrylamide, hydroxyalkyl acrylate, vinyl acetate. , Vinyl alcohol, N-ethylmethacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone and the like can be copolymerized as monomers.

Specific examples of the dye polymer preferably used in the present invention are shown below, but are not limited thereto. L ¹ in * 1 positions bonded to the carbon atom of the polymer backbone, * 2 denotes respectively the coupling position with the D ^1, * 3 in the D ¹ represents a bonding position to L ^1.

(Aqueous dispersion of dye polymer)
The aqueous dispersion of the dye polymer contains at least water and (A) the dye polymer, and preferably contains (B) an aqueous organic solvent. In addition, depending on the method for producing the aqueous dispersion of the dye polymer, (C) the low molecular surfactant or the high molecular dispersant may be used in combination or not (so-called self-dispersing). Also good.

(A) Dye polymer In the present invention, the above-described dye polymer is used not in a state dissolved in water but in a state dispersed in water (water dispersion).
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 present invention, since a step of washing with water after printing is unnecessary, the dye polymer is a polymer that is substantially insoluble in water. In the aqueous dispersion of the present invention, the water-insoluble polymer is dispersed as particles, and the particle size is preferably 50 to 500 nm. If the polymer is dissolved in water, the polymer is not present as particles in water.
It is preferable to use ultrapure water as water.

(1-1) Dispersibility The dye polymer is readily compatible with water when dispersed in water as a property of the dye polymer itself or by adsorption with a low molecular surfactant or polymer dispersant used together (easy to wet). ), Electrostatic repulsion (repulsive force) and steric repulsion prevent the re-aggregation of fine particles of the dye polymer and have a function of suppressing sedimentation.

(1-2) Average particle diameter The dye polymer is in the form of particles in the aqueous dispersion. The dye polymer in the aqueous dispersion is a particulate dye polymer, and the average particle diameter of the particulate dye polymer is preferably 50 to 500 nm, more preferably 50 to 300 nm, and 50 to 200 nm. It is particularly preferred. Within this range, it is possible to directly print on a fabric provided with an aqueous pretreatment liquid by an 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 aqueous dispersion is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, and particularly preferably 3 to 25% by mass. Within this range, a high-density colored cloth can be obtained in printing while ensuring storage stability as an inkjet ink.
The water content in the water 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 aqueous dispersion and the ejection stability as an inkjet ink can be imparted. The stability of the aqueous dispersion indicates that precipitation or the like hardly occurs.

(B) Aqueous organic solvent As the aqueous organic solvent, water solubility at 25 ° C. is preferably 10 g / 100 g-H ₂ O or more, more preferably 20 g / 100 g-H ₂ O or more, water and optional Those which are mixed at a ratio of Examples of the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, 1,2,6 -Hexanetriol, thioglycol, hexylene glycol, glycerin, diglycerin, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol monoethyl ether, Examples thereof include ethylene glycol monobutyl ether and acetonitrile. Preferred are trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, 2-pyrrolidone, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol monobutyl ether, more preferably ethylene. Glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, 2-pyrrolidone and ethylene glycol monobutyl ether are preferred, with ethylene glycol, glycerin and 2-pyrrolidone being particularly preferred.
The content of the aqueous organic solvent in the 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 aqueous dispersion and the ejection stability as an inkjet ink can be imparted.

(C) Low molecular surfactant or polymer dispersant As the low molecular surfactant or polymer dispersant, a low molecular surfactant or polymer dispersant having a hydrophobic group and an ionic group is preferable. And preferably have the following characteristics.

(2-1) Dispersibility A low molecular surfactant or polymer dispersant is added when dispersing a dye polymer, so that the low molecular surfactant or polymer dispersant is adsorbed on the surface of the dye polymer. The dye polymer fine particles blended (wet) with water and ground by mechanical action prevent the fine particles from reaggregating by electrostatic repulsion (repulsive force) or steric repulsion, and have a function of suppressing sedimentation.

(2-2) Molecular Weight In the case of a polymer type dispersant, there is an optimum molecular weight for the dispersion effect with respect to the dye polymer. As the polymeric dispersant, it is preferable to use a dispersant having a weight average molecular weight of 2,000 to 50,000. The weight average molecular weight of the polymeric dispersant is measured by the same method as the weight average molecular weight of the dye polymer. When the weight average molecular weight is 50,000 or less, it is difficult to cause bridging between the dye polymer and the dye polymer, and it is difficult to cause aggregation of the dye polymer. On the other hand, when the weight average molecular weight is 2,000 or more, desorption from the dye polymer hardly occurs and the effect as a dispersant is easily exhibited.

(2-3) Structure and form The low molecular weight surfactant or polymer type dispersant is composed of a hydrophobic group (an electrically neutral nonpolar group having a low affinity with water) and an ionic group (electrical). It is preferable to have an ionic polar group having high affinity with water. The structure may be linear or branched. In the case of a high molecular weight surfactant, the structure may be random, alternating, periodic, or block, and may be a graft polymer designed with a trunk and branch structure.
The low molecular surfactant and the polymer dispersant can be used in any form of an aqueous solution, a dispersion, or an emulsion when mixed with water or an aqueous organic solvent.

(2-4) Forming Method and Obtaining Method For example, the following can be used as the low molecular surfactant or the polymeric dispersant.
Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. Examples of the anionic surfactant include fatty acid soap (for example, sodium oleate), N-acyl glutamate, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfoacetate, sulfated oil, higher alcohol sulfate ester And alkyl phosphate ester salts. Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, and imidazolinium betaine. A suitable example is an amine oxide type such as N, N-dimethyl-N-alkylamine oxide.
Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid Examples include esters, propylene glycol fatty acid esters, and acetylene glycols. A suitable example is SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant. In addition, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. Those listed as surfactants in 308119 (1989) can also be used.
The content of the low molecular surfactant is preferably in the range of 0.001% by mass to 5.0% by mass with respect to the total mass of the aqueous dispersion, and the surface tension of the aqueous dispersion is arbitrarily set within this range. It is preferable to adjust to.

The polymeric dispersant can be produced by copolymerizing a hydrophobic group-containing monomer and an ionic group-containing monomer. Each monomer may be used alone or in combination of two or more. The hydrophobic group-containing monomer and the ionic group-containing monomer are the same as the monomer for the copolymer component of the dye polymer described above. As the polymer dispersant, DISPERBYK-194N (trade name) manufactured by Big Chemie Japan Co., Ltd. can be used.
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 aqueous dispersion, and the surface tension of the aqueous dispersion is arbitrarily adjusted within this range. It is preferable to do.

The method for producing an aqueous dispersion of a dye polymer is as follows:
(I) After mixing a dye polymer powder or paste and, if necessary, a low molecular surfactant or a high molecular dispersant in water or an aqueous organic solvent, glass beads, zirconia beads, titania beads, Or a method of finely dispersing with an attritor or a mill with stainless steel balls,
(Ii) Water or an aqueous organic solvent, a polymerizable dye monomer that is hardly soluble in water or an aqueous organic solvent, and a copolymerization monomer and an emulsifier (surfactant) as necessary are mixed, and water or an aqueous organic solvent is mixed there. Using emulsion polymerization performed by adding a polymerization initiator (usually a radical generator) soluble in
(Iii) a method of obtaining a water dispersion of a dye polymer by synthesizing a dye polymer in an organic solvent and then emulsifying water and optionally a surfactant to remove the organic solvent;
(Iv) a method of obtaining an aqueous dispersion of a dye polymer by synthesizing a dye polymer in an organic solvent and then adding water, optionally a surfactant or solvent, and removing the solvent other than water;
(V) A method of obtaining an aqueous dispersion of a dye polymer by adding a monomer of a dye polymer in water, a polymerization initiator, and optionally adding a surfactant to emulsify, initiating polymerization to polymerize,
(Vi) A dye polymer monomer, a polymerization initiator, an organic solvent, and optionally a surfactant added in water to emulsify, start polymerization, polymerize, and simultaneously with polymerization or after polymerization To obtain an aqueous dispersion of a dye polymer by removing
(Vii) a method of obtaining an aqueous dispersion of a dye polymer by adding a monomer of a dye polymer in water, optionally adding a surfactant and emulsifying, adding a polymerization initiator, starting polymerization and polymerizing,
(Viii) a monomer of a dye polymer in water, optionally adding a surfactant or an organic solvent to emulsify, adding a polymerization initiator or optionally a polymerization initiator solution, initiating polymerization to polymerize, There is a method of obtaining an aqueous dispersion of a dye polymer by removing an organic solvent simultaneously with polymerization or after polymerization, and these can be suitably used.
In addition, a glycol solvent as a wetting agent, for example, ethylene glycol, propylene glycol, diethylene glycol, glycerin, polyethylene glycol, etc., and urea, hyaluronic acid, sucrose, etc. may be added to these dispersions as necessary. it can. In addition, the above-mentioned nonionic surfactants and anionic surfactants can be added as dispersion aids, but these surfactants are used in a small amount so as not to lower the performance as dispersion stability. It is preferable to mix.

(Inkjet ink)
The ink-jet ink used in the present invention contains at least a dye polymer aqueous dispersion. That is, the inkjet ink used in the present invention is a dispersion liquid in which a dye polymer is dispersed in a liquid containing water. In addition, the dye polymer is in the form of particles in the inkjet ink, and the preferable average particle diameter of the particulate dye polymer is the same as that described above.
The ink-jet ink used in the present invention contains an aqueous dispersion of the dye polymer, and preferably further contains water or an aqueous organic solvent. Moreover, you may contain components, such as another coloring agent, an organic solvent, surfactant, a crosslinking agent, and various additives as needed.

The ink-jet ink used in the present invention may further contain a colorant (dye or pigment) other than the dye polymer. When other colorants are included, the content of the dye polymer is preferably 50% by mass or more, more preferably 80% by mass or more, further 100% by mass, based on the total mass of the colorant including the dye polymer. That is, it is preferable to contain only a dye polymer.
The content of the colorant (including the dye polymer and other colorant) in the ink-jet ink is such that a good dyeing density is obtained, and the storage stability of the ink-jet ink is taken into consideration, with respect to the total mass of the ink-jet ink. 0.1 to 20% by mass is preferable, 1 to 15% by mass is more preferable, and 3 to 12% by mass is further preferable.
0.1-20 mass% is preferable, as for content of the dye polymer in an inkjet ink, 1-15 mass% is more preferable, and it is still more preferable that it is 3-12 mass%.
The water content 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.

<Organic solvent>
Examples of the organic solvent that can be contained in the inkjet ink used in the present invention include polyhydric alcohols (for example, ethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, tetraethylene). Glycol, triethylene glycol, tripropylene glycol, 1,2,4-butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 1,2-hexanediol, 1,5-pentane Diol, 1,2-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol 3-methyl-1,3-butanedio And 2-methyl-1,3-propanediol etc.), amines (eg ethanolamine and 2- (dimethylamino) ethanol etc.), monohydric alcohols (eg methanol, ethanol and butanol etc.), Alkyl ethers of polyhydric alcohols (for example, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, And dipropylene glycol monomethyl ether), 2,2′-thiodiethanol, amides (for example, N, N-di) Thioformamide, etc.), sulfolane, dimethylsulfoxide, sulfur-containing compounds such as 3-sulfolene, heterocycles (2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N- Ethyl morpholine) and acetonitrile. These may be used alone or in combination of two or more.
The organic solvent that can be contained in the inkjet ink used in the present invention is preferably the aforementioned aqueous organic solvent.
The content of the organic solvent in the inkjet ink is preferably 1% by mass to 60% by mass and more preferably 2% by mass to 50% by mass with respect to the total mass of the inkjet ink.

<Surfactant>
The inkjet ink used in the present invention can further use various surfactants from the viewpoint of enhancing storage stability, ejection stability, ejection accuracy, and the like. As the surfactant, any of cationic, anionic, amphoteric and nonionic surfactants can be used.

  Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts.

  Examples of anionic surfactants include fatty acid soaps, N-acyl glutamates, alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfoacetates, sulfated oils, higher alcohol sulfates, and alkyl phosphates. Etc.

  Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, and imidazolinium betaine. A suitable example is an amine oxide type such as N, N-dimethyl-N-alkylamine oxide.

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid Examples include esters, propylene glycol fatty acid esters, and acetylene glycols. A suitable example is Surfynol (trade name, manufactured by Air Products) which is an acetylene-based polyoxyethylene oxide surfactant.
In addition, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. Those listed as surfactants in 308119 (1989) can also be used.

When each of these surfactants is used, one surfactant may be used alone, or two or more surfactants may be mixed and used.
The content of the surfactant in the inkjet ink used in the present invention is preferably in the range of 0.001% by mass to 5.0% by mass with respect to the total mass of the inkjet ink. It is preferable to arbitrarily adjust the surface tension.

<Various additives>
The ink-jet ink used in the present invention may contain various other conventionally known additives. Examples of additives include pH adjusters such as acid bases and buffer solutions, fluorescent brighteners, surface tension adjusters, antifoaming agents, drying inhibitors, lubricants, thickeners, ultraviolet absorbers, anti-fading agents, Examples thereof include an antistatic agent, a matting agent, an antioxidant, a specific resistance adjuster, an antirust agent, an inorganic pigment, a reduction inhibitor, an antiseptic, an antifungal agent, a chelating agent, and a crosslinking agent.

(UV absorber)
As ultraviolet absorbers, they are described in JP-A-58-185777, JP-A-61-190537, JP-A-2-782, JP-A-5-197075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, JP-B-56 -21141, JP-A-10-88106, etc., cinnamic acid compounds, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10- Triazine compounds described in Japanese Patent No. 182621, Japanese National Publication No. Hei 8-501291, etc., Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used. When the inkjet ink contains an ultraviolet absorber, image storability can be improved.

(Anti-fading agent)
As an anti-fading agent, various organic and metal complex anti-fading agents can be used. Examples of organic fading inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex include a nickel complex and a zinc complex. More specifically, Research Disclosure No. No. 17643, VII, I and J, No. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. Included in the general formulas and compound examples of the compounds described in the patent cited in US Pat. No. 15162, and representative compounds described in JP-A-62-215272, pages 127 to 137, and US Pat. No. 5,356,443. Can be used. When the ink-jet ink contains an anti-fading agent, image storability can be improved.

(Preservatives and antifungal agents)
The ink-jet ink used in the present invention may contain at least one of a preservative and an antifungal agent in order to maintain long-term storage stability of the ink. When the ink-jet ink contains a preservative or an antifungal agent, long-term storage stability can be enhanced. Examples of antiseptics and antifungal agents include aromatic halogen compounds (for example, Priventol CMK; trade name, manufactured by LANXESS), methylene dithiocyanate, halogen-containing nitrogen sulfur compounds, 1,2-benzisothiazolin-3-one (For example, Proxel GXL; manufactured by Arch Chemicals, trade name), sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, And salts thereof.
A preservative and an antifungal agent may be used individually by 1 type, and may use 2 or more types together. When the inkjet ink contains a preservative and an antifungal agent, the content of the antiseptic and the antifungal agent is preferably 0.02% by mass to 1.00% by mass with respect to the total mass of the inkjet ink.

(Anti-drying agent)
As the drying inhibitor, an aqueous organic solvent having a vapor pressure lower than that of water can be suitably used. When the inkjet ink contains an anti-drying agent, clogging due to drying of the ink can be prevented at the ejection port of the nozzle of the ejection head that ejects the ink when used for inkjet recording.
Specific examples of the drying inhibitor include, for example, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol. , Acetylene glycol derivatives, glycerin, polyhydric alcohols typified by trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) Lower alkyl ethers of polyhydric alcohols such as ethers, heterocycles such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N-ethylmorpholine, Horan, dimethyl sulfoxide, and sulfur-containing compounds such as sulfolane, diacetone alcohol, and polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred.
Moreover, a drying inhibitor may be used individually by 1 type, and may use 2 or more types together. When said inkjet ink contains a drying inhibitor, 10 mass%-50 mass% are preferable with respect to the total mass of an inkjet ink.

(PH adjuster)
As a pH adjuster, neutralizers, such as an organic base and an inorganic alkali, can be used, for example. When the inkjet ink is used for recording, the storage stability of the inkjet ink can be improved by containing a pH adjuster in the inkjet ink. The pH adjuster is preferably added so that the pH of the inkjet ink is 5 to 12, and more preferably added so that the pH is 5 to 9.

(Surface tension modifier and antifoaming agent)
Examples of the surface tension adjusting agent include various surfactants such as nonionic surfactants, cationic surfactants, and anionic surfactants. Preferred examples of the surfactant are the same as those exemplified in the above-mentioned surfactant column.
As the antifoaming agent, fluorine-based and silicone-based compounds are preferable.

The surface tension of the inkjet ink used in the present invention is preferably adjusted to 20 mN / m to 70 mN / m, and more preferably adjusted to 25 mN / m to 60 mN / m. The viscosity of the inkjet ink is preferably adjusted to 40 mPa · s or less, more preferably adjusted to 30 mPa · s or less, and particularly preferably adjusted to 20 mPa · s or less.
Surface tension and viscosity are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant, a surfactant and the like.

(Chelating agent)
The chelating agent is preferably used for the purpose of preventing the generation of precipitates such as precipitates in the ink-jet ink, and for the purpose of improving storage stability and clogging recovery. When dyes are used as colorants for inkjet inks, the metal ions (Ca, Mg, Si, Fe, etc.) contained in the ink can cause precipitation and reduce clogging recovery. It is known that it is necessary to manage below the amount. In addition, when a copper complex dye is used, even if the amount of metal ions is controlled, if the amount of free copper ions is not controlled, the occurrence of precipitates and a reduction in clogging recovery may be observed. (See JP 2000-355665, JP 2005-126725, etc.).
Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, uramildiacetic acid, and metal salts thereof (for example, sodium salt).

(Crosslinking agent)
Although it does not specifically limit as a crosslinking agent, It is preferable that it is at least 1 sort (s) chosen from a block isocyanate type crosslinking agent, an epoxy type crosslinking agent, and a methylol type crosslinking agent.

<Heat treatment process>
The ink jet textile printing method of the present invention preferably further includes a heat treatment step. In particular, the dye polymer particles can be melted (or softened) and the adhesion to the fibers can be improved by performing a heat treatment after printing on the fabric in the printing process (that is, by performing heat treatment, Can be worn). 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 this heat treatment step, a crosslinking reaction is performed using a reactive group introduced into the dye polymer (for example, a blocked isocyanate group) or a crosslinking agent (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent) used in combination as an additive. Is preferable from the viewpoint of friction resistance.
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>
A fabric colored with an ink-jet ink containing an aqueous dispersion of the dye polymer of the present invention is excellent in texture flexibility or fastness (washing resistance, sweat resistance, friction resistance, and dry cleaning resistance), but necessary Accordingly, by subjecting the colored cloth to a padding treatment on the entire surface, a colored cloth having further improved texture flexibility or fastness (particularly friction resistance) can be obtained. Post-treatment agents for the purpose of softening include cationic surfactants, anionic surfactants, nonionic surfactants, dimethyl silicone oil, amino silicone oil, carboxy modified silicone oil, hydroxy modified silicone oil, fatty acid , Fatty acid amide, mineral oil, vegetable oil, animal oil, plasticizer and the like.
Further, as a post-treatment agent for improving the smoothness of the colored fabric surface, metal soap, paraffin wax, carnauba wax, microstalline wax, dimethyl silicone oil, amino silicone oil, carboxy modified silicone oil, hydroxy modified silicone oil, etc. Is mentioned.
In the padding treatment, these post-treatment agents are emulsified, thermally emulsified, or dispersed in a water solvent by stirring with a mixer, and a colored cloth is dipped, dried with mangles, dried and heat treated.
Moreover, the friction resistance of a colored cloth can be improved by mix | blending a small amount of resin emulsion as a fixing agent in a post-processing agent. The blending amount with respect to the post-treatment agent is preferably less than 5%, which is preferable because the softness of the texture of the colored fabric is not easily impaired.
The resin emulsion blended into the post-treatment agent as a sticking agent is not particularly limited, but is an acrylic ester resin emulsion, a urethane resin emulsion, an ethylene / vinyl acetate copolymer resin (EVA resin) emulsion, a silicone / acrylic resin emulsion. Polyester resin emulsion or the like can be used, and in order to soften the texture of the colored cloth, the glass transition point of these resin emulsions is preferably 0 ° C. or lower.

[Method for producing colored fabric]
The method for producing a colored fabric according to the present invention comprises an inkjet ink comprising a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to a fabric, and an aqueous dispersion of a dye polymer having a repeating unit containing a structure derived from a dye. And a printing step of printing on the fabric provided with the aqueous pretreatment liquid by an ink jet method.

<Fabric>
Examples of the fabric to which the inkjet printing method and the colored fabric manufacturing 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.
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.

  The colored cloth produced by the ink jet printing method and colored cloth producing method of the present invention can provide excellent color development, washing fastness, sweat fastness, friction fastness, dry cleaning fastness, and printing workability. In any of the properties, since excellent effects are exhibited, the inkjet printing method and the colored cloth manufacturing method of the present invention are highly valuable.

[Colored fabric]
The present invention also relates to a colored fabric having an image including a flocculant and a dye polymer having a repeating unit including a structure derived from a dye on at least a part of the surface of the fabric.

[Preparation of aqueous pretreatment liquid A (1) containing flocculant]
An aqueous pretreatment liquid A (1) was prepared by mixing and stirring the following components.
Cachiomaster PD-7 (flocculating agent; manufactured by Yokkaichi Synthesis, solid content 50% by mass)
50g
BYK348 (by Big Chemie Japan) 5g
Glycerin 100g
845g of water

[Preparation of aqueous pretreatment liquid A (2) containing flocculant]
An aqueous pretreatment liquid A (2) was prepared by mixing and stirring the following components.
Unisense FPA100L (Senka, solid content 27% by mass)
37g
BYK348 (by Big Chemie Japan) 5g
Glycerin 100g
858g of water

[Preparation of aqueous pretreatment liquid A (3) containing flocculant]
An aqueous pretreatment liquid A (3) was prepared by mixing and stirring the following components.
(2-hydroxyethyl) trimethylammonium chloride (manufactured by Tokyo Chemical Industry) 100 g
Citric acid (Wako Pure Chemical Industries) 50g
BYK348 (by Big Chemie Japan) 5g
Glycerin 100g
745g of water

[Preparation of aqueous pretreatment liquid A (4) containing flocculant]
An aqueous pretreatment liquid A (4) was prepared by mixing and stirring the following components.
(2-hydroxyethyl) trimethylammonium chloride (manufactured by Tokyo Chemical Industry) 100 g
Unisense FPV1000L (Senka, solid content 20% by mass)
500g
BYK348 (by Big Chemie Japan) 5g
150 g of propylene glycol
245g of water

[Preparation of aqueous pretreatment liquid A (5) containing flocculant]
An aqueous pretreatment liquid A (5) was prepared by mixing and stirring the following components.
250 g malonic acid (Wako Pure Chemicals)
Emulgen P109 (made by Kao) 10g
200 g of diethylene glycol monomethyl ether (Wako Pure Chemical Industries, Ltd.)
540g of water

[Preparation of aqueous pretreatment liquid A (6) containing flocculant]
Aqueous pretreatment liquid A (6) was prepared by mixing and stirring the following components.
Calcium nitrate tetrahydrate (Wako Pure Chemical Industries) 200g
BYK348 (by Big Chemie Japan) 5g
150 g of propylene glycol
245g of water

[Preparation of aqueous pretreatment liquid A (7) containing flocculant]
An aqueous pretreatment liquid A (7) was prepared by mixing and stirring the following components.
Cachio Master PD-7 (flocculating agent; manufactured by Yokkaichi Synthesis, solid content 50% by mass) 100 g
BYK348 (by Big Chemie Japan) 5g
Glycerin 100g
Triethylene glycol monobutyl ether 50g
1,2-hexanediol 20g
30 g of trimethylolpropane (Wako Pure Chemical Industries)
695 g of water

[Preparation of aqueous pretreatment liquid A (8) containing flocculant]
Aqueous pretreatment liquid A (8) was prepared by mixing and stirring the following components.
Cachio Master PD-7 (flocculating agent; manufactured by Yokkaichi Synthesis, solid content 50% by mass) 50 g
NBP-211 (Meisei Chemical Co., Ltd., solid content 40% by mass) 13 g
BYK348 (by Big Chemie Japan) 5g
Glycerin 100g
832 g of water

(Synthesis of dye polymer (Y-2-1))
10 mL of N-methylpyrrolidone (NMP) was added to a 100 mL three-necked flask, and the internal temperature was raised to 85 ° C. In NMP, 9.0 g of polymerizable monomer YM-1 (synthesized by the method described in Japanese Patent No. 5315267), 1.0 g of polymerizable monomer methacrylic acid (MAA), V-601 (manufactured by Wako Pure Chemicals, Product name) 0.126 g and a solution prepared by dissolving 0.443 g of 1-dodecanethiol in 13.24 g of NMP were added dropwise over 3 hours. After completion of dropping, the reaction solution A was obtained by reacting at 85 ° C. for 1 hour. Then, V-601 (0.098g) was added to the reaction liquid A, and also it was made to react at 85 degreeC for 2 hours, and the reaction liquid B was obtained. The reaction solution B is allowed to cool to room temperature (20 ° C.), poured into 500 mL of water, the crystals are precipitated, and the crystals are filtered off by filtration, and then the filtered crystals are dried for 1 day in a 60 ° C. blower dryer. A yellow powder of the exemplified compound (Y-2-1), which is a dye polymer, was obtained. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of Exemplified Compound (Y-2-1) in tetrahydrofuran (THF) was 441 nm. Moreover, the weight average molecular weight (Mw) in the gel permeation chromatography (GPC) measurement of exemplary compound (Y-2-1) was 10,500 (polystyrene conversion). The Tg of Exemplified Compound (Y-2-1) in DSC (Differential Scanning Calorimetry) was 160 ° C. The exemplified compound (Y-2-1) was a polymer that melted at 200 ° C.

(Synthesis of dye polymer (R-1-1) and (B-3-1))
The exemplary compounds (R-1-1) and (B-3-1) of the dye polymer described above were synthesized according to the method for synthesizing the dye polymer (Y-2-1). Clear Tg of the exemplary compounds (R-1-1) and (B-3-1) in DSC (differential scanning calorimetry) could not be observed. On the other hand, as the melting temperature, the exemplified compounds (R-1-1) and (B-3-1) were both polymers that melt at 170 to 180 ° C.

(Preparation of aqueous dispersion of dye polymer)
<Preparation of dye polymer aqueous dispersion (1)>
0.5 g of exemplified compound (Y-2-1), 0.325 g of EFKA7422 (manufactured by BASF), 4.125 g of ultrapure water, and 10 g of zirconia beads having a diameter of 0.1 mm are mixed, and a planetary fine particle crusher (Fritsch) is mixed. A dispersion liquid was obtained by dispersing for 10 hours at 400 rpm (rotation per minute) using Pulversette 7). Zirconia beads were removed from the resulting dispersion using a filter cloth to obtain a dye polymer aqueous dispersion (1).

<Preparation of dye polymer aqueous dispersion (2)>
1.0 g of exemplified compound (R-1-1), 1.38 g of demole NL (manufactured by Kao), 2.62 g of ultrapure water, and 10 g of zirconia beads having a diameter of 0.1 mm are mixed, and an aqueous dye polymer dispersion (1) In the same manner as above, a dye polymer aqueous dispersion (2) was obtained.

<Preparation of dye polymer aqueous dispersion (3)>
A dye polymer aqueous dispersion (3) was prepared in the same manner as the dye polymer aqueous dispersion (2) except that the dye polymer was changed to the type shown in Table 2 below.
Further, the weight average molecular weight of the used dye polymer and the average particle diameter of the particulate dye polymer in the obtained dye polymer aqueous dispersion were as shown in Table 2.

<Preparation of Dye Polymer Water Dispersion (4)>
According to the method described in Example 1 of JP-T-2002-509957, a brown 25% by weight dye polymer aqueous dispersion (4) was prepared. The weight average molecular weight of the dye polymer contained in the dye polymer aqueous dispersion (4) was 5,100, and the volume average particle diameter was 164 nm. The melt temperature of the dye polymer obtained by freeze-drying the dye polymer aqueous dispersion (4) was 120 ° C., and the Tg by DSC (differential scanning calorimetry) was 90 ° C.

<Preparation of dye polymer aqueous dispersion (5)>
According to the method described in Example 6 of JP-T-2002-509957, a 25% by weight dye polymer aqueous dispersion (5) of yellow color was prepared. The weight average molecular weight of the dye polymer contained in the dye polymer aqueous dispersion (5) was 3,300, and the volume average particle diameter was 84 nm. The melting temperature of the dye polymer obtained by freeze-drying the dye polymer aqueous dispersion (5) was 160 ° C., and the Tg in DSC (differential scanning calorimetry) was 120 ° C.

<Preparation of dye polymer aqueous dispersion (6)>
According to the method described in Example 8 of JP-T-2002-509957, a magenta 25% by mass dye polymer aqueous dispersion (6) was prepared. The weight average molecular weight of the dye polymer contained in the dye polymer aqueous dispersion (6) was 4,010, and the volume average particle diameter was 134 nm. The melting temperature of the dye polymer obtained by freeze-drying the dye polymer aqueous dispersion (6) was 170 ° C., and the Tg of DSC (differential scanning calorimetry) was 100 ° C.

<Preparation of dye polymer aqueous dispersion (7)>
According to the method described in Example 11 of JP-T-2002-509957, a 25% by mass dye polymer aqueous dispersion (7) of navy color was prepared. The weight average molecular weight of the dye polymer contained in the dye polymer aqueous dispersion (7) was 4,600, and the volume average particle diameter was 144 nm. The melt temperature of the dye polymer obtained by freeze-drying the dye polymer aqueous dispersion (7) was 180 ° C., and the Tg of DSC (differential scanning calorimetry) was 120 ° C.

[Preparation of inkjet ink for textile printing]
<Preparation of inkjet ink B (1) for textile printing>
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a membrane filter (average pore size 0.8 μm) to prepare inkjet ink B (1) for printing.
Dye polymer aqueous dispersion (1) 2.5g
Trimethylolpropane 0.056g
1.413 g 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

<Preparation of inkjet inks B (2) to B (3) for textile printing>
The dye polymer aqueous dispersion (1) was changed to the types and amounts shown in Table 3 below, and the amount of ultrapure water was adjusted accordingly, in the same manner as the inkjet ink B (1) for printing. Inkjet inks B (2) to B (3) were prepared.

<Preparation of inkjet ink B (4) for textile printing>
Textile inkjet ink B (4) was prepared in the same manner as textile inkjet ink B (1) except that the crosslinking agent shown in Table 3 below was added and the amount of ultrapure water was adjusted accordingly.

<Preparation of inkjet ink B (5) for textile printing>
The type and amount of the dye polymer aqueous dispersion was changed from “2.5 g of dye polymer water dispersion (1)” to “0.5 g of dye polymer water dispersion (4)”, and the amount of ultrapure water was changed to “1”. Textile printing ink-jet ink B (5) was prepared in the same manner as textile printing ink-jet ink B (1) except that it was changed from “.413 g” to “3.412 g”.

<Preparation of inkjet ink B (6) for textile printing>
A printing inkjet ink B (6) was prepared in the same manner as the printing inkjet ink B (5) except that the dye polymer aqueous dispersion (4) was changed to the dye polymer aqueous dispersion (5).

<Preparation of inkjet ink B (7) for textile printing>
A printing inkjet ink B (7) was prepared in the same manner as the printing inkjet ink B (5) except that the dye polymer aqueous dispersion (4) was changed to the dye polymer aqueous dispersion (6).

<Preparation of inkjet ink B (8) for textile printing>
A textile printing inkjet ink B (8) was prepared in the same manner as the textile printing ink jet B (5) except that the dye polymer aqueous dispersion (4) was changed to the dye polymer aqueous dispersion (7).

(Example 1)
[Pretreatment process]
The prepared aqueous pretreatment liquid A (1) was squeezed onto a cotton fabric (with cotton broad sill, manufactured by Color Dye Co., Ltd., product code A02-01002) by a padding method and dried for 24 hours. .
The squeezing rate (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid relative to the fabric after the cloth containing the aqueous treatment liquid is squeezed.

[Printing process]
The ink jet ink B (1) for textile printing obtained as described above is filled in an ink cartridge, and an image is printed on the cotton fabric after the pretreatment step using an ink jet printer (PX-045A, manufactured by Seiko Epson Corporation). Recorded.

[Heating process]
The colored fabric after the above printing process is dried at 20 ° C. for 12 hours, and then heated at 200 ° C. for 60 seconds using a heat press machine (desktop automatic flat press machine AF-54TEN type, manufactured by Asahi Textile Machinery Co., Ltd.). Heating was performed to fix the ink, and the crosslinking reaction was allowed to proceed.

(Examples 2-4, 6, 8, 9)
The fabric was the same as in Example 1 except that the type of aqueous pretreatment liquid, the method of applying the aqueous pretreatment liquid to the fabric, and the type of inkjet ink for textile printing were changed to the types shown in Table 5 below, respectively. Was ink jet printed.

(Example 5)
Example 1 except that the pretreatment step was changed to a step of applying the prepared aqueous pretreatment liquid A (5) to a cotton fabric using a bar coater (manufactured by Matsuo Sangyo Co., Ltd., # 16) and drying it for 24 hours. A colored fabric was obtained in the same manner.

(Example 7)
In the pretreatment step, the prepared aqueous pretreatment liquid A (7) is filled into an ink cartridge, applied to a cotton fabric using an inkjet printer (PX-045A, manufactured by Seiko Epson Corporation), and dried for 24 hours. A colored fabric was obtained in the same manner as in Example 3 except that the process was changed.

(Example 10)
A colored cloth was obtained in the same manner as in Example 1 except that the textile printing ink-jet ink B (1) was changed to the textile printing ink-jet ink B (5).

(Example 11)
A colored fabric was obtained in the same manner as in Example 1, except that the inkjet ink B (1) for textile printing was changed to the inkjet ink B (6) for textile printing.

Example 12
A colored fabric was obtained in the same manner as in Example 1 except that the inkjet ink B (1) for textile printing was changed to the inkjet ink B (7) for textile printing.

(Example 13)
A colored fabric was obtained in the same manner as in Example 7 except that the textile printing ink-jet ink B (3) was changed to the textile printing ink-jet ink B (8).

(Comparative Example 1)
<Preparation of pigment dispersion>
Styrene-acrylic acid copolymer Joncryl 678 (manufactured by BASF) (3 parts by mass), dimethylaminoethanol (1.3 parts by mass), and water (80.7 parts by mass) were stirred at 70 ° C. and mixed. Next, C.I. I. Pigment Blue 15: 3 (15 parts by mass) and zirconia beads having a particle size of 0.5 mm were filled by 50% by volume and dispersed using a sand glider mill to obtain a 15% cyan pigment dispersion.

<Preparation of inkjet ink P (1) for textile printing>
The pigment dispersion (20 parts by mass), polyurethane resin WBR-2101 (manufactured by Taisei Fine Chemical Co., Ltd., solid content 25%) (24 parts by mass), glycerin (12 parts by mass), triethylene glycol monobutyl ether (2 parts by mass) , 2-pyrrolidone (3 parts by mass), Surfynol 465 (1 part by mass), 1,2-hexanediol (2 parts by mass), and water (36 parts by mass) are mixed, and a membrane filter (pore size: 0. 0 parts). 8 μm) to obtain an inkjet ink P (1) for textile printing.

<Inkjet printing process>
Ink jet textile printing was carried out in the same manner as in Example 1 except that the ink jet ink P (1) for textile printing was used without performing the pretreatment process.

<Heating process>
The colored fabric was heat-treated in the same manner as in Example 1 except that the heating conditions were changed to 150 ° C. and 3 minutes.

(Comparative Example 2)
C. I. Pigment Blue 15: 3 to C.I. I. Printing was carried out in the same manner as in Comparative Example 1 except that Pigment Red 122 was used to prepare inkjet ink P (2) for printing, and this was used.

(Comparative Example 3)
C. I. Pigment Blue 15: 3 to C.I. I. Printing was performed in the same manner as in Comparative Example 1 except that Pigment Yellow 74 was used to prepare inkjet ink P (3) for printing, and this was used.

(Comparative Example 4)
After carrying out the pretreatment step by the same method as in Example 1, inkjet printing was carried out in the same manner as in Comparative Example 3.

The evaluation results of Examples 1 to 13 and Comparative Examples 1 to 4 are shown in Tables 5 to 7. The evaluation of the colored fabric is the result of the following method.
Color developability: The optical density (OD (Optical Density) value) was measured using a colorimeter (Gretag Macbeth Spectrolino, manufactured by X-Rite). The OD value is a numerical value obtained by logarithmizing the ratio of the reflected light to the irradiated light, and the higher the OD value, the higher the density image is obtained. In this example and comparative examples, the OD was evaluated in four stages as described in Table 4 below.

-Washing resistance: Evaluated based on JIS L-0844 A-2 (revised in 2011). The evaluation result of washing resistance indicates that the larger the value, the better the fastness.
-Sweat resistance: Evaluated based on JIS L-0848 (revised in 2004). The evaluation result of sweat resistance indicates that the larger the value, the better the fastness.
-Friction resistance: Evaluated based on JIS L-0849 type II (revised in 2013). The evaluation result of friction resistance shows that the larger the value, the better the fastness.
-Dry cleaning resistance: Evaluated based on JIS L-0860 A-1 method (revised in 2008). The evaluation result of dry cleaning resistance indicates that the larger the value, the better the fastness.

(Example 14)
The cotton fabric used in Example 1 (with cotton broad sill, manufactured by Color Dyeing Co., Ltd., product code A02-01002) was converted into a polyester fabric (polyester tropical (made by Teijin Ltd.), manufactured by Color Dyeing Co., Ltd., product code A02. A colored fabric was obtained in the same manner except that it was changed to -01019). The obtained colored fabric showed high colorability as well as the colored fabric using cotton fabric, and showed excellent washing resistance, sweat resistance, friction resistance, and dry cleaning resistance.

(Example 15)
The cotton fabric used in Example 1 (with cotton broad sill, manufactured by Color Dye Co., Ltd., product code A02-01002) is a 65% cotton 35% blended fabric (blended polyester 65 / cotton 35 broad, Color Dye Co., Ltd.). A colored cloth was obtained in the same manner except that the product code was changed to product code A02-01030). The obtained colored fabric showed high colorability as well as the colored fabric using cotton fabric, and showed excellent washing resistance, sweat resistance, friction resistance, and dry cleaning resistance.

  As is apparent from the above results, the inkjet printing method according to the embodiment of the present invention does not require the application of printing paste and washing with water, and wastewater and waste materials are not generated, so there is little environmental load and there is no problem in workability. It is possible to obtain a colored fabric having excellent color development and fastness.

Claims (19)

  The aqueous pretreatment liquid was applied to a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to the fabric, and an inkjet ink containing an aqueous dispersion of a dye polymer having a repeating unit containing a structure derived from a dye. An ink-jet printing method comprising: a printing step of printing on a fabric by an ink-jet method.   The ink-jet printing method according to claim 1, further comprising a heat treatment step.   The inkjet printing method according to claim 1 or 2, wherein the pretreatment step is a step of applying the aqueous pretreatment liquid to a fabric by a coating method, a padding method, a spray method, a screen printing method, or an inkjet method.   The inkjet printing method according to any one of claims 1 to 3, wherein the flocculant is at least one selected from organic acids, polyvalent metal salts, and cationic compounds.   The inkjet printing method according to any one of claims 1 to 4, wherein a content of the flocculant is 0.1 to 50% by mass with respect to a total amount of the aqueous pretreatment liquid.   The inkjet printing method according to any one of claims 1 to 5, wherein the aqueous pretreatment liquid further contains a crosslinking agent.   The inkjet printing method according to any one of claims 1 to 6, wherein the inkjet ink containing the aqueous dispersion of the dye polymer further contains a crosslinking agent.   The inkjet printing method according to claim 6 or 7, wherein the crosslinking agent is at least one selected from a blocked isocyanate crosslinking agent, an epoxy crosslinking agent, and a methylol crosslinking agent.   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, indophenol dye, nigrosine dye, oxazine dye Inkjet printing according to any one of claims 1 to 8, which is at least one dye selected from the group consisting of thiazine dyes, anthraquinone dyes, indigo dyes, quinophthalone dyes, porphyrin dyes, cyanine dyes and phthalocyanine dyes Method. The dye polymer according to any one of claims 1 to 9, wherein the dye polymer is a dye polymer comprising a repeating unit represented by the following general formula (1) or (10) as a repeating unit including a structure derived from the dye. 2. The ink jet printing method according to item 1.

In General Formula (1), X ¹ represents a linking group, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye.

In general formula (10), X ² and X ³ each independently represent a linking group, and D ² represents a dye residue obtained by removing two arbitrary hydrogen atoms from a dye. D ¹ in the general formula (1) or D ² in the general formula (10) is an arbitrary hydrogen atom from the dye represented by any one of the following general formulas (M1) to (M9) or The inkjet printing method according to claim 10, which represents a dye residue from which two are removed.

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 ^{401 to} R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent.

In General Formula (M5), R ^{501 to} R ⁵¹¹ each independently represent a hydrogen atom or a substituent.

In General Formula (M6), R ^{601 to} R ⁶⁰⁸ each independently represent a hydrogen atom or a substituent.

In General Formula (M7), R ^{701 to} R ⁷⁰⁸ each independently represent a hydrogen atom or a substituent.

In General Formula (M8), R ^{801 to} R ⁸⁰⁹ each independently represent a hydrogen atom or a substituent.

In General Formula (M9), R ^{901 to} R ⁹¹³ each independently represent a hydrogen atom or a substituent.   The inkjet printing method according to claim 1, wherein the dye polymer is an acrylic polymer, a urethane polymer, or a styrene polymer.   The inkjet printing method according to any one of claims 1 to 12, wherein the amount of the ionic group in the dye polymer is 0.1 to 1.8 mmol / g.   The inkjet printing method according to any one of claims 1 to 13, wherein the glass transition point of the dye polymer is 200 ° C or lower.   The inkjet printing method according to any one of claims 1 to 14, wherein the dye polymer melts at 200 ° C or lower.   The inkjet according to any one of claims 1 to 15, wherein the dye polymer in the aqueous dispersion of the dye polymer is a particulate dye polymer, and the average particle diameter of the particulate dye polymer is 50 to 500 nm. Printing method.   The inkjet printing method according to any one of claims 1 to 16, wherein the dye polymer has a weight average molecular weight of 3,000 to 2,000,000.   The aqueous pretreatment liquid was applied to a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to the fabric, and an inkjet ink containing an aqueous dispersion of a dye polymer having a repeating unit containing a structure derived from a dye. A method for producing a colored fabric, comprising: a printing step of printing on the fabric by an inkjet method. A colored cloth having an image including a flocculant and a dye polymer having a repeating unit including a structure derived from a dye on at least a part of the surface of the cloth.