WO2017146071A1

WO2017146071A1 - Inkjet textile printing method, coloring composition, inkjet ink, ink cartridge, and dye polymer

Info

Publication number: WO2017146071A1
Application number: PCT/JP2017/006443
Authority: WO
Inventors: 征夫谷; 藤江　賀彦; 未奈子原
Original assignee: 富士フイルム株式会社
Priority date: 2016-02-26
Filing date: 2017-02-21
Publication date: 2017-08-31
Also published as: JPWO2017146071A1

Abstract

The present invention provides: a dye polymer which includes a structure derived from a dye having an anthraquinone skeleton; an inkjet textile printing method comprising a step for printing an inkjet ink, which contains an aqueous dispersion of the dye polymer, directly on a cloth by inkjet printing; a coloring composition and an inkjet ink each of which contains the aqueous dispersion of the dye polymer; and an ink cartridge filled with the inkjet ink.

Description

Inkjet textile printing method, coloring composition, inkjet ink, ink cartridge, and dye polymer

The present invention relates to an inkjet printing method, a coloring composition, an inkjet ink, an ink cartridge, and a dye polymer.

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, Inkjet systems have been used. In particular, the inkjet method does not need to prepare a plate 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 printing using dyes needs to be pre-applied with a printing paste as a pretreatment agent in order to prevent bleeding (improve sharpness), and in addition, the dye is fixed after dyeing. Therefore, it is necessary to steam-heat the colored fabric, and then wash the excess dye and the printing paste as the pretreatment agent 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 and 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 dispersing agent are mixed in water and then finely dispersed with an attritor or a mill machine together with glass beads, zirconia beads, titania beads, 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). In addition, a large amount of emulsion resin must be used as a fixing agent, the texture of the colored cloth becomes stiff, and the quality as clothing is inferior to the colored cloth dyed with a dye. 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 specific anthraquinone dyes and describe their use in camera and ophthalmic lens materials.
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 ink-jet ink containing polyurethane having a colorant structure.

Japanese Unexamined Patent Publication No. 2002-348502 Japanese Patent Laid-Open No. 10-58638 Japanese Unexamined Patent Publication No. 2010-37700 US Patent Application Publication No. 2011-0149128 International Publication No. 2011/074501 Japan Special Table 2004-534106 Japan Special Table 2002-509957

As described above, coloring with a dye is excellent in the quality (texture, fastness) of the colored cloth, but it is necessary to select a dye depending on the fiber type, and the process such as a pretreatment process is complicated. There are some problems, problems that require equipment, and inferior environmental load 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).
Further, Patent Documents 6 and 7 do not specifically disclose textile printing, and do not describe any of the above problems.

That is, the problem of the present invention is that various kinds of fabrics can be dyed, a pretreatment process is unnecessary, there is little environmental load, there is no problem in workability, and the sharpness and robustness of the obtained image are improved. An object of the present invention is to provide an ink-jet printing method that is excellent in color cloth quality (texture). In addition, another problem of the present invention is that various types of fabrics can be dyed, a pretreatment process is unnecessary, there is little environmental load, there is no problem in workability, and excellent sharpness and fastness. It is an object to provide a dye polymer, a coloring composition and an inkjet ink capable of providing a colored cloth excellent in image and quality (texture), and an ink cartridge filled with the inkjet ink.

The inventors of the present invention have made extensive studies to solve the above problems, and by using a water dispersion of a dye polymer containing a structure derived from a dye having an anthraquinone skeleton, a method of directly printing on a fabric by an inkjet method, It has been found that various types of fabrics can be dyed, a pretreatment process is unnecessary, there is little environmental load, there is no problem in workability, and an excellent quality colored fabric can be obtained.
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.
Since the aqueous dispersion of the dye polymer uses the dye polymer as an aqueous dispersion instead of an aqueous solution, bleeding does not occur as in the case of the pigment particles, a pretreatment process is unnecessary, and no water washing process is required, so no waste water is generated. In addition, since printing is performed directly on the fabric, 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 the present invention, “directly printing” an inkjet ink on a fabric by an inkjet method does not require a transfer process, and the inkjet ink is directly printed on a fabric and a pretreatment process is not necessary. Ink jet ink is directly printed on a fabric.
Specifically, the object of the present invention has been achieved by the following means.

<1>
An ink jet printing method comprising a step of directly printing an ink jet ink containing an aqueous dispersion of a dye polymer having a structure derived from a dye having an anthraquinone skeleton on an ink jet system.
<2>
The ink-jet printing method according to <1>, wherein the dye polymer further has a repeating unit containing —COOM. However, said M represents a hydrogen atom or a counter cation.
<3>
Furthermore, the inkjet textile printing method as described in <1> or <2> including a heat treatment process.
<4>
The inkjet printing method according to any one of <1> to <3>, wherein the inkjet ink further contains an aqueous organic solvent.
<5>
The inkjet printing method according to any one of <1> to <4>, wherein the dye polymer is a dye polymer having a repeating unit represented by the following general formula (1).

In the 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 hydrogen atom from a dye having an anthraquinone skeleton. Represents.
<6>
The inkjet printing method according to any one of <1> to <4>, wherein the dye polymer further has a urethane bond.
<7>
The inkjet printing method according to <6>, wherein the dye polymer is a dye polymer having a repeating unit represented by the following general formula (1-2).

In General Formula (1-2), L ² and L ³ each independently represent a linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye having an anthraquinone skeleton.
<8>
In the above general formula (1) or (1-2), D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from the dye represented by the following general formula (M1), <5> or <7 > Ink-jet textile printing method.

In general formula (M1), R ¹⁰¹ to R ¹⁰⁸ each independently represents a hydrogen atom or a substituent.
<9>
The inkjet printing method according to <6>, wherein the dye polymer is a dye polymer having a repeating unit represented by the following general formula (1-3).

In General Formula (1-3), L ³ represents a linking group, L ⁴ and L ⁵ each independently represent a single bond or a linking group, and D ² represents ^two arbitrary hydrogen atoms from a dye having an anthraquinone skeleton. Represents the removed dye residue.
<10>
The inkjet printing method according to <9>, wherein D ² in the general formula (1-3) represents a dye residue obtained by removing two arbitrary hydrogen atoms from a dye represented by the following general formula (M1).

In general formula (M1), R ¹⁰¹ to R ¹⁰⁸ each independently represents a hydrogen atom or a substituent.
<11>
A coloring composition comprising an aqueous dispersion of a dye polymer having a structure derived from a dye having an anthraquinone skeleton.
<12>
An ink-jet ink comprising an aqueous dispersion of a dye polymer having a structure derived from a dye having an anthraquinone skeleton.
<13>
Furthermore, the inkjet ink as described in <12> containing an aqueous organic solvent.
<14>
<12> wherein the dye polymer in the aqueous dispersion of the dye polymer having a structure derived from the dye having the anthraquinone skeleton is a particulate dye polymer, and the average particle diameter of the particulate dye polymer is 30 to 500 nm The inkjet ink as described in <13>.
<15>
Any one of <12> to <14>, wherein the weight average molecular weight of the dye polymer in the aqueous dispersion of the dye polymer having a structure derived from the dye having the anthraquinone skeleton is 2,000 to 2,000,000. The inkjet ink as described.
<16>
The inkjet ink according to <15>, which is for textile printing.
<17>
An ink cartridge filled with the inkjet ink according to any one of <12> to <16>.
<18>
A dye polymer having a structure derived from a dye having an anthraquinone skeleton, a repeating unit derived from a monomer represented by the following general formula (1A), and a repeating unit containing —COOM. However, said M represents a hydrogen atom or a counter cation.

In General Formula (1A), R _1a represents a hydrogen atom or a methyl group. When R _1a represents a hydrogen atom, R _2a represents a linear, branched or cyclic alkyl group that may have a substituent, and when R _1a represents a methyl group, R _2a has an aromatic ring. It represents a linear, branched or cyclic alkyl group which may have a substituent having 3 or more nuclear atoms.
<19>
A dye polymer having a structure derived from a dye having an anthraquinone skeleton and having a urethane bond.
<20>
The dye polymer according to <19>, wherein the dye polymer further has a repeating unit containing —COOM. However, said M represents a hydrogen atom or a counter cation.

According to the present invention, various types of fabrics can be dyed, no pretreatment process is required, environmental impact is excellent, workability is not a problem, and the resulting image has excellent clarity and fastness. In addition, it is possible to provide an ink-jet printing method that is excellent in the quality (texture) of the colored fabric. In addition, according to the present invention, various kinds of fabrics can be dyed, no pretreatment process is required, the environmental load is excellent, the workability is not problematic, and the image is excellent in sharpness and fastness. It is possible to provide a dye polymer, a coloring composition, an inkjet ink, and an ink cartridge filled with the inkjet ink, which can provide a colored fabric excellent in quality (texture).

Hereinafter, the present invention will be described in detail.
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.

In the present specification, the substituent group A includes the following substituents.

(Substituent group A)
The substituents included in Substituent Group A are shown below.
A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a C1-C48, more preferably a C1-C24 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 a vinyl group, an 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 heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, 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) 3-18 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 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, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 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 a carbon number of 2 to 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 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, such as N, N-diethylsulfamoyloxy group and 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 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 carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms such as an acetamide 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, such as 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 having 7 to 24 carbon atoms) Aryloxycarbonylamino group of, for example, phenoxycarbonylamino group), sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as 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), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 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 a heterocyclic thio group having 1 to 32 carbon atoms, more preferably 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 linear, branched or cyclic alkyl having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms). 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, phosphonyl group (preferably phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphino An ylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group).

<Dye polymer having structure derived from dye having anthraquinone skeleton>
The inkjet textile printing method of the present invention uses at least a dye polymer including a structure derived from a dye having an anthraquinone skeleton.
The dye polymer containing a structure derived from a dye having an anthraquinone skeleton used in the present invention (also simply referred to as “dye polymer”) is not particularly limited as long as it has a structure derived from a dye having an anthraquinone skeleton in the molecule. It may be a linear polymer or a network polymer.
The structure derived from a dye having an anthraquinone skeleton is a group (dye residue) formed by removing one or more arbitrary hydrogen atoms from an organic compound used as a dye having an anthraquinone skeleton.
The dye having an anthraquinone skeleton may have various substituents as long as the properties as a dye are not impaired. Examples of such a substituent include the substituents shown in the above-mentioned substituent group A, or a substituent formed by combining a plurality of these, and a substituent consisting of 50 or less atoms.
The dye polymer is preferably a dye multimer containing a structure derived from a dye having an anthraquinone skeleton as a repeating unit.
As the dye polymer, a polymer having a structure derived from a dye having an anthraquinone skeleton in the main chain or side chain is preferably used. Although it does not specifically limit as a polymer which comprises the principal chain in the polymer which has a structure derived from the dye which has an anthraquinone frame | skeleton in a side chain, An acrylic polymer, a urethane polymer, or a styrene polymer is used preferably. The polymer constituting the main chain in the polymer having a structure derived from a dye having an anthraquinone skeleton in the main chain is not particularly limited, but a urethane polymer is preferably used.
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. Moreover, the urethane polymer in this invention is a polymer which has a urethane bond in a principal chain, and is formed by reaction of a polyol compound and a polyisocyanate compound. Sometimes called polyurethane. 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 structure derived from a dye having an anthraquinone skeleton is arbitrary, and a monomer having a structure derived from a dye having an anthraquinone skeleton may be polymerized or copolymerized to obtain a multimer. In addition, after forming a polymer, a structure derived from a dye having an anthraquinone skeleton 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) 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 hydrogen atom from a dye having an anthraquinone skeleton. Represents.

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. Examples of X ¹ include 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 the like. Preferably, an unsaturated ethylene group is polymerized. A linking group formed as described above. Specific examples include, but are not limited to, the following linking groups. In the following (X-1) to (X-15), it is linked to L ¹ at the site indicated by *.

The repeating unit represented by the general formula (1) is preferably a repeating unit represented by any one of the following general formulas (1-11) to (1-17). It is more preferable that it is the repeating unit represented by these.

In the general formulas (1-11) to (1-17), 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 represents an anthraquinone skeleton. The dye residue which remove | eliminated one arbitrary hydrogen atom from the dye which has is represented.
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 a combination thereof, 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 (1-11) to (1-17), 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 particularly limited as long as the effects of the present invention can be obtained, but it 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, naphthalene group, etc.), substituted Or 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 preferable. In particular, a linking group represented by any one of the following general formulas (2) to (10) and (2-2) to (10-2) is preferable.
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 general formula (3), general formula (3-2), general formula (4), and general formula (4-2), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. General formula (2), general formula (2-2), general formula (3), general formula (3-2), general formula (4), general formula (4-2), general formula (8), general formula In (8-2), general formula (9), and general formula (9-2), R ³ represents a substituent. k represents an integer of 0 to 4. When k represents an integer of 2 or more, the plurality of R ³ may be the same or different.
In general formula (2) and general formula (2-2), R ₂₁ and R ₂₂ each independently represents a hydrogen atom or a substituent. t represents an integer of 1 to 10. When t represents an integer of 2 or more, the plurality of R ₂₁ and the plurality of R ₂₂ may be the same or different.
In the general formulas (5) and (5-2), R ₅₁ and R ₅₂ each independently represent a hydrogen atom or a substituent. t represents an integer of 1 to 10. When t represents an integer of 2 or more, the plurality of R ₅₁ and the plurality of R ₅₂ may be the same or different.
In general formula (6) and general formula (6-2), R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a substituent. u and v each independently represents an integer of 1 to 10. When u represents an integer of 2 or more, the plurality of R ⁶¹ and the plurality of R ⁶² may be the same or different. When v represents an integer of 2 or more, the plurality of R ⁶³ and the plurality of R ⁶⁴ may be the same or different.
In general formula (7) and general formula (7-2), R ⁷¹ , R ⁷² and R ⁷³ each independently represents a hydrogen atom or a substituent. w represents an integer of 1 to 10. When w represents an integer of 2 or more, the plurality of R ⁷¹ and R ⁷² may be the same or different.
In general formula (8) and general formula (8-2), R ₈₁ and R ₈₂ each independently represents a hydrogen atom or a substituent. t represents an integer of 1 to 10. When t represents an integer of 2 or more, the plurality of R ₈₁ and the plurality of R ₈₂ may be the same or different from each other.
In general formula (9) and general formula (9-2), R ₉₁ and R ₉₂ each independently represent a hydrogen atom or a substituent. t represents an integer of 1 to 10. When t represents an integer of 2 or more, the plurality of R ₉₁ and the plurality of R ₉₂ may be the same or different.
In general formula (10) and general formula (10-2), R ₁₀₁ and R ₁₀₂ each independently represents a hydrogen atom or a substituent. t represents an integer of 1 to 10. When t represents an integer of 2 or more, the plurality of R ₁₀₁ and the plurality of R ₁₀₂ may be the same or different. u represents an integer of 1 to 10. When u represents an integer of 2 or more, a plurality of — [O— (CR ₁₀₁ R ₁₀₂ ) t] — may be the same as or different from each other.
* 1 in general formulas (2) to (10) and (2-2) to (10-2) is X ¹ in general formula (1) or in general formulas (1-11) to (1-17). The position bonded to the carbon atom or nitrogen atom of the polymer main chain is represented, and * 2 represents the position bonded to D ¹ in the general formulas (1) and (1-11) to (1-17).

Examples of the alkyl group, aryl group, or heterocyclic group when R ² represents an alkyl group, aryl group, or heterocyclic group include the alkyl group, aryl group, or heterocyclic group described in Substituent Group A Is mentioned.
R ³ , R ₂₁ , R ₂₂ , R ₅₁ , R ₅₂ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁷¹ , R ⁷² , R ⁷³ , R ₈₁ , R ₈₂ , R ₉₁ , R ₉₂ , R ₁₀₁ And the substituent represented by R ₁₀₂ includes a substituent selected from the substituent group A.
t, u, v, and w are each preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

In the general formulas (1) and (1-11) to (1-17), D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye having an anthraquinone skeleton.
D ¹ is not limited as long as it exhibits the effects of the present invention, and represents a dye residue obtained by removing one hydrogen atom from a dye having an anthraquinone skeleton represented by the general formula (M1) or (M2). More preferably, it represents a dye residue obtained by removing one hydrogen atom from any one of R ¹⁰⁵ to R ^{108 in} the general formula (M1) or any one of R ¹⁰⁵ to R ^{109 in} the general formula (M2). It is particularly preferable to represent a dye residue obtained by removing one hydrogen atom from R ¹⁰⁵ or R ¹⁰⁶ of the general formula (M1) or R ¹⁰⁹ of the general formula (M2).

In general formula (M1), R ¹⁰¹ to R ¹⁰⁸ each independently represents a hydrogen atom or a substituent.

Examples of the substituent when R ¹⁰¹ to R ¹⁰⁸ in the general formula (M1) represent a substituent include a substituent selected from the substituent group A.
R ¹⁰¹ to R ¹⁰⁸ in formula (M1) are preferably each independently a hydrogen atom, amino group, hydroxyl group, cyano group, or alkoxy group, and more preferably a hydrogen atom, amino group, hydroxyl group, or alkoxy group. It is. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 6 carbon atoms.
In general formula (M1), R ¹⁰¹ to R ¹⁰⁴ are preferably hydrogen atoms, R ¹⁰⁵ to R ¹⁰⁸ each independently represent a hydrogen atom or a substituent, and R ¹⁰¹ to R ¹⁰⁴ are preferably hydrogen atoms, More preferably, R ¹⁰⁵ to R ¹⁰⁸ each independently represent a hydrogen atom, an amino group, a hydroxyl group, a cyano group, or an alkoxy group.

When R ¹⁰¹ to R ^{108 in} formula (M1) represent a substituent, the substituent may further have a substituent, and examples of the further substituent include a substituent selected from substituent group A. 2 When it has two or more substituents, these substituents may be the same or different.

Further, when R ¹⁰¹ to R ¹⁰⁸ in the general formula (M1) represent a substituent, at least two of the substituents are bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated ring, or A saturated ring may be formed. In the present invention, it is also preferred that R ¹⁰⁶ and R ¹⁰⁷ are bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated or unsaturated ring. When the formed 5-membered, 6-membered or 7-membered ring is a further substitutable group, it may have a substituent, and the substituent is a substituent selected from Substituent Group A Group, and when it is substituted with two or more substituents, these substituents may be the same or different. That is, the dye having an anthraquinone skeleton represented by the general formula (M1) is also preferably represented by the following general formula (M2).

In general formula (M2), R ¹⁰¹ to R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁸ , and R ¹⁰⁹ each independently represent a hydrogen atom or a substituent.
^R 101 ^~ R ¹⁰⁴ in the general formula ^{^{(M2), R 105, R}} 108 is also respectively general formula (M1) in the same meaning as ^{^{^{R 101 ~ R 104, R 105}}} , R 108 specific examples and preferred ranges It is.
R ¹⁰⁹ in formula (M2) preferably represents a hydrogen atom or an alkyl group, preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably represents a hydrogen atom.

Specific examples of the monomer having a structure derived from a dye having an anthraquinone skeleton are shown below, but are not limited thereto.

A monomer having a structure derived from a dye having an anthraquinone skeleton can be synthesized by a conventionally known method (for example, Japanese Patent Publication No. 7-49583, Japanese Patent Publication No. 5-5257, Japanese Patent No. 5715380, WO2010 / 110199, WO2015 / 016265, etc.). The synthesis method is specifically illustrated in the examples.

(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. The weight average molecular weight (Mw) is preferably about 2,000 to 2,000,000, preferably about 2,000 to 1,000,000, depending on the type of dye polymer used. More preferably, 3,000 to 80,000 are used, more preferably 3,000 to 30,000, and most preferably 3,000 to 15,000. preferable. The dispersity (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0. Mn represents a number average molecular weight.
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 Corporation), columns measured with TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation), The average molecular weight was calculated by polystyrene conversion. The carrier may be appropriately selected, but NMP (N-methylpyrrolidone) was used as long as it was soluble.

(Structure of dye polymer)
The dye polymer may have a structure derived from a dye having an anthraquinone skeleton 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 having an anthraquinone skeleton in the dye polymer is preferably 10 to 90% by mass, more preferably 25 to 90% by mass, and particularly preferably 50% by mass. ~ 90% by mass. If the content rate of the repeating unit which has a structure derived from the dye which has an anthraquinone skeleton 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.
The dye polymer preferably contains a repeating unit derived from a monomer represented by the following general formula (1A) from the viewpoint of familiarity with fibers, that is, the softness of the dye polymer.

In General Formula (1A), R _1a represents a hydrogen atom or a methyl group. When R _1a represents a hydrogen atom, R _2a represents a linear, branched or cyclic alkyl group that may have a substituent, and when R _1a represents a methyl group, R _2a is an aliphatic group, A linear, branched or cyclic alkyl group which may have a substituent having 3 or more nucleus atoms.

The number of nuclear atoms means the number of atoms other than hydrogen atoms.

When R _1a represents a hydrogen atom, R _2a is preferably a linear or branched alkyl group, more preferably a linear alkyl group. When R _2a has a substituent, the substituent preferably does not contain an aromatic ring, and is preferably a hydroxyl group or an alkoxyl group.
When R _1a represents a methyl group, R _2a is preferably an unsubstituted linear or branched alkyl group, more preferably a linear alkyl group. When R _2a has a substituent, the substituent preferably does not contain an aromatic ring, and is preferably a hydroxyl group or an alkoxyl group.

Specific examples of the monomer (b) represented by the general formula (1A) include acrylic monomers (R ₁ = hydrogen atom): methyl acrylate, ethyl acrylate, propyl acrylate, iso-propyl acrylate, butyl acrylate Tert-butyl acrylate, isobutyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate homopolymer, iso-octyl acrylate, lauryl acrylate, tetradecyl acrylate, hexadecyl acrylate, Stearyl acrylate, benzyl acrylate, vinyl acetate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate , 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, ethoxyethyl acrylate, ethoxydiethyleneglycol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, carboxyethyl acrylate; methacrylic monomer (R 1 ₌ methyl group): propyl methacrylate, iso-propyl methacrylate homopolymer, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, isoamyl acrylate, hexyl methacrylate, cyclohexyl acrylate, octyl acrylate, iso-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate homopolymer, lauryl methacrylate Tetradecyl methacrylate, hexadecyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate homopolymer, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, ethoxyethyl Methacrylate, methoxy methacrylate, carboxyethyl methacrylate;

The content of the repeating unit derived from the monomer represented by the general formula (1A) in the dye polymer is preferably 5 to 90% by mass, more preferably 5 to 50% by mass, Particularly preferred is 10 to 30% by mass. If the content of the repeating unit derived from the monomer represented by the general formula (1A) is 5% by mass or more, the dye polymer as particles is melted in the heat treatment process at the time of printing and the fiber is coated. The friction resistance can be improved. Moreover, it is easy to control an average particle diameter as it is 90 mass% or less.

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

(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 unsaturated amine-containing monomers 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.

(Anionic group-containing monomer)
As an anionic group-containing monomer, a monomer containing —COOM (M represents a hydrogen atom or a counter cation), an unsaturated sulfonic acid monomer, an unsaturated phosphoric acid monomer, or an anhydride thereof And a monomer containing —COOM is preferable. —COOM represents a carboxyl group (when M represents a hydrogen atom) or a salt thereof (when M represents a counter cation). When M represents a counter cation, ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) are listed. Lithium ion, sodium ion, potassium ion and ammonium ion are preferable, and lithium ion or sodium ion is more preferable.
Examples of the monomer containing —COOM include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, carboxyethyl acrylate, and the like. Among these, (meth) acrylic acid is preferable.
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. Is mentioned.
Examples of the unsaturated phosphoric acid monomer include vinylphosphonic acid, phosphoric acid ester of hydroxyalkyl (meth) acrylate (2 to 6 carbon atoms), and (meth) acrylic acid alkylphosphonic acid.

The dye polymer of the present invention preferably has a repeating unit containing —COOM.
A monomer containing —COOM can be used to introduce a repeating unit containing —COOM into the dye polymer.
The content of the repeating units including —COOM in the dye polymer with respect to all repeating units is preferably 5 to 90% by mass, more preferably 5 to 50% by mass, and particularly preferably 5 to 20% by mass. When the content of the repeating unit containing a carboxyl group or a salt thereof is 5% by mass or more, the dispersibility of the dye polymer in the ink can be improved. Moreover, it is easy to control an average particle diameter as it is 90 mass% or less.

[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.

The dye polymer preferably has at least one type each of a structure derived from a dye having an anthraquinone skeleton, a repeating unit derived from the monomer represented by the general formula (1A), and a repeating unit containing —COOM. A polymer obtained by copolymerizing a monomer having a structure derived from a dye having an anthraquinone skeleton, a monomer represented by the general formula (1A), and a monomer containing —COOM Is preferred.

Specific examples of the dye polymer preferably used in the present invention are shown below, but are not limited thereto.

[Dye polymer having a structure derived from a dye having an anthraquinone skeleton and having a urethane bond]
The dye polymer in the present invention is preferably a dye polymer having a structure derived from a dye having an anthraquinone skeleton and having a urethane bond (also referred to as “dye polymer having a urethane bond”). The dye polymer having a urethane bond is a urethane polymer.
The dye polymer having a urethane bond may be a linear polymer having a urethane bond in the main chain, or may be a network polymer having a urethane bond.
Preferred examples of the dye polymer having a urethane bond include a dye polymer having a repeating unit represented by the following general formula (1-2) or a dye polymer having a repeating unit represented by the following general formula (1-3). Can be mentioned.

In General Formula (1-2), L ² and L ³ each independently represent a linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye having an anthraquinone skeleton.

In General Formula (1-3), L ³ represents a linking group, L ⁴ and L ⁵ each independently represent a single bond or a linking group, and D ² represents ^two arbitrary hydrogen atoms from a dye having an anthraquinone skeleton. Represents the removed dye residue.

In general formula (1-2), L ² and L ³ each independently represent a linking group, and the linking group is not limited as long as the effects of the present invention can be achieved, but has 1 to 30 carbon atoms. A substituted or unsubstituted linear, branched or cyclic aliphatic hydrocarbon group (which may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group), a C 6-30 substituted or An unsubstituted aromatic group (which may be an aromatic hydrocarbon group or an aromatic heterocyclic group) 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-, and the like.
L ² is preferably a trivalent linking group. L ² is preferably an aliphatic hydrocarbon group or a linking group formed by combining an aliphatic hydrocarbon group and —O—. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable, and an aliphatic hydrocarbon group having 1 to 6 carbon atoms is more preferable.
L ³ is preferably a divalent linking group. L ³ is preferably an alkylene group, an arylene group or a combination thereof, more preferably an alkylene group, and still more preferably an alkylene group having 1 to 10 carbon atoms.
The linking group represented by L ² and L ³ may have a substituent, and examples of the substituent include a substituent selected from the substituent group A.

In the general formula (1-2), D ¹ represents a dye residue obtained by removing one hydrogen atom from a dye having an anthraquinone skeleton, and is not particularly limited. In the general formula (M1) or (M2), It is preferable to represent a dye residue obtained by removing one arbitrary hydrogen atom from the represented dye. The description regarding the general formula (M1) or (M2) is as described above.

In general formula (1-3), L ⁴ and L ⁵ each independently represent a single bond or a linking group. The linking group is not particularly limited as long as the effects of the present invention can be achieved. However, the linking group is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, 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, naphthalene group, etc.), substituted or unsubstituted heterocyclic group, —CH═CH—, and A linking group formed by linking two or more of these is preferred. 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-, and the like.
L ⁴ and L ⁵ are preferably a divalent linking group. L ⁴ and L ⁵ are preferably an alkylene group or a linking group formed by combining an alkylene group and —O—. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable.
L ³ is the same as ^{L 3} in the above general formula (1-2).
When L ³ , L ⁴ , and L ⁵ represent a linking group, the linking group may have a substituent, and examples of the substituent include a substituent selected from the substituent group A.

In the general formula (1-3), D ² represents a dye residue obtained by removing two arbitrary hydrogen atoms from a dye having an anthraquinone skeleton. Although not particularly limited, in the general formula (M1) or (M2), It is preferable to represent a dye residue obtained by removing two arbitrary hydrogen atoms from the represented dye. The description of the general formula (M1) or (M2) is as described above. In particular, any one of R ¹⁰⁵ to R ^{108 in} the general formula (M1) or R ¹⁰⁵ to R ^{109 in} the general formula (M2). more preferably represent a removing two dye residue a hydrogen atom from the general formula ^{R 105} and ^{R 108} of the (M1), removing two dyes from ^{R 105} and ^{R 108} hydrogen atoms of the general formula (M2) It is particularly preferred to represent a residue.

Although the dye polymer having a urethane bond varies depending on the type of the dye polymer used, it is preferable to use a polymer having a weight average molecular weight (Mw) of 2,000 to 2,000,000. It is more preferable to use 3,000,000, more preferably 3,000 to 80,000, particularly preferably 3,000 to 60,000, and 5,000 to 30,000. Most preferably, 000 is used. The dispersity (Mw / Mn) is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, still more preferably 1.0 to 5.0, and particularly preferably Is 1.0 to 3.0. Mn represents a number average molecular weight.

<Method for measuring molecular weight of dye polymer having urethane bond>
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 uses HLC-8220GPC (manufactured by Tosoh Corp.), and the column is measured with TSKgel SuperAW4000, TSKgel SuperAW3000, TSKgel SuperAW2500 (manufactured by Tosoh Corp.), and the number average molecular weight. Was calculated in terms of polymethyl methacrylate. The carrier may be selected as appropriate, but a 5 mmol / L sodium trifluoroacetate solution in trifluoroethanol is used as long as it can be dissolved.

The dye polymer having a urethane bond preferably contains 40 to 96% by mass of the repeating unit represented by the above general formula (1-2) or (1-3) with respect to all the repeating units. More preferably, it is contained in an amount of 60% to 90% by mass.

The dye polymer having a urethane bond may have other repeating units, and preferably has a repeating unit containing an acidic group. As the acidic group, in particular, —COOM (M is a hydrogen atom or a counter cation). Are preferred). —COOM represents a carboxyl group (when M represents a hydrogen atom) or a salt thereof (when M represents a counter cation). When M represents a counter cation, ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium ion, tetra Butyl ammonium ion), lithium ion, sodium ion, potassium ion and ammonium ion are preferable, and potassium ion or sodium ion is more preferable.

The repeating unit having —COOM is preferably a repeating unit represented by the following general formula (Z).

In general formula (Z), L ⁶ represents a linking group. M represents a hydrogen atom or a counter cation.

In general formula (Z), L ⁶ represents a linking group, and specific examples and preferred ranges thereof are the same as those of L ² in general formula (1-2). Specific examples and preferred ranges of M are as described above.

The content of the repeating unit including —COOM in the dye polymer is preferably 2 to 29% by mass, more preferably 2 to 24% by mass, and particularly preferably 5 to 19% by mass. When the content of the repeating unit containing a carboxyl group or a salt thereof is 2% by mass or more, the dispersibility of the dye polymer in the ink can be improved. Moreover, it is easy to control an average particle diameter as it is 29 mass% or less.

(Method for producing dye polymer having urethane bond)
The dye polymer having a urethane bond has a structure derived from a dye having an anthraquinone skeleton, and a polyaddition reaction between a compound having two or more hydroxyl groups and a compound having two or more isocyanate groups (—NCO) Can be manufactured.
As an example of a compound having a structure derived from a dye having an anthraquinone skeleton and having two or more hydroxyl groups, a compound represented by the following general formula (M12) or general formula (M13) is preferable.

In general formula (M12), R ¹⁰¹ to R ¹⁰⁸ each independently represents a hydrogen atom or a substituent. L ² represents a linking group. However, -L ^2- (OH) ₂ is substituted for any one of R ¹⁰¹ to R ¹⁰⁸ .

^R 101 ^{~ R 108} in the formula (M12) is the same as ^R 101 ^{~ R 108} in the general formula (M1).
^{L 2} in the general formula (M12) is the same as ^{L 2} in the general formula (1-2).

In general formula (M13), R ¹⁰¹ to R ¹⁰⁸ each independently represents a hydrogen atom or a substituent. L ⁴ and L ⁵ each independently represents a single bond or a linking group. However, any one of R ¹⁰¹ to R ¹⁰⁸ is substituted with -L ⁴ -OH, and any one of R ¹⁰¹ to R ¹⁰⁸ is substituted with -L ⁵ -OH.

^R 101 ^{~ R 108} in the formula (M13) is the same as ^R 101 ^{~ R 108} in the general formula (M1).
^{L 4} and ^{L 5} in formula (M13) is the same as ^{L 4} and ^{L 5} in the general formula (1-3).

The compound represented by the general formula (M12) or the general formula (M13) is, for example,
US2628963, 1951;
EP1538154A1,2005;
European Journal of Medicinal Chemistry, 1999, vol. 34, # 7-8 p. 597-615; European Journal of Organic Chemistry, 2008, # 13 p. 2213-2219; US Pat. No. 5,354,876 A1, 1994; Appl. Chem. USSR (Engl. Transl.), 1976, vol. 49, p. 904,946.
Specific examples of the compound having a structure derived from a dye having an anthraquinone skeleton and having two or more hydroxyl groups are shown below, but are not limited thereto.

(Compound having two or more isocyanate groups)
The compound having two or more isocyanate groups (—NCO) is preferably a compound represented by the following general formula (J).

In general formula (J), L ³ represents a linking group.

^{L 3} in the general formula (J) is the same as ^{L 3} in the above general formula (1-2) and (1-3).

Moreover, in order to introduce the repeating unit represented by the general formula (Z), a compound represented by the following general formula (MZ) is added as a raw material, and a compound having two or more isocyanate groups is polyadded. Can be reacted.

In General Formula (MZ), L ⁶ represents a linking group. M represents a hydrogen atom or a counter cation.

The ^{L 6} and M in the general formula (MZ) is similar to ^{L 6} and M in the general formula (Z).

The dye polymer having a urethane bond has a structure derived from a dye having an anthraquinone skeleton, and contains 68 to 23% by mass of a structural unit derived from a compound having two or more hydroxyl groups based on the total structural unit. The content is preferably 64 to 30% by mass, more preferably 61 to 38% by mass.
The dye polymer having a urethane bond preferably contains 32 to 48% by mass, more preferably 33 to 46% by mass, of structural units derived from a compound having two or more isocyanate groups. The content is preferably 34 to 43% by mass.

Specific examples of the dye polymer having a urethane bond preferably used in the present invention are shown below, but are not limited thereto.

<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. Further, depending on the method for producing the aqueous dispersion of the dye polymer, (C) either a low molecular surfactant or a high molecular dispersant may be used together, or not used (so-called self-dispersing). Also good.

(A) Dye polymer In the present invention, the above-mentioned dye polymer is used not in a state dissolved in water but in a state dispersed in water (water dispersion).
It is preferable to use ultrapure water as water.

(1-1) Dispersibility Dye polymers tend to become familiar 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 preferably in the form of particles in an aqueous dispersion. The average particle diameter of the particulate dye polymer in the aqueous dispersion of the dye polymer is preferably 30 to 500 nm, more preferably 30 to 400 nm, still more preferably 30 to 300 nm, and more preferably 30 to 200 nm. Particularly preferred is 30 to 100 nm. Within this range, the fabric can be directly printed by the ink jet method.
The value measured using the particle size distribution analyzer (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 dyed cloth can be obtained in printing while ensuring storage stability as an inkjet ink.
The content of water in the aqueous dispersion is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and particularly preferably 60 to 90% by mass. Within this range, the stability of the 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 The aqueous organic solvent preferably has a water solubility of 10 g / 100 g-H ₂ O or more at 25 ° C., more preferably 20 g / 100 g-H ₂ O, and water and an optional solvent. Those mixed in proportions are particularly preferred. 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 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. This causes aggregation of the dye polymer. On the other hand, if the molecular weight is smaller than the optimum molecular weight, desorption from the dye polymer is likely to occur, and the effect as a dispersant is reduced. Further, when the molecular weight is small, the effect as a fixing agent after crosslinking is weakened. Accordingly, it is preferable to use a polymer type 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.

(2-3) Structure and form The low molecular weight surfactant or polymer type dispersant is composed of a hydrophobic group (electrically neutral nonpolar group having 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 polymer type dispersing agent.
Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. As an anionic surfactant, for example, 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. 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 polymeric dispersant, DISPERBYK-194N (trade name) manufactured by BYK Japan, Inc. 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.

A method for producing an aqueous dispersion of a dye polymer is as follows: (A) a dye polymer powder or paste, and, if necessary, a low molecular weight surfactant or a polymeric dispersant mixed in water or an aqueous organic solvent. Later, glass beads, zirconia beads, titania beads, stainless steel spheres and other fine dispersion methods using an attritor or a mill, or (B) water or an aqueous organic solvent and poorly soluble in water or an aqueous organic solvent Emulsion polymerization is carried out by mixing a dye monomer and, if necessary, a copolymerization monomer and an emulsifier (surfactant), and adding a polymerization initiator (usually a radical generator) that can be dissolved in water or an aqueous organic solvent. There are methods, 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.

<Coloring composition>
The invention also relates to a colored composition comprising an aqueous dispersion of a dye polymer. The coloring composition containing the aqueous dispersion of the dye polymer contains the aqueous dispersion of the dye polymer described above, and preferably further contains water or an aqueous organic solvent. Moreover, you may contain components, such as another coloring agent, an organic solvent, surfactant, and various additives as needed.
Since the coloring composition containing the aqueous dispersion of the dye polymer of the present invention has excellent light resistance, it is used not only for fiber dyeing but also for paper media dyeing, plastic dyeing, paints, coatings, and building materials. be able to.

The colored composition of the present invention may further contain a colorant (dye, pigment, etc.) 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 coloring agent (including the dye polymer and other coloring agents) in the coloring composition is such that a good dyeing concentration is obtained, and considering the storage stability of the coloring composition, the entire coloring composition The content is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and still more preferably 3% by mass to 12% by mass with respect to the mass.
The content of the dye polymer in the coloring composition is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 3 to 12% by mass with respect to the total mass of the coloring composition. .
The content of water in the coloring composition is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and particularly preferably 50 to 80% by mass.

<Organic solvent>
Examples of the organic solvent that can be contained in the coloring composition of 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-pentanediol 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-butanediol and 2-methyl 1,3-propanediol, etc.), amines (eg, ethanolamine, 2- (dimethylamino) ethanol, etc.), monohydric alcohols (eg, methanol, ethanol, 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, dipropylene glycol monomethyl ether, etc. ), 2,2'-thiodiethanol, amides (eg, N, N-dimethylformamide, etc.) , Sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, 3-sulfolene, heterocycles (2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine, etc.) And acetonitrile. These may be used alone or in combination of two or more.
The organic solvent that can be contained in the colored composition of the present invention is preferably the aforementioned aqueous organic solvent.
The content of the organic solvent in the colored composition of the present invention 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 colored composition. preferable.

<Surfactant>
The colored composition of the present invention can further use various surfactants from the viewpoint of improving 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 the anionic surfactant 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 colored composition of 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 colored composition. It is preferable to arbitrarily adjust the surface tension of the object.

<Various additives>
In addition, the coloring composition of the present invention may contain various 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-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, 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 coloring composition contains an ultraviolet absorber, the storability of the image 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. Can be used. When the coloring composition contains an anti-fading agent, image storability can be improved.

(Preservatives and antifungal agents)
The colored composition of the present invention may contain at least one of a preservative and an antifungal agent in order to maintain the long-term storage stability of the colored composition. When the coloring composition 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; manufactured by LANXESS, trade name), 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 pyridinethion-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 coloring composition contains an antiseptic 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 coloring composition.

(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 coloring composition contains an anti-drying agent, clogging due to drying of the coloring composition at the nozzle outlet of the discharge head that discharges the coloring composition is prevented when used for inkjet recording applications. be able to. 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 ether, 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 the colored composition contains an anti-drying agent, the content of the anti-drying agent is preferably 10% by mass to 50% by mass with respect to the total mass of the total mass of the colored composition.

(PH adjuster)
As a pH adjuster, neutralizers, such as an organic base and an inorganic alkali, can be used, for example. When using a coloring composition for inkjet recording, the storage stability of a coloring composition can be improved by containing a pH adjuster in a coloring composition. The pH adjusting agent is preferably added so that the pH of the coloring composition 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.

When the colored composition of the present invention is used for inkjet (inkjet ink), the surface tension of the colored composition is preferably adjusted to 20 mN / m to 70 mN / m, and adjusted to 25 mN / m to 60 mN / m. More preferably. When the colored composition is used for inkjet, the viscosity of the colored composition is preferably adjusted to 40 mPa · s or less, more preferably adjusted to 30 mPa · s or less, and adjusted to 20 mPa · s or less. It is particularly preferable to do this.
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 coloring composition, and for the purpose of improving storage stability and clogging recovery. When a dye is used as the colorant of the coloring composition, the metal (Ca, Mg, Si, Fe, etc.) contained in the coloring composition may cause the generation of precipitates and the reduction in clogging recovery. It is known that ions need to be managed below a certain 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. It is known (see JP 2000-355665 A, JP 2005-126725 A, 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)
For the purpose of improving the friction resistance and washing fastness of the colored fabric, the colored composition may contain a crosslinking agent. Examples of the crosslinking agent include blocked isocyanate crosslinking agents (for example, Meikanate CX, TP-10, DM-35HC, SU-268A, etc., all manufactured by Meisei Kogyo Co., Ltd., trade names) and polyfunctional epoxy crosslinking agents (for example, , Denacor EX-313, 314, 322, 411, etc., all manufactured by Nagase ChemteX Corporation, trade names).

The colored composition of the present invention can be suitably used as an inkjet ink in which the amount of colorant supplied onto the fabric is limited.

<Inkjet ink>
The present invention also relates to an inkjet ink including an aqueous dispersion of a dye polymer having a structure derived from at least a dye having an anthraquinone skeleton. The inkjet ink is preferably used for textile printing. The components contained in the inkjet ink are the same as those shown in the above-described coloring composition of the present invention.
The content of the dye polymer and other components in the ink-jet ink can be in the range of the content shown in the above-described coloring composition of the present invention.
The ink-jet ink containing the aqueous dispersion of the dye polymer of the present invention is particularly useful from the viewpoint of workability because it can directly print on a fabric without an undercoat.

<Ink cartridge>
The ink cartridge of the present invention is an ink cartridge filled with the ink jet ink of the present invention.

<Inkjet printing method>
The ink-jet printing method of the present invention is an ink-jet printing method including a step of directly printing an ink-jet ink containing an aqueous dispersion of a dye polymer having a structure derived from a dye having an anthraquinone skeleton directly on a fabric by an ink-jet method. .
The ink-jet printing method of the present invention produces an effect that direct printing can be performed on various types of fabrics without using waste materials such as waste water and transfer paper, with simple workability.
Further, by adding a heating step, the dye polymer is fused to the fiber, so that there is an advantage that it can be further integrated with the fiber, and further imparted with friction resistance without impairing the texture.

<Heat treatment process>
The ink jet textile printing method of the present invention preferably further includes a heat treatment step. In particular, by performing a heat treatment step after printing on the fabric, the dye polymer particles can be melted (or softened), and the adhesion to the fibers can be improved (that is, heat-treated for melt dyeing). Can do). The colored fabric is preferably dried and then heat treated for the purpose of melt dyeing, usually at 100 to 250 ° C., more preferably at 100 to 200 ° C., particularly preferably at 120 to 200 ° C. It is. 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.

<Post-processing>
The fabric colored with the ink-jet ink containing the aqueous dispersion of the dye polymer of the present invention is difficult to bleed and has excellent texture flexibility and fastness (friction resistance), but if necessary, a post-treatment agent may be added to the colored fabric. By performing the padding process on the entire surface, a colored cloth having further improved texture flexibility and 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.

<Fabric>
Examples of fabrics to which the inkjet printing method of the present invention can be applied include the following. Fabrics (fiber types) include synthetic fibers such as nylon, polyester and acrylonitrile, semi-synthetic fibers such as acetate and rayon, natural fibers such as cotton, silk and wool, and mixed fibers, woven fabrics, knitted fabrics, non-woven fabrics, etc. Is mentioned.
Apparel includes T-shirts, trainers, jerseys, pants, sweatsuits, dresses, blouses and the like. It is also suitable for bedding and handkerchiefs.

The colored fiber product produced by the inkjet printing method of the present invention exhibits excellent effects in any of the characteristics of texture, wash fastness, friction fastness, and printing workability. Therefore, the inkjet printing method and colored composition of the present invention Products and inkjet inks are of great value.

(Synthesis Example 1)
[Synthesis of Dye Polymer (D-1-1)]
Exemplary compound (D-1-1) was synthesized according to the following scheme.

10 g of N-methylpyrrolidone (NMP) was added to a 100 mL three-necked flask, and the internal temperature was raised to 85 ° C. Here, D-1 (synthesized by the method described in US2011 / 0149128) 7.5 g, 2-ethylhexyl methacrylate 2.0 g, methacrylic acid 0.5 g, V-601 (trade name, manufactured by Wako Pure Chemical Industries) 0.16 g, A solution prepared by dissolving 0.55 g of 1-dodecanethiol in 13.13 g of NMP was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was reacted at 85 ° C. for 1 hour, and then V-601 (0.16 g) was added, and further 1 hour later, V-601 (0.16 g) was added and reacted for 2 hours. The reaction solution is allowed to cool to 20 ° C., poured into 300 mL of hexane, crystals are precipitated, and the crystals are separated by filtration, and then dried for 1 day in an air dryer at 60 ° C. to give the exemplified compound (D-1-1) ) Yield 9.8 g. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum of the exemplified compound (D-1-1) in a diluted NMP solution was 671 nm. Moreover, the weight average molecular weight (Mw) in the gel permeation chromatography (GPC) measurement was 8,900 (polystyrene conversion).

(Synthesis Example 2)
[Synthesis of Dye Polymer (D-1-2)]
After adding 5.0 g of D-1-1 and 23.1 g of NMP to a 100 mL three-necked flask and stirring, 2.91 mL of a 1 mol / l sodium hydroxide aqueous solution was added dropwise and stirred for 30 minutes. The reaction solution was poured into 300 mL of hexane to precipitate crystals, and the crystals were separated by filtration, and then dried for 1 day with a blow dryer at 60 ° C. to obtain Exemplified Compound (D-1-2). Yield 4.9g. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of Exemplified Compound (D-1-2) in tetrahydrofuran (THF) was 670 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 8,900 (polystyrene conversion).

(Synthesis Example 3)
[Synthesis of Dye Polymer (D-2-2)]
Exemplary compound (D-2-2) was synthesized according to the following scheme.

Exemplified compound (D-2-2) was synthesized in the same manner except that D-1 in Synthesis Example 1 was changed to D-2. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of Exemplified Compound (D-2-2) in tetrahydrofuran (THF) was 521 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 10,400 (polystyrene conversion).

(Synthesis Example 4)
[Synthesis of Dye Polymer (D-3-2)]
Exemplary compound (D-3-2) was synthesized according to the following scheme.

Exemplified compound (D-3-2) was synthesized in the same manner except that D-1 in Synthesis Example 1 was changed to D-3 and 2-ethylhexyl methacrylate was changed to lauryl methacrylate. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of Exemplified Compound (D-3-2) in tetrahydrofuran (THF) was 581 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 11,800 (polystyrene conversion).

(Synthesis Example 5)
[Synthesis of Dye Polymer (D-4-2)]
Exemplary compound (D-4-2) was synthesized according to the following scheme.

Exemplified compound (D-4-2) was synthesized in the same manner except that D-1 in Synthesis Example 1 was changed to D-4 and 2-ethylhexyl methacrylate was changed to isobutyl methacrylate. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of Exemplified Compound (D-4-2) in tetrahydrofuran (THF) was 645 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 11,100 (polystyrene conversion).

(Synthesis Example 6)
[Synthesis of Dye Polymer (A-1-1)]
Exemplary compound (A-1-1) was synthesized according to the following scheme.

Exemplified compound (A-1-1) was synthesized in the same manner except that D-1 in Synthesis Example 1 was changed to A-1 and 2-ethylhexyl methacrylate was changed to benzyl methacrylate. The absorption maximum wavelength of the ultraviolet / visible absorption spectrum in a dilute solution of Exemplified Compound (A-1-1) in tetrahydrofuran (THF) was 671 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 10,200 (polystyrene conversion).

(Synthesis Example 7)
[Synthesis of Dye Polymer (A-2-1)]
Exemplary compound (A-2-1) was synthesized according to the following scheme.

Exemplified compound (A-2-1) was prepared by changing D-1 in Synthesis Example 1 to A-2, changing 2-ethylhexyl methacrylate to 2-hydroxyethyl methacrylate, and changing methacrylic acid to 3-tris (trimethylsiloxy). ) Synthesized in the same manner except that it was changed to silylpropyl methacrylate. The absorption maximum wavelength of the ultraviolet / visible absorption spectrum in a dilute solution of Exemplified Compound (A-2-1) in tetrahydrofuran (THF) was 583 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 86,200 (polystyrene conversion).

Example 1
[Preparation of aqueous dye polymer dispersion (1)]
0.25 g of exemplary compound (D-1-1), 10 g of zirconia beads (trade name YTZ ball, diameter 0.1 μm, manufactured by Nikkato), 0.05 g of sodium oleate, 0.5 g of glycerin, and 4.2 g of ultrapure water Was added and dispersed for 10 hours at a rotation speed of 400 rpm (revolution per minute) using a planetary fine pulverizer (Pulversette 7 manufactured by Fritsch). From the obtained dispersion, zirconia beads were removed using a filter cloth to obtain an aqueous dye polymer dispersion (1). The weight average molecular weight of the used dye polymer, the average particle diameter of the particulate dye polymer in the obtained dye polymer aqueous dispersion, and the time-lapse with respect to the initial average particle diameter of the particulate dye polymer in the aqueous dye polymer dispersion The ratio of the average particle size after (after 1000 hours at a temperature of 50 ° C.) was as shown in Table 1.
Ratio of average particle diameter after time = average particle diameter after time / initial average particle diameter

(Examples 2 to 7)
Dye polymer aqueous dispersions (2) to (7) were prepared in the same manner except that the dye polymer and the low molecular surfactant or polymer type dispersant were changed to the types and amounts shown in Table 1 below. did.

From Table 1 above, in addition to a repeating unit having a structure derived from a dye having an anthraquinone skeleton, a dye polymer comprising a repeating unit derived from a monomer represented by the general formula (1A) and a repeating unit containing —COOM It can be seen that in Examples 1 to 5 using the above, the ratio of the average particle diameter after aging to the initial average particle diameter of the particulate dye polymer in the dye polymer aqueous dispersion is closer to 1, and the stability is excellent. .

(Example 11)
[Preparation of ink liquid for ink jet textile printing (A1)]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a membrane filter (average pore diameter: 0.8 μm) to prepare ink jet printing ink (A1).
Dye polymer aqueous dispersion (1) 3.0 g
Trimethylolpropane 0.056g
0.913g of ultrapure water
1,12-hexanediol 0.112g
Glycerin 0.560g
Triethylene glycol monobutyl ether 0.112 g
2-pyrrolidone 0.168g
Propylene glycol 0.028g
Surfynol 465 (trade name, manufactured by Nissin Chemical Industry) 0.056g

[Inkjet printing method]
Ink for ink-jet textile printing (A1) is loaded into an ink cartridge, and polyester fabric (product name: polyester tropical (manufactured by Teijin Ltd.)) using an ink-jet printer (Calario PX-045A, product name) manufactured by Seiko Epson Corporation. Sold by Color Dyeing Co., Ltd., product code A02-01019), cotton fabric (with cotton broad sill, product code A02-01002), and polyester 65% cotton 35% blend (blend polyester 65 / cotton 35 broad) The image was printed on each of the products manufactured by Color Dye Co., Ltd., product code A02-01030) and dried at 20 ° C. for 12 hours. After drying, heat treatment is performed at a temperature of 120 ° C., a pressure of 0.20 N / cm ² , and a time of 60 seconds using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type). As a result, a clear image without blurring was obtained.

(Examples 12 to 17)
Inkjet textile printing inks (A2) to (A7) In the same manner as the inkjet textile printing ink (A1) except that the dye polymer aqueous dispersion liquid (1) is changed to the dye polymer aqueous dispersion liquids (2) to (7) Was prepared.
Inkjet printing was carried out in the same manner as in Example 11, except that the inkjet printing ink used was changed to the inkjet printing ink shown in Table 2 below.

(Comparative Example 1) Sublimation transfer printing After printing an image on transfer paper using a sublimation transfer printing printer SureColor F6000 (trade name, manufactured by Seiko Epson Corporation), a polyester fabric (product name: Polyester Tropical (Teijin Corporation) Manufactured by, Color Co., Ltd., product code A02-01019), cotton fabric (with cotton broad sill, product code A02-01002), polyester 65% cotton 35% blend (mixed polyester 65 / cotton) 35 Broad, manufactured by Color Dyeing Co., Ltd., product code A02-01030), and images were dried at 20 ° C. for 12 hours. After drying, heat treatment is performed using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type) at a temperature of 200 ° C., a pressure of 0.20 N / cm ² , and a time of 60 seconds. Thus, a transferred image was obtained. A clear image was obtained for the polyester fabric, but a 35% polyester 65% cotton blend produced a clear but low dyeing density image, and a cotton fabric gave a very blurred image. It was.

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

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

(Preparation of pigment ink and coloring by inkjet method)
46.6 g of the above pigment dispersion, 15 g of the above aqueous binder, 2.9 g of PDX-7664A (trade name, manufactured by BASF), 10 g of triethylene glycol monobutyl ether, 5 g of 1,2-hexanediol, 11.2 g of diethylene glycol, and olphine 465 (Product name, manufactured by Nissin Chemical Industry Co., Ltd.) 0.6 g was mixed, and ion-exchanged water was added thereto to prepare a total amount of 100 g, followed by filtration with a 0.8 μm filter to obtain a comparative pigment ink.
The obtained pigment ink is loaded into an ink cartridge, and a polyester fabric (product name: Polyester Tropical (manufactured by Teijin Ltd.)) is sold using an inkjet printer (Calario PX-045A, product name) manufactured by Seiko Epson Corporation. Tip Color Co., Ltd., product code A02-01019), cotton fabric (with cotton broad sill, product code A02-01002), polyester 65% cotton 35% blend (mixed polyester 65 / cotton 35 broad, color) Each of the images was printed on a dye code, product code A02-01030) and dried at 20 ° C. for 12 hours. After drying, heat treatment is performed using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type) at a temperature of 100 ° C., a pressure of 0.20 N / cm ² , and a time of 60 seconds. A colored fabric printed with pigment ink was obtained.

The evaluation results of Examples 11 to 17 and Comparative Examples 1 and 2 are shown in Table 2. The evaluation of the colored fabric is the result of the following method. Of the three types of fabrics, cotton fabrics were used in the evaluation of the texture and fastness to wet friction.
-Image clarity: The sensory evaluation was performed visually. The three types of fabrics were evaluated in four stages: A for the case of clearness, B for the case of clearness with two types, C for the case of only one type, and D for no clear image.
-Texture: The untreated cloth before dyeing and the colored cloth after dyeing were touched by hand, and the texture of the colored cloth was subjected to sensory evaluation. 10 points were given for the excellent texture of the colored fabric close to that of the untreated fabric, and 0 for the others, and this evaluation was performed by 10 people. The numerical values of the total points are shown in Table 2 below. A larger numerical value indicates an excellent texture close to the untreated cloth (100 (points)).
-Wet friction fastness: JIS L-0849 (revised in 2013) Evaluated based on the Gakushin type friction test (class 5 method).
The evaluation result of wet friction fastness shows that the larger the value, the better the fastness.

As is apparent from the above results, a dyed fabric having fabric versatility (giving clear images with various fabrics), good texture, and wet friction fastness can be obtained by the inkjet printing method according to the embodiment of the present invention. I know you give it. In addition, the ink jet textile printing method according to the embodiment of the present invention does not require a pretreatment process and does not generate waste water and waste materials.
In particular, in Examples 11 to 15, the wet friction fastness was very excellent.

Next, examples of dye polymers having urethane bonds will be shown.

(Synthesis Example 8)
[Synthesis of Dye Polymer (D-5-4)]
Exemplary compound (D-5-4) was synthesized according to the following scheme.

In a 200 mL three-necked flask, 5.0 g of D-5, 0.9 g of 2,2-bis (hydroxymethyl) propionic acid and 47 g of N-methylpyrrolidone (NMP) were added, and the internal temperature was raised to 90 ° C. To this, 0.12 g of Neostan U-600 (manufactured by Nitto Kasei, trade name) and 3.5 g of 1,6-hexamethylene diisocyanate were added. After completion of dropping, the reaction was carried out at 90 ° C. for 3 hours. The reaction solution was allowed to cool to 20 ° C., poured into 300 mL of a 0.1 mol / L aqueous sodium hydroxide solution, 100 mL of 1 mol / L aqueous hydrochloric acid was added, and the mixture was filtered. The obtained residue was added to a 0.1 mol / L aqueous sodium hydroxide solution and stirred for 10 minutes. Then, 1 mol / L aqueous hydrochloric acid was added to adjust the pH to 5.2, followed by filtration. The obtained residue was poured into 500 mL of water, stirred for 10 minutes, and then filtered. The obtained residue was dried with a vacuum dryer at 60 ° C. for 3 hours to obtain Example Compound (D-5-4). Yield 8.3g. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of the exemplified compound (D-5-4) in methanol / chloroform = 1/1 was 677 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 15,200 (polymethylmethacrylate conversion).

(Synthesis Example 9)
[Synthesis of Dye Polymer (D-6-5)]
Exemplary compound (D-6-5) was synthesized according to the following scheme.

Exemplified compound (D-6-5) was synthesized in the same manner except that D-5 in Synthesis Example 8 was changed to D-6. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of Exemplified Compound (D-6-5) in tetrahydrofuran (THF) was 645 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 12,900 (polymethylmethacrylate conversion).

(Examples 18 to 21)
The dye polymer, and the low molecular surfactant or polymer dispersant were changed to the types and amounts shown in Table 3 below, respectively, except that glycerin was not used and ultrapure water was changed to 3.8 g. Dye polymer aqueous dispersions (8) to (11) were prepared in the same manner as in Example 1.

From Table 3 above, Examples 18 to 21 using a dye polymer having a structure derived from a dye having an anthraquinone skeleton and having a urethane bond are the initial ones of the particulate dye polymer in the aqueous dye polymer dispersion. It can be seen that the ratio of the average particle diameter after aging to the average particle diameter is closer to 1, and the stability is excellent.

(Examples 22 to 25)
Inkjet printing inks (A8) to (A11) In the same manner as the inkjet printing ink (A1), except that the dye polymer aqueous dispersion (1) is changed to the dye polymer aqueous dispersions (8) to (11). Was prepared.
Inkjet printing was carried out in the same manner as in Example 11 except that the ink for inkjet printing used was changed to the ink for inkjet printing shown in Table 4 below, and the same evaluation was performed.

As is clear from the above results, the inkjet printing methods according to Examples 22 to 25 have fabric versatility (giving clear images on various fabrics), good texture, and excellent wet friction fastness. It can be seen that this gives a dyed fabric having the same. In addition, the ink jet textile printing methods according to Examples 22 to 25 do not require a pretreatment process and do not generate waste water and waste materials, so that they are excellent in environmental load and have no problem in workability.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on February 26, 2016 (Japanese Patent Application No. 2016-035892) and a Japanese patent application filed on July 28, 2016 (Japanese Patent Application No. 2016-148849). Is incorporated herein by reference.

Claims

An ink-jet printing method comprising a step of directly printing an ink-jet ink containing an aqueous dispersion of a dye polymer having a structure derived from a dye having an anthraquinone skeleton on an ink-jet method.
The inkjet printing method according to claim 1, wherein the dye polymer further has a repeating unit containing -COOM. However, said M represents a hydrogen atom or a counter cation.
The inkjet printing method according to claim 1, further comprising a heat treatment step.
The inkjet printing method according to any one of claims 1 to 3, wherein the inkjet ink further contains an aqueous organic solvent.
The inkjet printing method according to any one of claims 1 to 4, wherein the dye polymer is a dye polymer having a repeating unit represented by the following general formula (1).

In the 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 hydrogen atom from a dye having an anthraquinone skeleton. Represents.
The inkjet printing method according to any one of claims 1 to 4, wherein the dye polymer further has a urethane bond.
The ink-jet printing method according to claim 6, wherein the dye polymer is a dye polymer having a repeating unit represented by the following general formula (1-2).

In General Formula (1-2), L 2 and L 3 each independently represent a linking group, and D 1 represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye having an anthraquinone skeleton.
In the general formula (1) or (1-2), D 1 represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye represented by the following general formula (M1). The inkjet printing method as described.

In general formula (M1), R 101 to R 108 each independently represents a hydrogen atom or a substituent.
The inkjet printing method according to claim 6, wherein the dye polymer is a dye polymer having a repeating unit represented by the following general formula (1-3).

In General Formula (1-3), L 3 represents a linking group, L 4 and L 5 each independently represent a single bond or a linking group, and D 2 represents two arbitrary hydrogen atoms from a dye having an anthraquinone skeleton. Represents the removed dye residue.
Formula (1-3) D 2 in represents removing two dye residue arbitrary hydrogen atom from a dye represented by the following general formula (M1), ink-jet printing process according to claim 9.

In general formula (M1), R 101 to R 108 each independently represents a hydrogen atom or a substituent.
A coloring composition comprising an aqueous dispersion of a dye polymer having a structure derived from a dye having an anthraquinone skeleton.
An inkjet ink comprising an aqueous dispersion of a dye polymer having a structure derived from a dye having an anthraquinone skeleton.
The inkjet ink according to claim 12, further comprising an aqueous organic solvent.
The dye polymer in an aqueous dispersion of a dye polymer having a structure derived from a dye having an anthraquinone skeleton is a particulate dye polymer, and the average particle diameter of the particulate dye polymer is 30 to 500 nm. The inkjet ink according to 13.
The weight average molecular weight of the dye polymer in the aqueous dispersion of the dye polymer having a structure derived from the dye having the anthraquinone skeleton is 2,000 to 2,000,000. Inkjet ink.
The inkjet ink according to claim 15, which is used for textile printing.
An ink cartridge filled with the inkjet ink according to any one of claims 12 to 16.
A dye polymer having a structure derived from a dye having an anthraquinone skeleton, a repeating unit derived from a monomer represented by the following general formula (1A), and a repeating unit containing —COOM. However, said M represents a hydrogen atom or a counter cation.

In General Formula (1A), R 1a represents a hydrogen atom or a methyl group. When R 1a represents a hydrogen atom, R 2a represents a linear, branched or cyclic alkyl group which may have a substituent, and when R 1a represents a methyl group, R 2a has an aromatic ring. It represents a linear, branched or cyclic alkyl group which may have a substituent having 3 or more nuclear atoms.
A dye polymer having a structure derived from a dye having an anthraquinone skeleton and having a urethane bond.
The dye polymer according to claim 19, wherein the dye polymer further has a repeating unit containing -COOM. However, said M represents a hydrogen atom or a counter cation.