JP2018131697A - INKJET PRINTING METHOD, COLORING COMPOSITION, INKJET INK, INK CARTRIDGE, POLYMER, AND COLORED FABRIC - Google Patents

Abstract

Kind Code: A1 A colored cloth that can dye various kinds of fabrics, does not require a pretreatment process, has a low environmental burden, has no problem in workability, has excellent image clarity and fastness, and is colored. To provide an ink-jet printing method and the like capable of obtaining a colored fabric having excellent quality. An inkjet including a step of directly printing an inkjet ink including an aqueous dispersion of a dye polymer having a structure derived from a dicyanostyryl dye on a fabric by an inkjet method, and a step of heat-treating the fabric after printing. PRINTING METHOD, COLORED COMPOSITION AND INKJET INK CONTAINING AQUEOUS DISPERSION OF THE POLYMER, INK CARTRIDGE WITH INKJET INK, DYE POLYMER WITH STRUCTURE DERIVED FROM DICYANOSTYL DYE AND WATER DISPERSABLE GROUP, AND COLOR CONTAINING THE POLYMER cloth. [Selection figure] None

Description

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

  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 dispersant are mixed in water and then finely dispersed with an attritor or a mill machine together with glass beads, zirconia beads, titania beads, or stainless steel balls, etc., are used as a colorant. It has been. Then, this colorant is diluted with a reducer containing an emulsion resin for fixing the pigment, a pigment ink is prepared, adhered to the fiber by an ink jet method, and the resin is fused by a heating roller to fix the pigment. .
Unlike the coloring method using dyes, the coloring method using pigments does not require the selection of a colorant depending on the fiber type, and does not require a complicated steam heating (steaming) process or water washing process. The pigment can be fixed.
However, the pigment adheres to (is on) the fiber in the form of particles in which the dye molecules are gathered, and maintains fastness such as washing fastness and friction fastness of the colored cloth (colored cloth). 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 polyurethane colorants having a dicyanostyryl dye structure. 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.

JP 2002-348502 A JP-A-10-58638 JP 2010-37700 A JP-A-52-11297 US Pat. No. 5,194,463 Special table 2004-534106 gazette Special table 2002-509957 gazette

  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).

  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 to provide a 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. To provide a colored fabric.

In order to solve the above-mentioned problems, the present inventors have intensively studied and applied a water dispersion of a polymer containing a structure derived from a dicyanostyryl dye (hereinafter also referred to as “dye polymer”) to a fabric by an inkjet method. By directly printing, various types of fabrics can be dyed, no pretreatment process is required, environmental impact is low, workability is not a problem, and excellent quality colored fabrics can be obtained. I found it.
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, it does not cause bleeding even if it is directly printed on a fabric by an ink jet method, as in the case of pigment particles. Wastewater is not generated because no process is required. 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>
(I) a step of directly printing an ink-jet ink containing an aqueous dispersion of a polymer having a structure derived from a dicyanostyryl dye on a fabric by an ink-jet method; and (ii) a step of heat-treating the fabric after printing. Inkjet printing method.
<2>
The inkjet printing method according to <1>, wherein the polymer is a polymer having a structure represented by the following general formula (P0).

In General Formula (P0), R ¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. * Represents a bonding position.
<3>
The inkjet printing method according to <1> or <2>, wherein the polymer is at least one selected from an acrylic polymer, a urethane polymer, and a styrene polymer.
<4>
The polymer is a urethane polymer,
(A1) a compound represented by the following general formula (1);
(B) a polyisocyanate compound;
(C) at least one selected from dimethylolpropionic acid, dimethylolbutanoic acid, and salts thereof;
<3> The inkjet printing method according to <3>, wherein the polymer is a polymer obtained by reacting.

In General Formula (1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent linking group. Represents.
<5>
The polymer is an acrylic polymer,
(A2) a compound represented by the following general formula (2);
(D) Acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, and salts thereof, and alkoxy polyethylene glycol methacrylate At least one selected from
<3> The inkjet printing method according to <3>, wherein the polymer is a polymer obtained by reacting.

In general formula (2), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group.
<6>
A coloring composition comprising an aqueous dispersion of a polymer having a structure derived from a dicyanostyryl dye.
<7>
The colored composition according to <6>, wherein the polymer is a polymer having a structure represented by the following general formula (P0).

In General Formula (P0), R ¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. * Represents a bonding position.
<8>
The colored composition according to <6> or <7>, wherein the polymer is at least one selected from an acrylic polymer, a urethane polymer, and a styrene polymer.
<9>
The polymer is a urethane polymer,
(A1) a compound represented by the following general formula (1);
(B) a polyisocyanate compound;
(C) at least one selected from dimethylolpropionic acid, dimethylolbutanoic acid, and salts thereof;
<8> The colored composition according to <8>, which is a polymer obtained by reacting.

In General Formula (1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent linking group. Represents.
<10>
The polymer is an acrylic polymer,
(A2) a compound represented by the following general formula (2);
(D) Acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, and salts thereof, and alkoxy polyethylene glycol methacrylate At least one selected from
<8> The colored composition according to <8>, which is a polymer obtained by reacting.

In general formula (2), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group.
<11>
<6>-<10> The inkjet ink containing the coloring composition of any one of <10>.
<12>
The inkjet ink according to <11>, wherein the polymer in an aqueous dispersion of a polymer having a structure derived from the dicyanostyryl dye is a particulate polymer, and the average particle diameter of the particulate polymer is 50 to 500 nm.
<13>
The inkjet ink according to <11> or <12>, which is for textile printing.
<14>
<11>-<13> The inkjet ink cartridge which loaded the inkjet ink of any one of <13>.
<15>
A urethane polymer,
(A1) a compound represented by the following general formula (1);
(B) a polyisocyanate compound;
(C) at least one selected from dimethylolpropionic acid, dimethylolbutanoic acid, and salts thereof;
Polymer obtained by reacting

In General Formula (1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent linking group. Represents.
<16>
<15> The polymer according to <15>, wherein the polymer has a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (1-2).

In General Formula (1-1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent group. Represents a linking group, and L ¹³ represents a linking group.

In General Formula (1-2), L ¹³ represents a linking group, R ¹³ represents a methyl group or an ethyl group, and M represents a hydrogen atom or a counter cation.
<17>
An acrylic polymer,
(A2) a compound represented by the following general formula (2);
(D) Acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, and salts thereof, and alkoxy polyethylene glycol methacrylate At least one selected from
Polymer obtained by reacting

In general formula (2), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group.
<18>
<17> The polymer according to <17>, wherein the polymer has a repeating unit represented by the following (a2-1) and at least one repeating unit selected from the following (d1) to (d6).

In general formula (a2-1), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. Represents an unsubstituted alkylcarbonylamino group having 2 to 5 carbon atoms, and R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group.

In general formulas (d1) to (d5), M represents a hydrogen atom or a counter cation.
In General Formula (d6), p represents an integer of 2 to 100, and R ²⁶ represents an alkyl group having 1 to 18 carbon atoms.
<19>
A colored fabric comprising a fabric and a polymer having a structure derived from a dicyanostyryl dye.

  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 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). Furthermore, the above-mentioned excellent quality colored cloth can be provided.

  Hereinafter, the present invention will be described in detail.

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

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

<Polymer having structure derived from dicyanostyryl dye>
The structure derived from a dicyanostyryl dye is a group (dicyanostyryl dye residue) obtained by removing one or more arbitrary hydrogen atoms from an organic compound used as a dicyanostyryl dye.
The dicyanostyryl dye 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 polymer having a structure derived from a dicyanostyryl dye is not particularly limited as long as the polymer has a structure derived from a dicyanostyryl dye in the molecule, and may be a linear polymer or a network polymer. May be.
The dye polymer is preferably a pigment multimer containing a structure derived from a dicyanostyryl dye as a repeating unit.
As the dye polymer, a polymer having a structure derived from a dicyanostyryl dye in the main chain or side chain is preferably used. The polymer constituting the main chain in the polymer having a structure derived from a dicyanostyryl dye in the side chain is not particularly limited, but an acrylic polymer, a urethane polymer, or a styrene polymer is preferable, an acrylic polymer or a urethane polymer is more preferable, and a urethane polymer Is particularly preferably used. The polymer constituting the main chain in the polymer having a structure derived from a dicyanostyryl dye in the main chain is not particularly limited, but a urethane polymer is preferably used.
The acrylic polymer in the present invention has at least one repeating unit among a group consisting of a repeating unit obtained by polymerizing (meth) acrylic acid and a repeating unit obtained by polymerizing (meth) acrylic acid ester. It is a polymer. Moreover, the urethane polymer in this invention is a polymer which has a urethane bond, 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 obtained by superposing | polymerizing styrene.

  The dicyanostyryl dye may be a water-soluble dye or a water-insoluble dye, but is a water-insoluble dye from the viewpoint of the water resistance and washing resistance of the dye polymer. It is preferable. Moreover, it is preferable that it is a dye which does not have ionic groups, such as a carboxyl group, a sulfo group, a phosphoric acid group, these salts, and an ammonium group.

  In the dye polymer, a method for introducing a structure derived from a dicyanostyryl dye is arbitrary, and a monomer having a structure derived from a dicyanostyryl dye may be polymerized or copolymerized to obtain a multimer. After the formation, a structure derived from a dicyanostyryl dye may be introduced by a polymer reaction or the like.

  The structure derived from the dicyanostyryl dye in the present invention may be a structure introduced using a commercially available dicyanostyryl dye. However, as described above, this case is not limited to the structure that is commercially available as a dicyanostyryl dye. For example, when a commercially available dicyanostyryl dye has a substituent, a structure in which the substituent is removed or a structure in which the substituent is changed to another substituent is also included.

As the polymer having a structure derived from a dicyanostyryl dye, a conventionally known compound described in Polymer (1999) Vol. 40, No. 17, page 4923 and the like can be used.
The polymer having a structure derived from a dicyanostyryl dye is preferably a polymer having a structure represented by the following general formula (P0).

In General Formula (P0), R ¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. * Represents a bonding position.

  The polymer having a structure derived from a dicyanostyryl dye is preferably at least one selected from an acrylic polymer, a urethane polymer and a styrene polymer, more preferably an acrylic polymer or a urethane polymer. It is more preferable that the polymer is a urethane polymer having a structure represented by (II) or an acrylic polymer having a structure represented by the general formula (P0).

As the urethane polymer having a structure represented by the general formula (P0), the following dye polymer (P1) is preferable.
As the acrylic polymer having a structure represented by the general formula (P0), a dye polymer (P2) described later is preferable.

[Dye polymer (P1)]
The dye polymer used in the present invention is a urethane polymer,
(A1) a compound represented by the following general formula (1);
(B) a polyisocyanate compound;
(C) One of preferred embodiments is a polymer (dye polymer (P1)) obtained by reacting at least one selected from dimethylolpropionic acid, dimethylolbutanoic acid, and salts thereof. .

In General Formula (1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent linking group. Represents.

  In addition, description of the said carbon number shall not include carbon contained in a substituent, when each group has a substituent.

(A1) Compound represented by general formula (1) In general formula (1), R ¹¹ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. An alkoxy group having 1 to 4 carbon atoms is represented.
Examples of the halogen atom represented by R ¹¹ include a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom is preferable.
Examples of the substituted or unsubstituted alkyl group having 1 to 4 carbon atoms represented by R ¹¹ include a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted isopropyl group, and the like. An ethyl group is preferred.
Examples of the substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms represented by R ¹¹ include a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted isopropoxy group, and the like. Group and ethoxy group are preferred.
Examples of the substituent when the alkyl group or alkoxy group represented by R ¹¹ has a substituent include a halogen atom and a substituted or unsubstituted phenyl group.
R ¹¹ is preferably a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, or a chlorine atom, and more preferably a methyl group or a chlorine atom.

In General Formula (1), R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms.
Examples of the substituted or unsubstituted alkyl group having 1 to 4 carbon atoms represented by R ¹² include a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms represented by R ¹¹ , and preferred examples thereof are also the same.
Examples of the substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms represented by R ¹² include a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms represented by R ¹¹ , and preferred examples thereof are also the same.
R ¹² is preferably a hydrogen atom, a methoxy group, or an ethoxy group, and more preferably a hydrogen atom.

In General Formula (1), L ¹¹ and L ¹² each independently represent a divalent linking group.
The divalent linking group represented by L ¹¹ and L ¹² is not particularly limited as long as the effects of the present invention can be achieved, but is a substituted or unsubstituted linear, branched or cyclic alkylene having 1 to 30 carbon atoms. Group (for example, methylene group, ethylene group, trimethylene group, propylene group, butylene group, cyclohexylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, phenylene group, naphthalene group, etc.), A substituted or unsubstituted heterocyclic group, —CH═CH—, and a linking group formed by linking two or more of these are preferable. In these linking groups, —O—, —S—, —NR— (R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C (═O) — , -SO -, - SO ₂ - may have the like.
L ¹¹ and L ¹² are preferably a linear, branched or cyclic alkylene group, more preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and a straight chain having 1 to 6 carbon atoms. More preferably, it is a chain, branched or cyclic alkylene group.
In addition, description of the said carbon number shall not include carbon contained in a substituent, when each group has a substituent.

  Examples of the compound represented by the general formula (1) include the following exemplified compounds.

(B) Polyisocyanate Compound The polyisocyanate compound is a compound having two or more isocyanate groups (—NCO), and a compound represented by the following general formula (B) is preferable.

In the general formula (B), L ¹³ represents a linking group.

In the general formula (B), the linking group represented by L ¹³ is not particularly limited as long as the effects of the present invention can be achieved, but is a substituted or unsubstituted linear, branched or cyclic group having 1 to 30 carbon atoms. An aliphatic hydrocarbon group (which may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group), a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms (aromatic hydrocarbon group) Or may be an aromatic heterocyclic group), a heterocyclic group, and a linking group formed by linking two or more of these. In these linking groups, —O—, —S—, —NR— (R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C (═O) — , -SO -, - SO ₂ - may have the like.
L ¹³ is preferably a divalent linking group. L ¹³ 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 ¹³ may have a substituent, and examples of the substituent include a substituent selected from the substituent group A.
In addition, description of the said carbon number shall not include carbon contained in a substituent, when each group has a substituent.

  Examples of the polyisocyanate compound include the following exemplary compounds.

(C) At least one diol component selected from dimethylolpropionic acid, dimethylolbutanoic acid, and salts thereof (c) The diol component is represented by the following general formula (C).

In the general formula (C), R ¹³ represents a methyl group or an ethyl group, and M represents a hydrogen atom or a counter cation.

In general formula (C), -COOM (M represents a hydrogen atom or a counter cation) is included as a water-dispersible group. -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 lithium ion or sodium ion is more preferable.
M is preferably a hydrogen atom or a sodium ion.

  By including -COOM in the dye polymer (P1), the dispersibility of the dye polymer in the ink can be improved, and the ink ejection property when used as an inkjet ink is improved, and a clear image without fading is obtained. Can be obtained.

The dye polymer (P1) has a urethane bond. A polymer having a urethane bond generally has a low Tg (glass transition point) and is soft, and thus has high followability to a fabric. For this reason, it is thought that by using a dye polymer having a urethane bond, it is possible to improve the friction resistance and texture of the colored fabric after printing.
The dye polymer (P1) may be a linear polymer having a urethane bond in the main chain, or may be a network polymer having a urethane bond.

  Preferable examples of the dye polymer (P1) include a polymer having a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (1-2).

In General Formula (1-1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent group. Represents a linking group, and L ¹³ represents a linking group.

In General Formula (1-2), L ¹³ represents a linking group, R ¹³ represents a methyl group or an ethyl group, and M represents a hydrogen atom or a counter cation.

In the general formula ^{(1-1), R 11, R} 12, L 11 and ^{L 12} are respectively synonymous with ^{R 11, R 12, L} 11 and ^{L 12} in the general formula (1), preferable examples It is.
In the general formula ^{(1-1), L 13} have the same meanings as defined in formula (B) ^{L 13} of, and preferred examples are also the same.

In the general formula ^{(1-2), R 13} and M are respectively the same as ^{R 13} and M in the general formula (C), and so are the preferable examples.
In the general formula ^{(1-2), L 13} have the same meanings as defined in formula (B) ^{L 13} of, and preferred examples are also the same.

The weight average molecular weight (Mw) of the dye polymer (P1) is preferably 3,000 to 2,000,000, more preferably 3,000 to 1,000,000, and 3,000 to 80,000. 000 is more preferable, 3,000 to 60,000 is particularly preferable, and 5,000 to 30,000 is most preferable.
The dispersity (Mw / Mn) of the dye polymer (P1) is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, and still more preferably 1.0 to 5.0. And particularly preferably 1.0 to 3.0. Mn represents a number average molecular weight.
The weight average molecular weight of the dye polymer (P1) can be calculated from gel permeation chromatography (GPC) measurement. In this specification, unless otherwise specified, GPC is measured using HLC-8220GPC (manufactured by Tosoh Corp.) 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 appropriately selected. As long as the carrier can be dissolved, a 5 mmol / L sodium trifluoroacetate trifluoroethanol solution was used.

  The dye polymer (P1) preferably contains 24 to 96% by mass, more preferably 34 to 91% by mass of the repeating unit represented by the general formula (1-1) with respect to all the repeating units. Preferably, it is contained 57 to 91% by mass.

  In addition, the dye polymer (P1) preferably has the repeating unit represented by the general formula (1-2) in an amount of 1 to 29% by mass, more preferably 2 to 24% by mass, based on all the repeating units. Preferably 2-19 mass% is contained. When the content of the repeating unit represented by the general formula (1-2) is 1% 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.

  The dye polymer (P1) may have other repeating units. Examples of other repeating units include repeating units represented by the following general formula (1-3).

In General Formula (1-3), L ¹³ represents a linking group, and L ¹⁴ represents a divalent linking group.

In General Formula (1-3), L ¹³ has the same meaning as L ¹³ in General Formula (B), and preferred examples are also the same.
In the general formula (1-3), L ¹⁴ represents a divalent linking group, and the divalent linking group is not limited as long as the effects of the present invention can be achieved, but in the general formula (1) And divalent linking groups that can be taken by L ¹¹ and L ¹² .
L ¹⁴ is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms.

  When dye polymer (P1) has another repeating unit, it is preferable that the content rate of another repeating unit shall be 5-30 mass% with respect to all the repeating units.

  The dye polymer (P1) may have a hydroxyl group, or may have a hydroxyl group in a structure derived from a dicyanostyryl dye.

[Method for producing dye polymer (P1)]
The dye polymer (P1) includes a compound represented by the general formula (1), a polyisocyanate compound represented by the general formula (B), and a diol component represented by the general formula (C). It can be produced by addition reaction.

  In the reaction solvent, the compound represented by the general formula (1), the polyisocyanate compound represented by the general formula (B), and the diol component represented by the general formula (C) are dissolved or dispersed. The solvent is not particularly limited as long as it does not inhibit the polyaddition reaction, but preferably tetrahydrofuran, dioxane, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl Pyrrolidone, 1,3-dimethylimidazolone, toluene, ethyl acetate, butyl acetate and nitrobenzene.

  The reaction temperature is not particularly limited as long as the polyaddition reaction proceeds, but is preferably 50 ° C or higher and 150 ° C or lower, more preferably 60 ° C or higher and 130 ° C or lower.

  In order to accelerate the reaction, a reaction catalyst may be used in combination. Examples of the reaction catalyst include amine-based catalysts (for example, N, N-dimethylcyclohexylamine, N-methylmorpholine, N, N-diethylethanolamine, diazabicycloundecene and their circles) and metal-based (dibutyltin dilaurate, bismuth, etc.). Tris (2-ethylhexanoate) and the like. The catalyst amount is preferably 0.001 to 10% by mass with respect to the mass of the polyisocyanate compound.

Although the preferable specific example of dye polymer (P1) is shown to following Table 1 and 2, it is not limited to these. In the following specific examples, the dye polymer (P1) is shown using a monomer structure, but the dye polymer (P1) has a structural unit corresponding to each monomer obtained by reacting them. The urethane polymer which has a ratio is shown. M of the diol component represents M in the general formula (C).
Abbreviations of diol components used in Tables 1 and 2 below represent the following compounds.
DMPA: dimethylolpropionic acid DMBA: dimethylolbutanoic acid NPG: neopentyl glycol EG: ethylene glycol DEA: diethanolamine

[Dye polymer (P2)]
The dye polymer in the present invention is an acrylic polymer,
(A2) a compound represented by the following general formula (2);
(D) Acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, and salts thereof, and alkoxy polyethylene glycol methacrylate At least one selected from
It is also a preferred embodiment that the polymer is a polymer obtained by reacting (Dye polymer (P2)).

In general formula (2), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group.

  In addition, description of the said carbon number shall not include carbon contained in a substituent, when each group has a substituent.

(A2) Compound represented by general formula (2) In general formula (2), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. A 1-4 alkoxy group or a substituted or unsubstituted C2-C5 alkylcarbonylamino group is represented.
As the halogen atom represented by R ²¹ , a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹¹ in the general formula (1) represents Examples include a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms.
Examples of the substituted or unsubstituted alkylcarbonylamino group having 2 to 5 carbon atoms represented by R ²¹ include an acetylamino group and a propionylamino group, and is preferably an acetylamino group.
Examples of the substituent when the alkylcarbonylamino group represented by R ²¹ has a substituent include a halogen atom and a phenyl group.
R ²¹ is preferably a hydrogen atom, a halogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, or an unsubstituted alkoxy group having 1 to 4 carbon atoms, and preferably a hydrogen atom, a chlorine atom, or a methyl group. More preferred.

In General Formula (2), R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms.
The substituted or unsubstituted alkyl group having 1 to 4 carbon atoms represented by R ²² or the substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms may be substituted or unsubstituted represented by R ¹² in the general formula (1). Examples thereof include a substituted alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms.
R ²² is preferably a hydrogen atom, a substituted or unsubstituted alkoxy group, and more preferably a hydrogen atom.

In general formula (2), R ²³ represents a substituted or unsubstituted alkyl group.
Examples of the substituted or unsubstituted alkyl group represented by R ²³ include a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms is preferable.
Examples of the substituent when R ²³ has a substituent include a halogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group, a hydroxyl group, a cyano group, and a substituted or unsubstituted alkoxy having 2 to 8 carbon atoms. In addition to a carbonyl group and a substituted or unsubstituted acyloxy group having 2 to 10 carbon atoms, —O (CO) —C (CH ₃ ) ═CH ₂ is preferably exemplified.
R ²³ is preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and more preferably an unsubstituted alkyl group having 2 to 4 carbon atoms. Further, -O (CO) -C as a substituent _(CH 3) = CH ₂ is also preferable.

In the general formula (2), R ²⁴ represents a hydrogen atom, or a substituted or unsubstituted alkyl group.
As the substituted or unsubstituted alkyl group represented by R ²⁴ , a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms is preferable, and an unsubstituted alkyl group having 1 to 3 carbon atoms is preferable.
Examples of the substituent when R ²⁴ has a substituent include a halogen atom, a substituted or unsubstituted phenyl group, and a carboxyl group.
R ²⁴ is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the general formula (2), L ²¹ represents a divalent linking group.
The divalent linking group represented by L ²¹ is not particularly limited as long as the effects of the present invention can be achieved, but 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 (for example, phenylene group, naphthylene group, etc.), substituted or unsubstituted heterocyclic group, -CH = CH- and a linking group formed by linking two or more of these are 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 - may have the like.
In addition, description of the said carbon number shall not include carbon contained in a substituent, when each group has a substituent.
L ²¹ is preferably —R ²⁵ OC (═O) —L ²² — (R ²⁵ represents an alkylene group, and L ²² represents a single bond or a divalent linking group). The alkylene group represented by R ²⁵ is more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms. Examples of the divalent linking group represented by L ²² include the groups listed as the divalent linking group represented by L ²¹ . L ²² is preferably a single bond or a 1,4-phenylene group, and more preferably a single bond.

Examples of the compound represented by the general formula (2) include the following exemplified compounds. In the following ^{L 21,} * represents a linking site to the N, ** represents a linking site with C. AC represents an acetyl group.

  Next, (d) acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, and salts thereof, and methacrylic acid At least one monomer selected from alkoxy polyethylene glycol (also referred to as “monomer (d)”) will be described.

  When the monomer (d) is a carboxylate, the counter cation forming the carboxylate includes ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethyl). Ammonium ion, tetramethylguanidinium ion, tetramethylphosphonium ion, tetrabutylammonium ion), lithium ion, sodium ion, potassium ion, and ammonium ion are preferable, and lithium ion or sodium ion is more preferable.

The dye polymer (P2) contains —COOM (M represents a hydrogen atom or the above-mentioned counter cation) or an ethyleneoxy group (—CH ₂ CH ₂ O—) as a water-dispersible group. The dispersibility of the ink can be improved, the ink dropability when used as an inkjet ink is improved, and a clear image without fading can be obtained.

  The dye polymer (P2) may be a linear polymer or a network polymer.

  Preferable examples of the dye polymer (P2) include a polymer containing a repeating unit represented by the following (a2-1) and at least one repeating unit selected from the following (d1) to (d6).

In general formula (a2-1), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. Represents an unsubstituted alkylcarbonylamino group having 2 to 5 carbon atoms, and R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group.

In general formulas (d1) to (d5), M represents a hydrogen atom or a counter cation.
In General Formula (d6), p represents an integer of 2 to 100, and R ²⁶ represents an alkyl group having 1 to 18 carbon atoms.

In formula ^{(a2-1), R 21, R} 22, R 23, R 24, and ^{L 21} are, ^R 21 in the general formula ^{(2), R 22, R} 23, R 24, and the ^{L 21} The same is true for the preferred examples.

In general formulas (d1) to (d5), M represents a hydrogen atom or a counter cation. Examples of the counter cation include counter cations that can be used when the monomer (d) is a carboxylate.
M is preferably a hydrogen atom or an alkali metal ion.

In General Formula (d6), p represents an integer of 2 to 100, and R ²⁶ represents an alkyl group having 1 to 18 carbon atoms. p is preferably an integer of 4 to 90. R ²⁶ is preferably an alkyl group having 1 to 4 carbon atoms.

  The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the dye polymer (P2) are the same as the preferred range of the dye polymer (P1), and the calculation method is the same as that of the dye polymer (P1).

  The dye polymer (P2) preferably contains the repeating unit represented by the above (a2-1) in an amount of 24 to 96% by mass, more preferably 34 to 91% by mass, based on all the repeating units. It is more preferable to contain 57-91 mass%.

  The dye polymer (P2) preferably has at least one repeating unit selected from the above general formulas (d1) to (d6) based on all repeating units, preferably 1 to 29% by mass, more preferably 2 to 24%. It is contained by mass%, particularly preferably 2-19 mass%. When the content of at least one repeating unit selected from the general formulas (d1) to (d6) is 1% 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.

  The dye polymer (P2) may have other repeating units. Examples of other repeating units include repeating units represented by the following general formula (e1).

In the general formula (e1), R ²⁷ represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms.
In addition, description of the said carbon number shall not include carbon contained in a substituent, when each group has a substituent.
Examples of the substituent in the case where R ²⁷ has a substituent include an aryl group, a heterocyclic carbonylamino group (the hetero ring may be substituted with an alkyl group), a cyclic ether group, a hydroxyl group, a dialkylamino group, and the like. Can be mentioned.
R ²⁷ is preferably an n-butyl group, a 2-ethylhexyl group, or a benzyl group.

  When dye polymer (P2) has another repeating unit, it is preferable that the content rate of another repeating unit is 5-30 mass% with respect to all the repeating units.

[Method for producing dye polymer (P2)]
The dye polymer (P2) can be produced by radical polymerization reaction of the compound represented by the general formula (2) and the monomer represented by the general formula (d).

  As the polymerization solvent, 2-butanone, cyclohexanone, ethyl lactate, propylene glycol-1-monomethyl ether, methylpropylene glycol, tetrahydrofuran, N-methylpyrrolidone, or the like is preferably used.

  The polymerization initiator is preferably an azo polymerization initiator (for example, azoisobutyronitrile (AIBN), V-601 (trade name, manufactured by Wako Pure Chemical Industries), V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.). ) Etc. are used.

  A chain transfer agent may be used in combination in order to control the molecular weight. As the chain transfer agent used in combination, 1-dodecanethiol, thiomalic acid and the like are preferably used.

  Although superposition | polymerization temperature is suitably adjusted with the half life of the polymeric compound and polymerization initiator to be used, Preferably it is the range of 50-100 degreeC.

  The addition method includes adding a heavy initiator to a solution (or dispersion) composed of a polymerizable compound and a polymerization solvent (collective polymerization), or dropping a solution in which the polymerization initiator and the polymerizable compound are dissolved in the solvent. The method (drop polymerization) is preferably used.

  Although the preferable specific example of dye polymer (P2) is shown to following Tables 3-7, it is not limited to these. In the following specific examples, the dye polymer (P2) is shown using a monomer structure, but the dye polymer (P2) has a structural unit corresponding to each monomer obtained by reacting them. An acrylic polymer having a ratio is shown. M of the copolymerization component represents M in the general formulas (d1) to (d5). p represents p in the general formula (d6).

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

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

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

(1-2) Average particle diameter It is preferable that the dye polymer is in the form of particles in the aqueous dispersion. The average particle diameter of the particulate dye polymer in the aqueous dispersion of the dye polymer is preferably 50 to 500 nm, more preferably 50 to 300 nm, still more preferably 50 to 200 nm, and 40 to 100 nm. It is particularly preferred. Within this range, the fabric can be directly printed by the ink jet method.
The value measured using the particle size distribution measuring apparatus (Nanotrack UPA EX150, 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 water content in the water dispersion is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and particularly preferably 60 to 90% by mass. Within this range, the stability of the aqueous dispersion and the ejection stability as an inkjet ink can be imparted. The stability of the aqueous dispersion indicates that precipitation or the like hardly occurs.

The (B) an aqueous organic solvent aqueous organic solvent is preferably not more 10g / _{100g-H 2} O or more as the water solubility at 25 ° C., more preferably those which are 20g / _{100g-H 2} O, water and any 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, and if the molecular weight exceeds the molecular weight, a bridge between the dye polymer and the dye polymer is caused. 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 (an electrically neutral nonpolar group having a low affinity with water) and an ionic group (electrical). It is preferable to have an ionic polar group having high affinity with water. The structure may be linear or branched. In the case of a high molecular weight surfactant, the structure may be random, alternating, periodic, or block, and may be a graft polymer designed with a trunk and branch structure.
The low molecular surfactant and the polymer dispersant can be used in any form of an aqueous solution, a dispersion, or an emulsion when mixed with water or an aqueous organic solvent.

(2-4) Forming Method and Obtaining Method For example, the following can be used as the low molecular surfactant or the polymeric dispersant.
Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. Examples of the anionic surfactant include fatty acid soap (for example, sodium oleate), N-acyl glutamate, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfoacetate, sulfated oil, higher alcohol sulfate ester And alkyl phosphate ester salts. Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, and imidazolinium betaine. A suitable example is an amine oxide type such as N, N-dimethyl-N-alkylamine oxide.
Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid Examples include esters, propylene glycol fatty acid esters, and acetylene glycols. A suitable example is SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant. In addition, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. Those listed as surfactants in 308119 (1989) can also be used.
As a nonionic surfactant, Emulgen A-60 (trade name) manufactured by Kao Corporation may be used.
The content of the low molecular surfactant is preferably in the range of 0.001% by mass to 5.0% by mass with respect to the total mass of the aqueous dispersion, and the surface tension of the aqueous dispersion is arbitrarily set within this range. It is preferable to adjust to.

The polymeric dispersant can be produced by copolymerizing a hydrophobic group-containing monomer and an ionic group-containing monomer. Each monomer may be used alone or in combination of two or more. The hydrophobic group-containing monomer and the ionic group-containing monomer are the same as the monomer for the copolymer component of the dye polymer described above. As the polymer dispersant, DISPERBYK-194N (trade name) manufactured by Big Chemie Japan Co., Ltd. can be used.
As a polymer type dispersant, Demol N (trade name) manufactured by Kao Corporation may 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 machine, 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 present invention also relates to a coloring composition comprising an aqueous dispersion of a polymer having a structure derived from a dicyanostyryl dye (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 not only used for fiber dyeing, but also for paper media dyeing, plastic dyeing, paint, coating film, coloring for building materials. It can be used as an agent.

The coloring composition of the present invention may further contain a colorant (dye or pigment) other than the dye polymer. The content of the dye polymer is preferably 50% by mass or more, more preferably 80% by mass or more, and more preferably 100% by mass with respect to the total mass of the colorant including the dye polymer. It is preferable to contain.
As the content of the dye polymer in the colored composition, a good dyeing density is obtained, and considering the storage stability of the colored composition, the content is 0.1 to 20% by mass with respect to the total mass of the colored composition. Preferably, 1-15 mass% is more preferable, and 3-12 mass% is further more preferable.
Moreover, content of the water in a coloring composition becomes like this. Preferably it is 40-90 mass%, More preferably, it is 50-85 mass%, Most preferably, it is 50-80 mass%.

<Organic solvent>
Examples of the organic solvent that can be contained in the colored 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.), polyhydric alcohol alkyl ethers (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 (for example, 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 anionic surfactants include fatty acid soaps, N-acyl glutamates, alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfoacetates, sulfated oils, higher alcohol sulfates, and alkyl phosphates. Etc.

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

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

When each of these surfactants is used, one surfactant may be used alone, or two or more surfactants may be mixed and used.
The content of the surfactant in the 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-5-197075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, JP-B-56 -21141, JP-A-10-88106, etc., cinnamic acid compounds, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10- Triazine compounds described in Japanese Patent No. 182621, Japanese National Publication No. Hei 8-501291, etc., Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used. When the coloring composition contains an ultraviolet absorber, it is possible to improve image storability.

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

(Preservative and antifungal agent)
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; trade name, manufactured by LANXESS), methylene dithiocyanate, halogen-containing nitrogen sulfur compounds, 1,2-benzisothiazolin-3-one (For example, Proxel GXL; manufactured by Arch Chemicals, trade name), sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, And salts thereof.
A preservative and an antifungal agent may be used individually by 1 type, and may use 2 or more types together. When the 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 ethers, heterocycles such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N-ethylmorpholine, Horan, dimethyl sulfoxide, and sulfur-containing compounds such as sulfolane, diacetone alcohol, and polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred.
Moreover, a drying inhibitor may be used individually by 1 type, and may use 2 or more types together. When said coloring composition contains a drying inhibitor, 10 mass%-50 mass% are preferable with respect to the total mass of the total mass of a coloring 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 as an inkjet ink, the surface tension of the colored composition is preferably adjusted to 20 mN / m to 70 mN / m, and more preferably adjusted to 25 mN / m to 60 mN / m. preferable. 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. (See JP 2000-355665, JP 2005-126725, etc.).
Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, uramildiacetic acid, and metal salts thereof (for example, sodium salt).

(Crosslinking agent)
For the purpose of improving the friction resistance and washing fastness of the colored fabric, the colored composition may contain a crosslinking agent. As the crosslinking agent, a blocked isocyanate crosslinking agent (for example, Meikanate CX, TP-10, DM-35HC, SU-268A, etc., all manufactured by Meisei Kogyo Co., Ltd., trade name), a polyfunctional epoxy crosslinking agent (for example, Denacol EX-313, 314, 322, 411, etc. are all manufactured by Nagase ChemteX Corp. and trade names).

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

<Inkjet ink>
The present invention also relates to an inkjet ink comprising the above-described coloring composition. That is, the inkjet ink of the present invention includes an aqueous dispersion of a polymer (dye polymer) having a structure derived from a dicyanostyryl dye. 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 preferable range of the content of the dye polymer and other components in the inkjet ink is the same as the preferable 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 inkjet printing method of the present invention comprises at least (i) a step of directly printing an inkjet ink containing an aqueous dispersion of a dye polymer having a structure derived from a dicyanostyryl dye on a fabric by an inkjet method; And a step of heat-treating the fabric after printing.
The ink-jet printing method of the present invention produces an effect that it can be directly printed on various kinds of fabrics without using waste water or waste paper such as transfer paper and with easy 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 inkjet printing method of the present invention includes a step of heat-treating the fabric after printing as step (ii). 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 treatment can be used for melt dyeing). ). The colored cloth is preferably dried and then subjected to heat treatment for the purpose of melting and dyeing, and the heating temperature and time are selected so that the dye polymer is sufficient to melt and the dye polymer is not thermally decomposed. It is preferable. It is preferable to perform heating temperature at 100-250 degreeC normally, More preferably, it is 100-200 degreeC, Most preferably, it is 120-200 degreeC. The heat treatment time is preferably 30 seconds to 3 minutes. In addition, when a reactive group is introduced into the dye polymer or a crosslinking agent is used as an additive, the reactive group (for example, a blocked isocyanate group) introduced into the dye polymer or an additive is used in this heat treatment step. From the viewpoint of friction resistance, it is preferable to cause a crosslinking reaction using a crosslinking agent (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent).

<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 fabrics, bedding, handkerchiefs, cushion covers, curtains, and the like.

  The colored fiber product (colored cloth) 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. Methods, coloring compositions, and inkjet inks are of great value.

<Colored cloth>
The present invention also relates to a colored fabric comprising a fabric and a polymer having a structure derived from a dicyanostyryl dye (dye polymer).
The fabric and the dye polymer are as described above.
The colored cloth of the present invention can be obtained by printing the cloth by the above-described ink jet printing method of the present invention.

(Synthesis Example 1: Synthesis of dye polymer (P1-4))
The dye polymer (P1-4) was synthesized according to the following scheme.

[Synthesis of Intermediate (1)]
N, N-bis (hydroxyethyl) -m-toluidine (19.5 g) was dissolved in N, N-dimethylformamide (60 mL), and phosphorus oxychloride (30 mL) was added dropwise while maintaining the internal temperature at 50 ° C. or lower. . After completion of the dropwise addition, the mixture was reacted at an external temperature of 100 ° C. for 3 hours, cooled to room temperature (20 ° C.), and poured into ice water (500 g). A 50% by mass aqueous sodium hydroxide solution was added thereto, and the precipitated crystals were separated by filtration and washed with water. The obtained crystals were recrystallized from ethanol (100 mL) to obtain Intermediate (1) in a yield of 18.0 g (81% yield). Mass spectrum (MS) (m / z) = 224 (M + 1, 100%).

[Synthesis of Exemplified Compound (1-4)]
Intermediate (1) (8.9 g), malononitrile (3.3 g), and 4 mL of a 4 mol / L aqueous sodium hydroxide solution were reacted in ethanol (100 mL) at 60 ° C. for 90 minutes. The precipitated crystals were collected by filtration and washed with ethanol to obtain 9.7 g (yield 10.9 g) of yellow crystals of the exemplified compound (1-4). MS (m / z) = 272 (M + 1, 100%).

[Synthesis of Dye Polymer (P1-4)]
Exemplary compound (1-4) (5.4 g) and dimethylolpropionic acid (DMPA) (0.6 g) were dissolved in N-methylpyrrolidone (30 mL) and heated to an internal temperature of 85 ° C. After adding Neostan U-600 (manufactured by Nitto Kasei Co., Ltd., trade name) (0.1 g), hexamethylene diisocyanate (HDI) (4.0 g) was added all at once, and the internal temperature increased to 95 ° C. . After adjusting the internal temperature to 85 ° C., the reaction was continued for 6 hours. 5 mL of diethylene glycol monomethyl ether was added to the reaction solution, and the mixture was stirred at an internal temperature of 85 ° C. for 30 minutes, and then added to dilute hydrochloric acid (500 mL), and the precipitated crystals were collected by filtration. The obtained crystals were vacuum-dried at 60 ° C. to obtain 9.8 g of a dye polymer (P1-4). As a result of gel permeation chromatography (GPC) measurement, the weight average molecular weight of the dye polymer (P1-4) was 15,600.

(Synthesis Example 2: Synthesis of Dye Polymer (P2-4))
The dye polymer (P2-4) was synthesized according to the following scheme.

(Synthesis of Exemplary Compound (2-4))
Intermediate (2) (synthesized by the method described in Patent Document CN105481623A, paragraph number 0051) (35.7 g), methacrylic anhydride (43.2 g) were added to toluene (500 mL), and pyridine (22 g) was added. In addition, the mixture was reacted at 80 ° C. for 8 hours. The reaction solution was cooled to room temperature, washed with water (200 mL), washed twice with a saturated aqueous sodium hydrogen carbonate solution (200 mL), further washed twice with dilute hydrochloric acid (200 mL), and then 4-hydroxy-1,1,2, , 2-Tetramethylpyridine-N-oxide (200 mg) was added, and toluene (400 mL) was distilled off using a rotary evaporator. After adding n-hexane to precipitate crystals, the crystals were filtered off and recrystallized twice with acetonitrile to obtain 32.6 g (yield 72%) of the yellow powder of the exemplified compound (2-4). . MS (m / z) = 324 (M + 1, 100%).

(Synthesis of dye polymer (P2-4))
Exemplary compound (2-4) (13.4 g) and methacrylic acid (MA) (6.6 g) were dissolved in N-methylpyrrolidone (80 mL), and the internal temperature was heated to 80 ° C. under a nitrogen atmosphere. Dodecanethiol (1.8 g) was added thereto, and azo polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) (1.0 g) was added all at once and reacted for 3 hours. V-601 (0.5 g) was further added and reacted for 3 hours, and then the internal temperature was set to 95 ° C. and stirred for 1 hour. The reaction solution was cooled to room temperature and reprecipitated with n-hexane (800 mL) to obtain a dye polymer (P2-4) in a yield of 19.8 g. As a result of gel permeation chromatography (GPC) measurement, the weight average molecular weight of the dye polymer (P2-4) was 14,800.

Example 1
[Preparation of dye polymer aqueous dispersion (1)]
0.25 g of dye polymer (P1-1), 10 g of zirconia beads (made by Nikkato, trade name YTZ ball, diameter 0.1 μm), 0.05 g of sodium oleate, 0.5 g of glycerin, and 4.2 g of ultrapure water are added. Then, it was dispersed for 6 hours at a rotation speed of 400 rpm (revolution per minute) using a planetary fine pulverizer (Pulverset 7 manufactured by Fritsch). From the obtained dispersion, zirconia beads were removed using a filter cloth to obtain a dye polymer aqueous dispersion (1).
In Example 1, sodium oleate is a low molecular surfactant.

(Examples 2 to 20)
The same procedure was performed except that the dye polymer and the low molecular surfactant were changed to the type and amount of the dye polymer shown in Table 8 below and the type and amount of the low molecular surfactant or polymer dispersant, respectively. Thus, dye polymer aqueous dispersions (2) to (20) were prepared. DEMAL NL and Emulgen A-60 are manufactured by Kao Corporation.

  The weight average molecular weight of the dye polymer used and the average particle diameter of the particulate dye polymer in the obtained dye polymer aqueous dispersion were as shown in Table 9.

(Example 21)
[Preparation of ink-jet printing ink (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]
Ink-jet textile printing ink (A1) is loaded into an ink cartridge, and polyester fabric (product name: polyester tropical (manufactured by Teijin Ltd.)) is sold using an ink-jet printer (Calario PX-045A, product name) manufactured by Seiko Epson Corporation. Tip Color dyeing company, product code A02-01019), Cotton fabric (with cotton broad sill, product code A02-01002), polyester 65% cotton 35% blend (blend 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 at a temperature of 150 ° 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: tabletop automatic flat press machine AF-54TEN type). Thus, a clear yellow image without blur was obtained.

(Examples 22 to 40)
Inkjet textile printing inks (A2) to (A20) In the same manner as the inkjet textile printing ink (A1) except that the dye polymer aqueous dispersion (1) is changed to the dye polymer aqueous dispersions (2) to (20) Was prepared.
In Examples 22 to 40, inkjet printing was performed in the same manner as in Example 21 except that the inkjet printing ink used was changed to the inkjet printing ink shown in Table 10 below. All were clear yellow.

(Example 41)
Unisense KHE104L (manufactured by Senka Co., Ltd., trade name) is applied to a cotton fabric (with cotton broad sill, manufactured by Color Dye Co., Ltd., product code A02-01002) so that the solid content is 0.2 g / m ^2. The pretreated cloth (T1) was prepared by drying at 20 ° C. for 12 hours or more. Inkjet printing was performed in the same manner except that the fabric of Example 21 was changed to a pretreatment fabric (T1). It had a clear yellow color.

(Example 42)
Unisense KHE100L (Senka Co., Ltd., trade name) was applied to a cotton fabric (with cotton broad sill, manufactured by Color Dyeing Co., Ltd., product code A02-01002) so that the solid content was 0.2 g / m ^2. The pre-treated cloth (T2) was created by drying at 20 ° C. for 12 hours or more. Inkjet printing was performed in the same manner except that the fabric of Example 21 was changed to a pretreated fabric (T2). It had a clear yellow color.

(Example 43)
Unisense FPV1000 (product name, manufactured by Senka Co., Ltd., product name) is applied to a cotton fabric (with cotton broad sill, manufactured by Color Dyeing Co., Ltd., product code A02-01002) so that the solid content is 0.2 g / m ^2. A pretreated cloth (T3) was prepared by drying at 20 ° C. for 12 hours or more. Inkjet printing was performed in the same manner except that the fabric of Example 21 was changed to a pretreated fabric (T3). It had a clear yellow color.

(Example 44)
[[[4- [Bis [2-hydroxyethyl] amino] 2-methylphenyl] methylenepropanedinitrile, a didianostyryl dye obtained from the reaction of 1,4, -butanediol and tolylene-2,4-diisocyanate Polymer synthesis)
According to the synthesis method described in Example 3 of US Pat. No. 5,194,463, [[4- [bis [2-hydroxyethyl] amino] 2-methylphenyl] methylenepropanedinitrile and 1,4, -butanediol And a didianostyryl dye polymer obtained from the reaction with tolylene-2,4-diisocyanate.

[[[4- [Bis [2-hydroxyethyl] amino] 2-methylphenyl] methylenepropanedinitrile, a didianostyryl dye obtained from the reaction of 1,4, -butanediol and tolylene-2,4-diisocyanate Preparation of aqueous dispersion of polymer)
[[4- [Bis [2-hydroxyethyl] amino] 2-methylphenyl] methylenepropanedinitrile, a didianostyryl dye polymer obtained from the reaction of 1,4, -butanediol and tolylene-2,4-diisocyanate 0.25 g, 10 g of zirconia beads (made by Nikkato, trade name YTZ ball, diameter 0.1 μm), 0.05 g of sodium oleate, 0.5 g of glycerin, and 4.2 g of ultrapure water are added, and a planetary fine granulator ( It was dispersed for 6 hours at a rotation speed of 400 rpm (revolution per minute) using a Pulversette 7) manufactured by Frichtu. From the resulting dispersion, zirconia beads were removed using a filter cloth to obtain a dye polymer aqueous dispersion (H1).

[Preparation of inkjet printing ink and inkjet printing]
A comparative inkjet printing ink (J1) was prepared in the same manner as the inkjet printing ink (A1) except that the dye polymer aqueous dispersion (1) of Example 21 was changed to the dye polymer aqueous dispersion (H1). Then, inkjet printing was performed. A faint image was obtained due to defective inkjet ejection.

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

(Comparative Example 2) Coloring by inkjet method using pigment (Preparation of pigment dispersion)
3 g of a styrene-acrylic acid copolymer (Johncrill 678, manufactured by BASF, trade name), 1.3 g of dimethylaminoethanol, and 80.7 g of ion-exchanged water were stirred and mixed at 70 ° C. Next, C.I. I. 15 g of Pigment Yellow 74 and 50% by volume of zirconia beads having a particle diameter of 0.5 mm were filled in 50% and dispersed using a sand grinder mill to obtain a pigment dispersion having a yellow 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 heated to 75 ° C., and a mixture of 80 g of n-butyl methacrylate, 20 g of acrylic acid, 50 g of 2-butanone and 0.5 g of azoisobutyronitrile was added for 3 hours. It was dripped over. After dropping, the mixture was heated to reflux for 5 hours, cooled to room temperature, and heated under reduced pressure to obtain a polymer residue. To this, 350 mL of ion-exchanged water and 1.05 times moles of sodium hydroxide of acrylic acid added as a monomer were added and dissolved. It diluted with ion-exchange water so that the whole quantity might be 500g, and obtained 20% aqueous solution of the aqueous | water-based binder.

(Preparation of pigment ink and coloring by inkjet method)
46.6 g of the pigment dispersion, 15 g of the aqueous binder, 2.9 g of PDX-7664A (trade name, manufactured by BASF), 10 g of triethylene glycol monobutyl ether, 5 g of 1,2-hexanediol, 11.2 g of diethylene glycol, 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 an ink jet printer (Calario PX-045A manufactured by Seiko Epson Corporation, trade name) is used to make a polyester fabric (polyester tropical (manufactured by Teijin Ltd.), Product code A02-01019), cotton fabric (with cotton broad sill, manufactured by Color Dye Co., product code A02-01002), and polyester 65% cotton 35% blend (mixed polyester 65 / cotton 35 broad, manufactured by Color Dye Co., Ltd.) Each image was printed on code A02-01030) and dried at room temperature for 12 hours. After drying, heat treatment is performed using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type) at a temperature of 100 ° C., a pressure of 0.20 N / cm ² , and a time of 60 seconds. Thus, a colored cloth printed with the pigment ink was obtained.

  The evaluation results of Examples 21 to 44 and Comparative Example 1 are shown in Table 10. The evaluation of the colored fabric is the result of the following method. In the evaluation, a cotton fabric was used among the three types of fabrics.

<Image fading>
Visual sensory evaluation was performed. A case where the image was not blurred and a clear yellow color was exhibited was evaluated in two stages, A, and a case where the image was blurred was evaluated in two stages.

<Dye fastness test for xenon arc lamp>
JIS (Japanese Industrial Standards) L0843: 2006 (1998 revision, 2010 confirmation) Evaluation was performed based on the A method and the third exposure method. An evaluation result shows that the one where a numerical value is large is excellent in dyeing | fastening fastness.

<Dye fastness test against friction>
JIS L0849: 2013 (revised 2004) Friction tester type II (Gakushin type, instrument method, vertical direction) was evaluated based on wet conditions. An evaluation result shows that the one where a numerical value is large is excellent in dyeing | fastening fastness.

  As is clear from the above, a dyed fabric that gives a clear image to the fabric by the inkjet printing method according to Examples 21 to 43 of the present invention, and has a fastness to dyeing against a xenon arc lamp and a fastness to dyeing against friction. I know you give it.

Claims (19)

  (I) a step of directly printing an ink-jet ink containing an aqueous dispersion of a polymer having a structure derived from a dicyanostyryl dye on a fabric by an ink-jet method; and (ii) a step of heat-treating the fabric after printing. Inkjet printing method. The inkjet printing method according to claim 1, wherein the polymer is a polymer having a structure represented by the following general formula (P0).

In General Formula (P0), R ¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. * Represents a bonding position.   The inkjet printing method according to claim 1, wherein the polymer is at least one selected from an acrylic polymer, a urethane polymer, and a styrene polymer. The polymer is a urethane polymer;
(A1) a compound represented by the following general formula (1);
(B) a polyisocyanate compound;
(C) at least one selected from dimethylolpropionic acid, dimethylolbutanoic acid, and salts thereof;
The ink-jet printing method according to claim 3, wherein the polymer is a polymer obtained by reacting.

In General Formula (1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent linking group. Represents. The polymer is an acrylic polymer;
(A2) a compound represented by the following general formula (2);
(D) Acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, and salts thereof, and alkoxy polyethylene glycol methacrylate At least one selected from
The ink-jet printing method according to claim 3, wherein the polymer is a polymer obtained by reacting.

In general formula (2), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group.   A coloring composition comprising an aqueous dispersion of a polymer having a structure derived from a dicyanostyryl dye. The coloring composition according to claim 6, wherein the polymer is a polymer having a structure represented by the following general formula (P0).

In General Formula (P0), R ¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. * Represents a bonding position.   The colored composition according to claim 6 or 7, wherein the polymer is at least one selected from an acrylic polymer, a urethane polymer, and a styrene polymer. The polymer is a urethane polymer;
(A1) a compound represented by the following general formula (1);
(B) a polyisocyanate compound;
(C) at least one selected from dimethylolpropionic acid, dimethylolbutanoic acid, and salts thereof;
The coloring composition according to claim 8, which is a polymer obtained by reacting the above.

In General Formula (1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent linking group. Represents. The polymer is an acrylic polymer;
(A2) a compound represented by the following general formula (2);
(D) Acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, and salts thereof, and alkoxy polyethylene glycol methacrylate At least one selected from
The coloring composition according to claim 8, which is a polymer obtained by reacting the above.

In general formula (2), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group.   The inkjet ink containing the coloring composition of any one of Claims 6-10.   The inkjet ink according to claim 11, wherein the polymer in an aqueous dispersion of a polymer having a structure derived from the dicyanostyryl dye is a particulate polymer, and the average particle diameter of the particulate polymer is 50 to 500 nm.   The inkjet ink according to claim 11 or 12, which is used for textile printing.   An ink-jet ink cartridge loaded with the ink-jet ink according to claim 11. A urethane polymer,
(A1) a compound represented by the following general formula (1);
(B) a polyisocyanate compound;
(C) at least one selected from dimethylolpropionic acid, dimethylolbutanoic acid, and salts thereof;
Polymer obtained by reacting

In General Formula (1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent linking group. Represents. The polymer according to claim 15, wherein the polymer has a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (1-2).

In General Formula (1-1), R ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, and L ¹¹ and L ¹² are each independently a divalent group. Represents a linking group, and L ¹³ represents a linking group.

In General Formula (1-2), L ¹³ represents a linking group, R ¹³ represents a methyl group or an ethyl group, and M represents a hydrogen atom or a counter cation. An acrylic polymer,
(A2) a compound represented by the following general formula (2);
(D) Acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, and salts thereof, and alkoxy polyethylene glycol methacrylate At least one selected from
Polymer obtained by reacting

In general formula (2), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group. The polymer according to claim 17, wherein the polymer has a repeating unit represented by the following (a2-1) and at least one repeating unit selected from the following (d1) to (d6).

In general formula (a2-1), R ²¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted group. Represents an unsubstituted alkylcarbonylamino group having 2 to 5 carbon atoms, and R ²² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. R ²³ represents a substituted or unsubstituted alkyl group, R ²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ²¹ represents a divalent linking group.

In general formulas (d1) to (d5), M represents a hydrogen atom or a counter cation.
In General Formula (d6), p represents an integer of 2 to 100, and R ²⁶ represents an alkyl group having 1 to 18 carbon atoms.   A colored fabric comprising a fabric and a polymer having a structure derived from a dicyanostyryl dye.