WO2018155597A1

WO2018155597A1 - Inkjet textile printing method, inkjet ink, ink cartridge, and colored fabric

Info

Publication number: WO2018155597A1
Application number: PCT/JP2018/006591
Authority: WO
Inventors: 健太牛島; 藤江　賀彦; 小林　博美; 誠大元; 理俊水村
Original assignee: 富士フイルム株式会社
Priority date: 2017-02-24
Filing date: 2018-02-22
Publication date: 2018-08-30

Abstract

The present invention provides: an inkjet textile printing method comprising a step for directly printing, on a cloth, an inkjet ink containing an aqueous dispersion of a dye polymer that has a repeating unit including a dye-derived structure and has a repeating unit including a non-ionic hydrophilic group, by an inkjet method; an inkjet ink containing an aqueous dispersion of the dye polymer; an ink cartridge filled with the inkjet ink; and a colored fabric.

Description

Inkjet textile printing method, inkjet ink, ink cartridge, and colored cloth

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

Conventionally, a colorant used for coloring a fabric is either a dye or a pigment, and a screen printing method, a roller printing method, a transfer method, as a method for industrially coloring the fabric using these colorants, 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 an ink is prepared by dissolving a dye in water and a fabric is dyed by an ink jet method.
Each dye molecule penetrates into the inside of the fiber by interacting with the fiber and is integrated with the fiber. Therefore, the fabric dyed with the dye is flexible and has a good texture, and is favored as a quality item for clothing. Yes. On the other hand, in inkjet printing using a dye, it is necessary to steam-heat a colored fabric to fix the dye after dyeing, and then wash the excess dye by a process such as water washing or soaping. For this reason, a process is complicated and an apparatus and time 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 improves the complexity of processes in the above-described ordinary ink-jet printing, the problem of time and labor required for the apparatus, and the problem of waste water (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, stainless steel balls, or the like is used as a colorant. ing. 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 based on the fiber type, and does not require complicated steam heating (steaming) and water washing processes, making it extremely simple to color fibers. 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 hard, and the quality as clothing is inferior to the colored cloth colored 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 Document 4 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 5 describes an ink-jet ink containing polyurethane having a colorant structure.

Japanese Laid-Open Patent Publication No. 2002-348502 Japanese Patent Laid-Open No. 10-58638 Japanese Unexamined Patent Publication No. 2010-37700 Japan Special Table 2004-534106 Japan Special Table 2002-509957

As mentioned above, coloring with dyes is excellent in the quality (texture) and fastness of the colored fabric, but it is necessary to select dyes based on the fiber type, and the process is complicated and the equipment is necessary. There are problems such as 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 I have a problem that the quality (texture) is inferior.
Further, Patent Document 4 does not specifically disclose textile printing, and does not describe any of the above problems.

The problem of the present invention is that various kinds of fabrics can be dyed, the environmental load is small, there is no problem in workability, the image obtained is excellent in sharpness and fastness, and the quality (texture) of the colored fabric. Another object of the present invention is to provide an ink jet textile printing method which is excellent. Further, another problem of the present invention is that various types of fabrics can be dyed, there is little environmental load, there is no problem in workability, the image obtained is excellent in sharpness and fastness, and the colored fabric is An object of the present invention is to provide an inkjet ink capable of providing a colored cloth excellent in quality (texture), an ink cartridge filled with the inkjet ink, and a colored cloth.

The present inventor has conducted research to solve the above problems, and has a polymer having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group (hereinafter also referred to as “dye polymer”). Various types of fabrics can be dyed by the method of directly printing on fabrics using an aqueous dispersion of the above, and there is little environmental burden, no problem in workability, and excellent quality colored fabrics It was found that can be obtained.
Although details are unknown as a mechanism that can solve the above problem by the above method, it is presumed as follows.
In the aqueous dispersion of the dye polymer in the present invention, since the dye polymer is not an aqueous solution but an aqueous dispersion, bleeding can be reduced in the same manner as the pigment particles, and no water washing step is required, so no waste water is generated. In addition, since printing is performed directly on the fabric, waste such as transfer paper is not generated. Since the emulsion resin as the fixing agent is not used unlike the pigment ink, the viscosity of the ink is not increased and the workability is excellent. Furthermore, it is considered that the dye polymer is integrated with the fiber at the molecular level so as to cover the surface of the fiber regardless of the fiber type. For this reason, it is thought that the cloth which consists of various kinds of fibers can be dyed, and the colored cloth of the excellent quality is obtained. The dye polymer in the present invention has a nonionic hydrophilic group as a dispersing group, so that it is necessary for the dispersion stability in water and the fastness of the colored fabric necessary for printing directly on the fabric by the ink jet method. It seems that it became possible to achieve both water resistance.
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 the 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]
Inkjet printing method comprising a step of directly printing an ink-jet ink containing an aqueous dispersion of a polymer having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group on a fabric by an inkjet method .
[2]
Furthermore, the inkjet textile printing method as described in [1] including a heat treatment process.
[3]
The inkjet printing method according to [1] or [2], wherein the inkjet ink further contains an aqueous organic solvent.
[4]
The inkjet printing method according to any one of [1] to [3], wherein the nonionic hydrophilic group is a group represented by the following general formula (A).

In general formula (A), n1 represents an integer of 5 to 150.
[5]
The inkjet printing method according to any one of [1] to [4], wherein the repeating unit including a structure derived from the dye is a repeating unit represented by the following general formula (1).

In General Formula (1), X ¹ represents a linking group, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye.
[6]
D ¹ of the above general formula (1) represents a removing one dye residue arbitrary hydrogen atom from a dye represented by any one of the following formulas (M1) ~ (M8), according to [5] Inkjet printing method.

In general formula (M1), R ¹⁰¹ to R ¹¹⁰ each independently represents a hydrogen atom or a substituent.
In general formula (M2), R ²⁰¹ to R ²¹⁵ each independently represent a hydrogen atom or a substituent, X ²⁰¹ represents a monovalent anion, and n201 represents 0 or 1.
In general formula (M3), R ³⁰¹ to R ³¹⁷ each independently represent a hydrogen atom or a substituent, X ³⁰¹ represents a monovalent anion, and n301 represents 0 or 1.
In General Formula (M4), R ⁴⁰² to R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent, Ar ⁴⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M5), R ⁵⁰¹ to R ⁵⁰⁸ each independently represent a hydrogen atom or a substituent.
In general formula (M6), R ⁶⁰¹ to R ⁶⁰³ each independently represents a hydrogen atom or a substituent, Ar ⁶⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M7), R ⁷⁰¹ to R ⁷⁰⁶ each independently represent a hydrogen atom or a substituent.
In general formula (M8), R ⁸¹¹ to R ⁸¹⁸ and R ⁸²¹ to R ⁸²⁸ each independently represent a hydrogen atom or a substituent.
[7]
The inkjet printing method according to any one of [1] to [6], wherein the glass transition temperature of the polymer is 100 ° C. or lower.
[8]
An inkjet ink for printing comprising a water dispersion of a polymer having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group.
[9]
The inkjet ink according to [8], wherein the nonionic hydrophilic group is a group represented by the following general formula (A).

In general formula (A), n1 represents an integer of 5 to 150.
[10]
The inkjet ink according to [8] or [9], wherein the repeating unit including a structure derived from the dye is a repeating unit represented by the following general formula (1).

In General Formula (1), X ¹ represents a linking group, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye.
[11]
In [10], D ¹ in the general formula (1) represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye represented by any one of the following general formulas (M1) to (M8). Inkjet ink.

In general formula (M1), R ¹⁰¹ to R ¹¹⁰ each independently represents a hydrogen atom or a substituent.
In general formula (M2), R ²⁰¹ to R ²¹⁵ each independently represent a hydrogen atom or a substituent, X ²⁰¹ represents a monovalent anion, and n201 represents 0 or 1.
In general formula (M3), R ³⁰¹ to R ³¹⁷ each independently represent a hydrogen atom or a substituent, X ³⁰¹ represents a monovalent anion, and n301 represents 0 or 1.
In General Formula (M4), R ⁴⁰² to R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent, Ar ⁴⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M5), R ⁵⁰¹ to R ⁵⁰⁸ each independently represent a hydrogen atom or a substituent.
In general formula (M6), R ⁶⁰¹ to R ⁶⁰³ each independently represents a hydrogen atom or a substituent, Ar ⁶⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M7), R ⁷⁰¹ to R ⁷⁰⁶ each independently represent a hydrogen atom or a substituent.
In general formula (M8), R ⁸¹¹ to R ⁸¹⁸ and R ⁸²¹ to R ⁸²⁸ each independently represent a hydrogen atom or a substituent.
[12]
The inkjet ink according to any one of [8] to [11], wherein the glass transition temperature of the polymer is 100 ° C. or lower.
[13]
The inkjet ink according to any one of [8] to [12], further comprising an aqueous organic solvent.
[14]
The inkjet ink according to any one of [8] to [13], wherein the polymer in the aqueous dispersion of the polymer is a particulate polymer, and the average particle diameter of the particulate polymer is 50 to 500 nm. .
[15]
The inkjet ink according to any one of [8] to [13], wherein the polymer has a weight average molecular weight of 3,000 to 2,000,000.
[16]
[8] An ink cartridge filled with the ink jet ink according to any one of [15].
[17]
A colored fabric comprising a fabric and a polymer having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group.

According to the present invention, various kinds of fabrics can be dyed, excellent in environmental load, no problem in workability, excellent in sharpness and fastness of the obtained image, and quality (texture) of the colored fabric. In addition, it is possible to provide an ink jet textile printing method which is excellent. In addition, according to the present invention, various types of fabrics can be dyed, the environmental load is excellent, there is no problem in workability, and the image is excellent in sharpness and fastness, and the color is excellent in quality (texture). Ink-jet ink that can provide a cloth, an ink cartridge filled with the ink-jet ink, and the colored cloth can be provided.

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

<Dye polymer>
The “structure derived from a dye” of the dye polymer in the present invention is a group (dye residue) formed by removing one or more arbitrary hydrogen atoms from a compound used as a dye.
The dye polymer in the present invention is a polymer having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group, a repeating unit containing a structure derived from an arbitrary dye, and any A multimer of a dye comprising a repeating unit containing a nonionic hydrophilic group.
The dye polymer of the present invention may be either linear or branched, the repeating unit may be random, alternating, periodic, or block, and may be a graft polymer or dendrimer with a trunk and branch structure designed. Moreover, you may have a crosslinked structure.
Although the kind of dye polymer is not particularly limited, acrylic polymer, styrene polymer, polyurethane, polyester, polyurea, polyamide, polycarbonate, polyether, and the like can be preferably used, and acrylic polymer and styrene polymer are more preferable.

The acrylic polymer in the present invention is a polymer having at least one type of repeating unit from the group consisting of repeating units derived from (meth) acrylic acid and repeating units derived from (meth) acrylic acid esters. Moreover, the styrene polymer in this invention means the polymer which has a repeating unit derived from styrene.
As a method for obtaining a dye polymer in the present invention, (1) a method of obtaining a multimer by polymerizing or copolymerizing a polymerizable dye monomer and / or a monomer having a nonionic hydrophilic group (2) After forming a polymer, a method of introducing a structure derived from a dye and / or a structure having a nonionic hydrophilic group by a polymer reaction can be used.

In the present invention, since the dye polymer is used in a state of being dispersed in water, the dye polymer has an optimum molecular weight range with respect to dispersibility, and re-aggregation of the dispersion hardly occurs if the molecular weight is below the upper limit of the molecular weight range. On the other hand, it is difficult to dissolve in water and an aqueous organic solvent as long as it is at least the lower limit of the optimum molecular weight range. The molecular weight of the dye polymer of the present invention is preferably a weight average molecular weight of 3,000 to 2,000,000, more preferably 5,000 to 1,000,000, and 8,000 to 200,000. More preferably, it is 000. Within the above range, the dispersion stability and fastness are excellent.
The weight average molecular weight of the dye polymer was calculated by gel permeation chromatography (GPC). In this specification, unless otherwise specified, GPC is measured using HLC-8220GPC (manufactured by Tosoh Corporation), and the column is measured with TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation), and the number average molecular weight is Calculated by polystyrene conversion. The carrier may be appropriately selected, but NMP (N-methylpyrrolidone) was used as long as it was soluble.

The dye polymer of the present invention preferably has a glass transition temperature not higher than the heating temperature of the heat treatment temperature, preferably not higher than 200 ° C, more preferably not higher than 150 ° C, and further preferably not higher than 100 ° C. preferable. When it is in the above range, it is excellent in fastness and quality (texture). The mechanism of excellent robustness is not clear, but is estimated as follows. The dye polymer deposited on the cloth is melted by heat treatment, and the dye polymer film and the cloth are fused to improve the strength of the dye polymer film, and the dye polymer film and the cloth are firmly adhered to each other. However, it is estimated that the robustness is further improved. Further, it is estimated that when the glass transition temperature of the dye polymer is low, the dye polymer film becomes flexible and the quality (texture) is further improved. The glass transition temperature (Tg) of the dye polymer can be measured by DSC (differential scanning calorimetry).

The structure derived from the dye is a structure derived from an organic dye as classified by the color index. For example, an azo dye (monoazo dye, disazo dye, trisazo dye, polyazo dye), stilbene, carotenoid, diarylmethane , Triarylmethane, xanthene, acridine, quinoline, methine (monomethine, polymethine), aniline, indoaniline, indamine, indophenol, azine, oxazine, thiazine, anthraquinone, indigo, quinophthalone, nigrosine, porphyrin, cyanine, dicyanostyryl dye, And phthalocyanine can be preferably used. From the viewpoint of coloring power and light resistance of the dye skeleton, azo dyes, stilbene, diarylmethane, triarylmethane, xanthene, indophenol, anthraquinone, quinophthalone, phthalocyanine, and the like can be preferably used.

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

[Repeating unit containing structure derived from dye]
The repeating unit including a structure derived from the dye is preferably a repeating unit represented by the following general formula (1).

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

[Repeating unit represented by general formula (1)]
The repeating unit represented by the general formula (1) will be described.
In general formula (1), X ¹ represents a linking group. X ¹ is a partial structure of the main chain of the polymer. The linking group for X ¹ is preferably represented by the following (X-1) or (X-2). In the general formula (X-1) or (X-2), it is linked to L ¹ at the site indicated by *.

In General Formula (1), L ¹ represents a single bond or a divalent linking group. In the case where L ¹ represents a divalent linking group, the divalent linking group is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group). , Propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthylene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH═CH—, — O—, —S—, —NR— (R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C (═O) —, —SO—, —SO ₂ —, and A linking group formed by linking two or more of these is preferably used. In particular, a linking group represented by any of the following general formulas (L2) to (L7) is preferably used.
When L ¹ represents a divalent linking group, the divalent linking group may have a substituent (for example, an alkyl group, an aryl group, a hydroxyl group, an acyloxy group, etc.).

In the general formulas (L2) to (L7), * 1 and * 2 each represent a position bonded to X ¹ in the general formula (1), and the other bonds to D ¹ in the general formula (1). Although it represents a position, * 1 represents a position bonded to X ¹ in the general formula (1), and * 2 preferably represents a position bonded to D ¹ in the general formula (1).
In general formula (L2), R ³ represents a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different.
In General Formula (L3), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different.
In General Formula (L4), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different.
In General Formula (L5), R ₅₁ and R ₅₂ each independently represent a hydrogen atom or a substituent. t represents an integer of 1 to 10. The t R ₅₁ and R ₅₂ may be the same or different.
In General Formula (L6), R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a substituent. u and v each independently represents an integer of 1 to 10. u R ⁶¹ and R ⁶² may be the same or different. The v R ⁶³ and R ⁶⁴ may be the same or different.
In general formula (L7), R ⁷¹ , R ⁷² and R ⁷³ each independently represents a hydrogen atom or a substituent. w represents an integer of 1 to 10. Each of w R ⁷¹ and R ⁷² may be the same or different.

In the general formula (1), D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye. D ¹ is not limited as long as it exhibits the effects of the present invention, and represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye represented by any one of the following general formulas (M1) to (M8). More preferably.

In general formula (M1), R ¹⁰¹ to R ¹¹⁰ each independently represents a hydrogen atom or a substituent.
In general formula (M2), R ²⁰¹ to R ²¹⁵ each independently represent a hydrogen atom or a substituent, X ²⁰¹ represents a monovalent anion, and n201 represents 0 or 1.
In general formula (M3), R ³⁰¹ to R ³¹⁷ each independently represent a hydrogen atom or a substituent, X ³⁰¹ represents a monovalent anion, and n301 represents 0 or 1.
In General Formula (M4), R ⁴⁰² to R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent, Ar ⁴⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M5), R ⁵⁰¹ to R ⁵⁰⁸ each independently represent a hydrogen atom or a substituent.
In general formula (M6), R ⁶⁰¹ to R ⁶⁰³ each independently represents a hydrogen atom or a substituent, Ar ⁶⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M7), R ⁷⁰¹ to R ⁷⁰⁶ each independently represent a hydrogen atom or a substituent.
In general formula (M8), R ⁸¹¹ to R ⁸¹⁸ and R ⁸²¹ to R ⁸²⁸ each independently represent a hydrogen atom or a substituent.

R ¹⁰¹ to R ¹¹⁰ in general formula (M1), R ²⁰¹ to R ²¹⁵ in general formula (M2), R ³⁰¹ to R ³¹⁷ in general formula (M3), and R ⁴⁰² to R in general formula (M4) Examples of the substituent when R ⁴⁰⁷ represents a substituent include a substituent selected from the following substituent group A.
The substituents included in Substituent Group A are shown below.

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

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

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

R ¹⁰¹ in the general formula (M1) is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydroxyl group.
R ¹⁰² in formula (M1) is preferably a hydrogen atom, a halogen atom, a carboxyl group, or an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably a hydrogen atom, a halogen atom, or a carboxyl group, particularly preferably. Is a hydrogen atom, a bromine atom, or a carboxyl group.
R ¹⁰⁴ in formula (M1) is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. And particularly preferably an unsubstituted alkyl group having 1 to 8 carbon atoms.
R ¹⁰⁸ in the general formula (M1) is preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, A substituted or unsubstituted carbamoyl group is represented.
R ¹⁰³ , R ¹⁰⁵ and R ¹⁰⁶ in the general formula (M1) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number 6 to 10 An aryl group, a halogen atom, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and particularly preferably a hydrogen atom.
R ¹⁰⁷ , R ¹⁰⁹ and R ¹¹⁰ in the general formula (M1) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number 6 to 10 An aryl group, a halogen atom, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted carbamoyl group, more preferably a hydrogen atom or a halogen atom, particularly preferably hydrogen. Atom, chlorine atom, bromine atom.

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

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

The heterocyclic group as Ar ⁴⁰¹ in the general formula (M4) is, for example, a hydrogen atom from pyrrole, furan, thiophene, imidazole, oxazole, thiazole, indole, benzimidazole, benzoxazole, benzothiazole, isoxazole, or isothiazole. And a group formed by removing one of them.
Examples of the substituent in the case where the phenyl group, naphthyl group, or heterocyclic group as Ar ⁴⁰¹ further has a substituent include substituents selected from the above-mentioned substituent group A.
Ar ⁴⁰¹ in the general formula (M4) is preferably a phenyl group or a heterocyclic group, more preferably a phenyl group, or pyrrole, furan, thiophene, imidazole, oxazole, thiazole, indole, benzimidazole, benzoxazole, A group formed by removing one hydrogen atom from benzothiazole, isoxazole, or isothiazole, and particularly preferably a group formed by removing one hydrogen atom from a phenyl group or thiophene, imidazole, or isothiazole. . The number of carbon atoms is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

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

R ⁵⁰¹ to R ⁵⁰⁸ in formula (M5) are preferably each independently a hydrogen atom, amino group, hydroxyl group, cyano group, or alkoxy group, more preferably a hydrogen atom, amino group, hydroxyl group, or alkoxy group. It is. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 6 carbon atoms.
In the general formula (M5), R ⁵⁰¹ to R ⁵⁰⁴ are preferably hydrogen atoms, and R ⁵⁰⁵ to R ⁵⁰⁸ are preferably each independently a hydrogen atom or a substituent, and R ⁵⁰¹ to R ⁵⁰⁴ are each a hydrogen atom, More preferably, R ⁵⁰⁵ to R ⁵⁰⁸ each independently represent a hydrogen atom, an amino group, a hydroxyl group, a cyano group, or an alkoxy group.

It is also preferred that R ⁵⁰⁶ and R ⁵⁰⁷ are bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated or unsaturated ring. The dye having an anthraquinone skeleton represented by the general formula (M5) is also preferably represented by the following general formula (M5A).

In general formula (M5A), R ⁵⁰¹ to R ⁵⁰⁴ , R ⁵⁰⁵ , R ⁵⁰⁸ , and R ⁵⁰⁹ each independently represent a hydrogen atom or a substituent.
^R 501 ^~ R ⁵⁰⁴ in formula ^{^{(M5A), R 505, R}} 508 is also similar to each general formula (M5) in the same meaning as ^{^{^{R 501 ~ R 504, R 505}}} , R 508 specific examples and preferred ranges It is.
R ⁵⁰⁹ in the general formula (M5A) preferably represents a hydrogen atom or an alkyl group, preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably represents a hydrogen atom.

R ⁶⁰¹ to R ^{602 in} formula (M6) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted carbon number of 1 to 20 alkoxy groups, substituted or unsubstituted amino groups, halogen atoms and cyano groups, more preferably hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, halogen atoms and cyano groups.
R ⁶⁰³ in general formula (M6) is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. is there.

Ar ⁶⁰¹ in the general formula (M6) has the same meaning as Ar ⁴⁰¹ in the general formula (M4), and specific examples and preferable ranges thereof are also the same.

R ⁷⁰¹ to R ⁷⁰² and R ⁷⁰⁵ to R ⁷⁰⁶ in formula (M7) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted group. An alkoxy group having 1 to 20 carbon atoms, a halogen atom, a substituted or unsubstituted amino group, more preferably a hydrogen atom, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom. is there. R ⁷⁰³ to R ⁷⁰⁴ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and more preferably a substituted or unsubstituted carbon number of 1 An alkyl group having ˜20, particularly preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
In the general formula (M8), R ⁸¹¹ to R ⁸¹⁸ and R ⁸²¹ to R ⁸²⁸ each independently represent a hydrogen atom or a substituent, preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl having 1 to 20 carbon atoms. Group, hydroxyl group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, halogen atom, substituted or unsubstituted amino group, cyano group, sulfo group, sulfonamido group, and alkylsulfonyl group, more preferably A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a halogen atom, a sulfo group, and a sulfonamide group, particularly preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, A halogen atom, a sulfo group, and a sulfonamide group;
The sulfo group may be a metal salt (for example, sodium salt, lithium salt, potassium salt, etc.), ammonium salt, or organic base salt.

Specific examples of the dyes represented by the general formulas (M1) to (M8) are shown below. Me represents a methyl group, Et represents an ethyl group, i-Pr represents an isopropyl group, and Bu represents an n-butyl group.

Some of the dyes represented by the general formulas (M1) to (M8) are classified by color index, and can be synthesized by a conventionally known method (for example, Japanese Patent Publication No. 7-49583, patent) No. 5715380, International Publication No. 2010/110199, and the like). The synthesis method is specifically illustrated in the examples.

[Repeating unit having nonionic hydrophilic group]
The nonionic hydrophilic group in the present invention is specifically a group represented by any one of the following general formulas (A) to (F), and the following general formulas (A) to (C): A group represented by any one is more preferable, and a group represented by the following general formula (A) is more preferable.

In the general formulas (A) to (F), n1 to n4 represent an integer of 5 to 150, and n5 and n6 represent an integer of 5 to 1000.
In general formula (E), R ^E each independently represents a hydrogen atom or a hydroxyethyl group.
In formula (F), R ^F each independently represents a hydrogen atom or a hydroxypropyl group.

n1 is preferably an integer of 5 to 150, more preferably an integer of 5 to 100, still more preferably an integer of 10 to 100, and particularly preferably an integer of 20 to 100.
n2 is preferably an integer of 5 to 150, more preferably an integer of 10 to 100, and still more preferably an integer of 20 to 100.
n3 is preferably an integer of 5 to 100, more preferably an integer of 10 to 80.
n4 is preferably an integer of 5 to 80, more preferably an integer of 10 to 40.
n5 is preferably an integer of 50 to 1,000, and more preferably an integer of 200 to 800.
n6 is preferably an integer of 50 to 1,000, and more preferably an integer of 200 to 800.

The general formula (A) is a structure derived from polyethylene glycol, the general formula (B) is a structure derived from polyvinyl alcohol, and the general formula (C) is a structure derived from polyglycerin. Formula (D) is a structure derived from polyvinyl pyrrolidone, general formula (E) is a structure derived from hydroxyethyl cellulose, and general formula (F) is a structure derived from hydroxypropyl cellulose.

The number average molecular weight (Mn) of the nonionic hydrophilic group is preferably 100 to 10,000, more preferably 200 to 8,000, still more preferably 800 to 5,000, Particularly preferred is 800 to 3,000. When the number average molecular weight is 100 or more, the dispersibility is excellent when an aqueous dispersion is obtained, and when the number average molecular weight is 10,000 or less, the fastness of the colored cloth is excellent. Although the mechanism excellent in dispersibility and fastness is not clear, if the number average molecular weight is 100 or more, the compatibility with water is improved and the function as a dispersing group can be sufficiently exerted, and the number average molecular weight is 10,000 or less. It is presumed that, after being deposited on the fabric, dissolution and dispersion in water are suppressed, water resistance is imparted, and fastness is excellent.
The number average molecular weight of the nonionic hydrophilic group can be calculated by size exclusion chromatography measurement.

As the repeating unit containing a nonionic hydrophilic group, a repeating unit represented by the following general formula (2) is particularly preferable.

In general formula (2), ^R901 represents any one of a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group. R ⁹⁰² represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a phenyl group. X ² represents a divalent linking group having 1 to 18 carbon atoms. Y ¹ and Y ² each independently represent a single bond or a group represented by any one of the following general formulas (G) to (J). n represents an integer of 5 to 150.

In general formulas (G) to (J), each m independently represents an integer of 1 to 20.
When Y ¹ represents a group represented by any ^one of the general formulas (G) to (J), * 1 represents a bonding position with X ² and * 2 represents a polyethylene oxide group in the general formula (2) Represents the binding position.
When Y ² represents a group represented by any one of the general formulas (G) to (J), * 1 represents a bonding position with the polyethylene oxide group in the general formula (2), and * 2 represents R ⁹⁰² Represents the binding position.

M preferably represents an integer of 1 to 10, more preferably an integer of 2 to 8.

R ⁹⁰¹ is preferably a hydrogen atom or a methyl group.
The linear or branched alkyl group having 1 to 18 carbon atoms and the phenyl group in R ⁹⁰² may further have a substituent, and the linear or branched alkyl group having 1 to 18 carbon atoms and the phenyl group may be Furthermore, as a substituent in the case of having a substituent, for example, a substituent selected from the above substituent group A can be mentioned.
R ⁹⁰² is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an unsubstituted or phenyl group substituted with an alkyl group having 1 to 9 carbon atoms, and further a hydrogen atom or a methyl group. preferable.

The divalent linking group as X ² is not particularly limited as long as the effects of the present invention can be obtained, but a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 8 carbon atoms (for example, Methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted arylene groups having 6 to 18 carbon atoms (eg, phenylene group, naphthylene group, etc.), —O—, —C (═O ) —NH—, —C (═O) —O—, and linking groups formed by linking two or more thereof.

The divalent linking group as X ² has 1 to 18 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
Note that the above carbon number does not include carbon atoms in —C (═O) —NH— and —C (═O) —O—.

The divalent linking group as X ² preferably contains —O—, —C (═O) —NH—, or —C (═O) —O—.

Further, the alkylene group or arylene group in X ² may be further substituted. As the substituent when the alkylene group or arylene group in X ² is substituted, for example, an alkyl group, an aryl group, and the like may be included. The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The aryl group is preferably an aryl group having 6 to 18 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

Y ¹ and Y ² each independently represent a single bond or a group represented by any one of the following general formulas (G) to (J). Y ¹ and Y ² are preferably each independently a single bond, a group represented by General Formula (G), or a group represented by General Formula (H), and more preferably a single bond.

N represents an integer of 5 to 150, preferably an integer of 5 to 100, more preferably 10 to 100, and still more preferably 20 to 100.

Specific examples of the repeating unit containing a nonionic hydrophilic group are shown below, but are not limited thereto.

The dye polymer of the present invention may have, as an essential component, a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group. Other repeating units may be introduced for the purpose of further improving the texture. As a method for introducing another repeating unit, from the viewpoint of the degree of freedom in design, a polymerizable dye monomer and / or a monomer having a nonionic hydrophilic group and another repeating unit are formed. It is preferable to introduce other monomers by copolymerization.

Examples of other monomers that can be suitably used in the dye polymer of the present invention include (meth) acrylic acid derivatives, (meth) acrylamide derivatives, styrene derivatives, and acrylonitrile. Derivatives are preferred.

Examples of (meth) acrylic acid derivatives include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Isobutyl acid, t-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, t-amyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, Isodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Tridecyl sulfonate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate , Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid 3-hydroxy-1-adamantyl, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 2-isopropyl-2-adamantyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, diethylene glycol Cole mono (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono (meth) acrylate, (meth) acrylic acid Vinyl, allyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-methoxydiethylene glycol (meth) acrylate, (meth ) Nonylphenoxydiethylene glycol acrylate, nonylphenoxytetraethylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, neopentyl glycol mono (meth) acrylate monobenzoate Perfume ester, phenylphenol diethylene glycol (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, (meth) acrylic acid 2 -Caprolactone of ethylhexyloxydiethylene glycol, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate Adduct, glycidyl methacrylate, γ-butyrolactone (meth) acrylate, methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8, -Tridecafluoro-n-octyl, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, (meth) acrylic acid 2-isocyanatoethyl, 2-[( 3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate, 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl (meth) acrylate, (meth) acrylic acid 2- (trimethylsilyloxy) Ethyl, 3- (trimethoxysilyl) propyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate, 3- [dimethoxy (methyl) silyl] propyl (meth) acrylate, (meth) acryl Acid 3- [diethoxy (methyl) silyl] propyl, (meth) acrylic acid 3- (meth And xyldimethylsilyl) propyl.

Examples of (meth) acrylamide derivatives include (meth) acrylamide, N-methyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) acrylamide, t-butyl (meth) acrylamide, and dodecyl. (Meth) acrylamide, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylamide, diacetone acrylamide, phenyl (meth) acrylamide, 3- (meth) acryloyl-2-oxazolidinone, and the like.
Examples of the styrene derivative include styrene, acetoxystyrene, methylstyrene, t-butylstyrene, methoxystyrene, octylstyrene, phenylstyrene, and the like.

More preferably, it is a hydrophobic monomer or a monomer having a low glass transition temperature of homopolymer, specifically, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, Isobutyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, t-amyl acrylate, neopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, Nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, tetradecyl acrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, isoa methacrylate , T-amyl methacrylate, neopentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, Lauryl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, stearyl methacrylate, behenyl methacrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (Meth) acrylic acid 2-phenoxydiethylene glycol, (meth) acrylic acid nonylphenoxydiethylene glycol, (meth) acrylic acid nonylpheno Citetraethylene glycol, ethoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, 2-ethylhexyloxydiethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy Examples include polypropylene glycol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and caprolactone adduct of 2-hydroxyethyl (meth) acrylate.

The content of the repeating unit including the structure derived from the dye in the dye polymer is preferably 10 to 98% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass. %. If the content rate of the repeating unit containing the structure derived from dye is 10 mass% or more, the coloring power per unit mass will improve and the dyeing density to a fabric will become high. Moreover, it is easy to express performance, such as dispersibility, fastness, quality (texture), as it is 98 mass% or less.
The content of the repeating unit containing a nonionic hydrophilic group in the dye polymer is preferably 1 to 30% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 30%. % By mass. When the content of the repeating unit containing a nonionic hydrophilic group is 1% by mass or more, the dispersion stability of the dispersion is excellent. Moreover, fastness is excellent in it being 30 mass% or less.

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

<Aqueous dispersion of dye polymer>
The aqueous dispersion of the dye polymer contains at least water and (A) the dye polymer, and preferably contains (B) an aqueous organic solvent. In some cases, (C) a surfactant (low molecular surfactant, polymer dispersant) may be contained.
A method for producing an aqueous dispersion of a dye polymer is obtained by synthesizing a dye polymer in an organic solvent, and then emulsifying by adding water and optionally a surfactant to remove the organic solvent to obtain an aqueous dispersion of the dye polymer. A method of synthesizing a dye polymer in an organic solvent, then adding water, optionally a surfactant or solvent, and removing the solvent other than water to obtain an aqueous dispersion of the dye polymer. A method for obtaining a water dispersion of a dye polymer, a monomer of a dye polymer in water, a polymerization initiator, A method of obtaining an aqueous dispersion of a dye polymer by adding an organic solvent, optionally a surfactant, emulsifying, polymerizing by starting polymerization, and removing the organic solvent simultaneously with polymerization or after polymerization, Dyeing Polymer monomer, optionally adding surfactant to emulsify, adding polymerization initiator, starting polymerization and polymerizing to obtain aqueous dispersion of dye polymer, single amount of dye polymer in water Body, optionally adding a surfactant or organic solvent to emulsify, adding a polymerization initiator or, optionally, a polymerization initiator solution, initiating polymerization to polymerize, and simultaneously with polymerization or after polymerization A method of obtaining an aqueous dispersion of a dye polymer by removing the solvent, synthesizing the dye polymer in an organic solvent, taking out the dye polymer, adding water, and optionally a surfactant, redispersing and / or glass beads or There is a method of obtaining an aqueous dispersion of a dye polymer by finely dispersing with zirconia beads or the like with an attritor or a mill, and these can be suitably used. When the dye polymer can be pulverized, the method of finely dispersing with the above-mentioned attritor or mill is more preferable. When the dye polymer is flexible and difficult to pulverize, it should be produced by any of the above methods other than the method of finely dispersing. Is preferred.

(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 the water.

(1-1) Dispersibility The dye polymer, when dispersed in water, tends to be compatible with water (easy to wet) due to the nature of the dye polymer itself or by the surfactant used in combination, and reaggregation of the fine particles of the dye polymer due to steric repulsion. And has the function of suppressing sedimentation.

(1-2) Average particle diameter The dye polymer is preferably in the form of particles in an aqueous dispersion. The average particle diameter of the particulate dye polymer in the aqueous dispersion of the dye polymer is preferably 10 to 500 nm, more preferably 30 to 300 nm, and still more preferably 50 to 200 nm. If it is within the above range, it can be directly printed on the fabric by the ink jet method.
As the average particle size in the present specification, a value measured using a particle size distribution measuring device (Nanotrack UPA EX150, manufactured by Nikkiso Co., Ltd., trade name) was used.

The content of the dye polymer in the aqueous dispersion is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, and particularly preferably 3 to 25% by mass. Within this range, a high-density dyed cloth can be obtained in printing while ensuring storage stability as an inkjet ink.
The content of water in the aqueous dispersion is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and particularly preferably 60 to 90% by mass. Within this range, the stability of the aqueous dispersion and the ejection stability as an inkjet ink can be imparted. The stability of the aqueous dispersion means that precipitation or the like hardly occurs.

(B) Aqueous organic solvent The aqueous organic solvent preferably has a solubility in water at 25 ° C. of 10 grams or more per 100 grams of water, more preferably 20 grams or more per 100 grams of water, Those which are mixed at an arbitrary ratio are particularly preferable. Examples of the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, 1,2,6 -Hexanetriol, thioglycol, hexylene glycol, glycerin, diglycerin, polyglycerin, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol monobutyl ether, Examples include acetonitrile. Preferably, 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, and ethylene glycol, glycerin and 2-pyrrolidone are more 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) Surfactant The aqueous dispersion of the dye polymer of the present invention may optionally contain a surfactant. The surfactant is preferably a low-molecular or high-molecular compound having a hydrophobic group and an ionic group and / or a nonionic hydrophilic group, and preferably has the following characteristics.

(2-1) Dispersibility Surfactant is added when dispersing the dye polymer, so that the surfactant is adsorbed on the surface of the dye polymer and is infiltrated (wet) with water, and the dye polymer fine particles are repelled by charge. (Repulsive force) and steric repulsion prevent fine particles from reaggregating and have the 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 for 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, when the molecular weight is smaller than the optimum molecular weight, the adsorption from the dye polymer is likely to occur, and the effect as a dispersing agent 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 surfactant to be added to the present invention comprises a hydrophobic group (an electrically neutral nonpolar group having a low affinity with water) and an ionic group (electrically ionic). It is preferably a polar group having a high affinity with water and / or a nonionic hydrophilic group (an electrically neutral polar group having a high affinity with water). This structure may be linear or branched. In the case of the polymeric dispersant, any of random, alternating, periodic, and block structures may be used, and a graft polymer designed with a trunk and branch structure may be used.
The surfactant 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) Formation Method and Obtaining Method For example, the following can be used as the low molecular surfactant and the high molecular 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 Salt, alkyl phosphate ester salt and the like. 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.
Examples of the nonionic surfactant include 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 Examples include fatty acid esters, propylene glycol fatty acid esters, and acetylene glycol. A suitable example is SURFYNOLS (Air Products & Chemicals, trade name), which is an acetylene-based polyoxyethylene oxide surfactant. In addition, pages 37 to 38 of JP-A-59-157636, Research Disclosure No. Those listed as surfactants in 308119 (1989) can also be used.
The content of the low molecular surfactant is preferably in the range of 0.001% by mass to 5.0% by mass with respect to the total mass of the aqueous dispersion, and the surface tension of the aqueous dispersion can be 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 above-mentioned hydrophobic group-containing monomer and ionic group-containing monomer are the same as the monomer of the copolymer component of the dye polymer described above. As the polymeric dispersant, DISPERBYK-194N (trade name) manufactured by BYK Japan, Inc. can be used.
The content of the polymeric dispersant is preferably in the range of 0.001% by mass to 50% by mass with respect to the total mass of the aqueous dispersion. It is preferable to adjust.

In the aqueous dispersion of the dye polymer of the present invention, if necessary, 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. Can be added. In addition, the above-mentioned nonionic surfactants and anionic surfactants can be added as dispersion aids, but these surfactants do not deteriorate the performance as dispersion stability. It is preferable to add a small amount.

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

The colored composition of the present invention may further contain a colorant (dye, pigment, etc.) other than the dye polymer. When the other colorant is included, the content of the dye polymer is preferably 50% by mass or more, more preferably 80% by mass or more, further 100% by mass, based on the total mass of the colorant including the dye polymer. That is, it preferably contains only a dye polymer.
The content of the dye polymer in the coloring composition is preferably from 0.1 to 20% by weight, preferably from 1 to 15% by weight, based on the total weight of the coloring composition, from the dyeing density and the storage stability of the coloring composition. Is more preferable, and 3 to 12% by mass is even more preferable.
The content of water in the coloring composition is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and particularly preferably 50 to 80% by mass.

<Organic solvent>
Examples of the organic solvent that can be contained in the coloring composition of the present invention include polyhydric alcohols (for example, ethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, tetraethylene glycol). , Triethylene glycol, tripropylene glycol, 1,2,4-butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, tetramethylene glycol, 1,6-hexanediol, 1,2-hexanediol, 1,5-pentane Diol, 1,2-pentanediol, 2,2-dimethyl1,3-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 alcohols Alkyl ethers (eg, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, and dipropylene glycol) Monomethyl ether, etc.), 2,2'-thiodiethanol, amides (eg N, N-dimethylforma) Sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, 3-sulfolene, heterocyclics (2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N-ethyl) Morpholine, 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 coloring composition of the present invention can further use a surfactant from the viewpoint of enhancing storage stability, ejection stability, ejection accuracy, and the like. As the surfactant, any of cationic, anionic, amphoteric and nonionic surfactants can be used.

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

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

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

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid Examples include esters, propylene glycol fatty acid esters, and acetylene glycols. A suitable example is SURFYNOLS (Air Products & Chemicals, trade name), which is an acetylene-based polyoxyethylene oxide surfactant. In addition, pages 37 to 38 of JP-A-59-157636, Research Disclosure No. Those listed as surfactants in 308119 (1989) can also be used.

When using these surfactants, the surfactant may be used alone or in combination of two or more.
The content of the surfactant in the colored composition of the present invention is preferably in the range of 0.001% by mass to 5.0% by mass with respect to the total mass of the colored composition. It is preferable to arbitrarily adjust the surface tension of the object.

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

(UV absorber)
As ultraviolet absorbers, they are described in JP-A-58-185777, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, JP-B-56 -21141, JP-A-10-88106, etc., cinnamic acid compounds, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10- Triazine compounds described in Japanese Patent No. 182621, Japanese National Publication No. Hei 8-501291, etc., Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used. When the coloring composition contains an ultraviolet absorber, 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.

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

(Anti-drying agent)
As the drying inhibitor, an aqueous organic solvent having a vapor pressure lower than that of water can be suitably used. When the coloring composition contains an anti-drying agent, clogging due to drying of the coloring composition at the nozzle outlet of the discharge head that discharges the coloring composition is prevented when used for inkjet recording applications. be able to. Specific examples of the drying inhibitor include, for example, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol. , Acetylene glycol derivatives, glycerin, polyhydric alcohols typified by trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) Lower alkyl ethers of polyhydric alcohols such as ether, heterocycles such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N-ethylmorpholine, Horan, dimethyl sulfoxide, and sulfur-containing compounds such as sulfolane, diacetone alcohol, and polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred.
Moreover, a drying inhibitor may be used individually by 1 type, and may use 2 or more types together. When the coloring composition contains an anti-drying agent, the content of the anti-drying agent is preferably 10% by mass to 50% by mass with respect to the total mass of the 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 surfactants such as nonionic surfactants, cationic surfactants, and anionic surfactants. Preferred examples of the surfactant are the same as those exemplified in the above-mentioned surfactant column.
As the antifoaming agent, fluorine-based and silicone-based compounds are preferable.

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

(Chelating agent)
The chelating agent is preferably used for the purpose of preventing the generation of precipitates such as precipitates in the coloring composition, and for the purpose of improving storage stability and clogging recovery. When a dye is used as the colorant of the coloring composition, the metal (Ca, Mg, Si, Fe, etc.) contained in the coloring composition may cause the generation of precipitates and the reduction in clogging recovery. It is known that ions need to be managed below a certain amount. In addition, when a copper complex dye is used, even if the amount of metal ions is controlled, if the amount of free copper ions is not controlled, the occurrence of precipitates and a reduction in clogging recovery may be observed. It is known (see JP 2000-355665 A, JP 2005-126725 A, etc.). Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, uramildiacetic acid, and metal salts thereof (for example, sodium salt).

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

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

<Inkjet ink>
The present invention also relates to an inkjet ink including an aqueous dispersion of a polymer (dye polymer) having at least a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group. The inkjet ink is preferably used for textile printing. The components contained in the inkjet ink are the same as those shown in the above-described coloring composition of the present invention.
The content of the dye polymer and other components in the ink-jet ink can be in the range of the content shown in the above-described coloring composition of the present invention.

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

<Inkjet printing method>
The ink jet printing method of the present invention is an ink jet method comprising an ink jet ink containing an aqueous dispersion of a polymer (dye polymer) having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group. An inkjet printing method including a step of directly printing on a fabric.
The ink-jet textile printing method of the present invention produces an effect that it does not produce waste materials such as waste water and transfer paper, is simple in workability, and is excellent in the quality (texture) of the colored cloth.

<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. These fabrics can be coated with a pretreatment agent for the purpose of further improving the color density and adjusting the hue. A commercially available cationic polymer or cationic oligomer can be used as the pretreatment agent.
Apparel includes T-shirts, trainers, jerseys, pants, sweatsuits, dresses, blouses and the like. It is also suitable for fabrics, bedding, handkerchiefs and the like.

<Heat treatment process>
The ink jet textile printing method of the present invention preferably further includes a heat treatment step. In particular, by performing a heat treatment step after printing on the fabric, the dye polymer particles can be melted (or softened) and the adhesion to the fibers can be improved (that is, heat-treated for melt dyeing). Can do). The colored 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. Usually, it is more preferable to perform heat treatment at 100 to 200 ° C. for 30 seconds to 3 minutes. If the glass transition temperature of the dye polymer is low, a colored cloth having a desired quality can be obtained at a low temperature within a short time within the above range. In addition, when the dye polymer or additive has a crosslinkable group or a reactive group (for example, blocked isocyanate, epoxy group, etc.), the dye polymer is cross-linked between the dye polymers or the fabric in this heat treatment step, and the fastness is obtained. Can be further improved.

<Post-processing>
The fabric colored with the ink-jet ink containing the aqueous dispersion of the dye polymer of the present invention is excellent in quality (texture) and fastness (friction resistance). By processing, a colored cloth having further improved quality (texture) 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 immersed in the resulting mixture, followed by squeezing with a mangle or the like and applying heat treatment.
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.

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

<Colored cloth>
The present invention also relates to a colored fabric comprising a fabric and a polymer having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group (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.

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited to these Examples at all.
In Examples of the present specification, “part” means “part by mass” unless otherwise specified.

(Synthesis Example 1)
[Dye polymer aqueous dispersion (1)]
Exemplary compound (Y-1-1) was synthesized according to the following scheme.

16 parts of N-methylpyrrolidone (NMP) was added to a three-necked flask and kept at 85 ° C. under nitrogen. Separately, 9.7 parts of dye monomer YM-1 (synthesized by the method described in Japanese Patent No. 5315267), polyethylene glycol monoallyl ether PEG-1 (product name: UNIOX PKA-5005, manufactured by NOF Corporation) Average molecular weight 1500). 0.3 part, 0.3 part of V-601 (manufactured by Wako Pure Chemical Industries, Ltd., trade name) and 24 parts of NMP (N-methylpyrrolidone) were mixed, and the mixture was added dropwise to the flask over 3 hours. After dropping, the mixture was further stirred for 2 hours. Thereafter, 0.3 part of V-601 was added and further stirred for 2 hours. Thereafter, the temperature was raised to 95 ° C., stirred for 2 hours, and then cooled to room temperature (20 ° C.). 500 parts of distilled water was added to the reaction solution to precipitate and remove the polymer, followed by drying with an air dryer at 60 ° C. for 24 hours to obtain 7.5 parts of exemplary compound (Y-1-1). The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of Exemplified Compound (Y-1-1) in tetrahydrofuran (THF) was 441 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 8,000. As a result of measuring the glass transition temperature of Exemplified Compound (Y-1-1) by DSC (Differential Scanning Calorimetry), it was confirmed to be about 160 ° C. The number of repetitions 33 in polyethylene glycol monoallyl ether PEG-1 is a value calculated as a molecular weight of 1500.

Illustrative compound (Y-1-1) 0.25 parts, zirconia beads (manufactured by Nikkato, trade name YTZ ball, diameter 0.1 μm) 10 parts, sodium oleate 0.05 parts, glycerin 0.5 parts, ultrapure water 4.2 parts were added, and the mixture was dispersed for 10 hours at a rotation speed of 400 rpm (revolution per minute) using a planetary fine pulverizer (Pulversette 7 manufactured by Fritsch). From the obtained dispersion, zirconia beads were removed using a filter cloth, and coarse particles were removed using a filter to obtain an aqueous dye polymer dispersion (1). The average particle diameter (Mv) of the polymer particles was 130 nm.

(Synthesis Example 2)
[Dye polymer aqueous dispersion (2)]
Exemplary compound (Y-2-2) was synthesized according to the following scheme.

16 parts of NMP was added to a three-necked flask and kept at 85 ° C. under nitrogen. Separately, 7.0 parts of dye monomer YM-1 (synthesized by the method described in Japanese Patent No. 5315267), 3.0 parts of methoxypolyethylene glycol methacrylate MPG-1 (manufactured by Aldrich, average molecular weight 2000), V-601 ( Wako Pure Chemical Industries, Ltd., trade name) 0.1 parts and NMP 24 parts were mixed, and the mixture was added dropwise to the flask over 3 hours. After dropping, the mixture was further stirred for 2 hours. Thereafter, 0.1 part of V-601 was added and further stirred for 2 hours. Thereafter, the temperature was raised to 95 ° C., stirred for 2 hours, and then cooled to room temperature. 500 parts of distilled water was added to the reaction solution to precipitate the polymer, and the polymer was then taken out and dried at 60 ° C. for 24 hours with a blast dryer to obtain 7.9 parts of exemplary compound (Y-2-2). (Exemplary Compound) The maximum absorption wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of Y-2-2 in THF was 442 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 25,000. As a result of measuring the glass transition temperature of Exemplified Compound (Y-2-2) by DSC (differential scanning calorimetry), it was confirmed to be about 120 ° C. The number of repetitions 45 in methoxypolyethylene glycol methacrylate MPG-1 is a value calculated as a molecular weight of 2000.

Illustrative compound (Y-2-2) 0.25 parts, zirconia beads (manufactured by Nikkato, trade name YTZ ball, diameter 0.1 μm) 10 parts, sodium oleate 0.05 parts, glycerin 0.5 parts, ultrapure water 4.2 parts were added, and the mixture was dispersed for 10 hours at a rotation speed of 400 rpm using a planetary fine pulverizer (Pulversette 7 manufactured by Fritsch). From the obtained dispersion, zirconia beads were removed using a filter cloth, and coarse particles were further removed using a filter to obtain an aqueous dye polymer dispersion (2). The average particle diameter (Mv) of the polymer particles was 90 nm.

(Synthesis Example 3)
[Dye polymer aqueous dispersion (3)]
The exemplified compound (Y-3-2) was synthesized according to the following scheme.

In a three-necked flask, dye monomer YM-1 (synthesized by the method described in Japanese Patent No. 5315267) 6.0 parts, methoxypolyethylene glycol methacrylate MPG-2 (product name: Bremer PME-1000, manufactured by NOF Corporation, average) 2.0 parts of molecular weight 1000), 2.0 parts of 2-ethylhexyl acrylate, 8 parts of MEK (methyl ethyl ketone) and 8 parts of THF were added and kept at 65 ° C. under nitrogen. 0.1 part of V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred for 2 hours. Thereafter, 0.1 part of V-65 was added and stirred for 2 hours, and further 0.1 part of V-65 was added and stirred for 2 hours. Thereafter, the mixture was stirred at 65 ° C. for 4 hours and then cooled to room temperature to obtain a MEK / THF solution of Exemplified Compound (Y-3-2). The absorption maximum wavelength of the ultraviolet-visible absorption spectrum of the exemplified compound (Y-3-2) in a dilute THF solution was 442 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 22,000. As a result of measuring the glass transition temperature of Exemplified Compound (Y-3-2) by DSC (Differential Scanning Calorimetry), it was confirmed to be about 60 ° C. The number of repetitions 23 in methoxypolyethylene glycol methacrylate MPG-2 is a value calculated as a molecular weight of 1000.

20 parts of MEK / THF solution of the above exemplified compound (Y-3-2), 10 parts of MEK, and 35 parts of ultrapure water were mixed and further stirred at 14000 rpm for 12 minutes, and then the organic solvent was distilled off at 50 ° C. and 100 mbar. . The coarse particles were removed with a filter to obtain an aqueous dye polymer dispersion (3). The average particle diameter (Mv) of the polymer particles was 120 nm. Note that 1 mbar is 100 Pa.

(Synthesis Example 4)
[Dye polymer aqueous dispersion (4)]
Exemplary compound (R-1-2) was synthesized according to the following scheme.

In a three-necked flask, 8 parts of MEK and 8 parts of THF were placed, and kept at 65 ° C. under nitrogen. Separately, dye monomer RDW R-13 (Wako Pure Chemical Industries, trade name) 8.0 parts, methoxypolyethylene glycol methacrylate MPG-3 (product name: Blemmer PME-4000, manufactured by NOF Corporation, average molecular weight 4000) ) 2.0 parts, V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 0.15 parts), MEK 12 parts, and THF 12 parts were mixed, and the mixture was added dropwise to the flask over 2 hours. After dropping, the mixture was stirred for 2 hours, 0.15 part of V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 2 hours. Thereafter, 0.15 part of V-65 was further added and stirred for 2 hours. Thereafter, the mixture was stirred at 65 ° C. for 4 hours and then cooled to room temperature to obtain a MEK / THF solution of Exemplified Compound (R-1-2). The absorption maximum wavelength of the ultraviolet-visible absorption spectrum of the exemplified compound (R-1-2) in a dilute THF solution was 562 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 21,000. As a result of measuring the glass transition temperature of Exemplified Compound (R-1-2) by DSC (Differential Scanning Calorimetry), it was confirmed to be about 140 ° C. The repeat number 90 in methoxypolyethylene glycol methacrylate MPG-3 is a value calculated as a molecular weight of 4000.

20 parts of MEK / THF solution of the above exemplified compound (R-1-2), 10 parts of MEK, and 35 parts of ultrapure water were mixed and further stirred at 14000 rpm for 12 minutes, and then the organic solvent was distilled off at 50 ° C. and 100 mbar. . The coarse particles were removed with a filter to obtain an aqueous dye polymer dispersion (4). The average particle diameter (Mv) of the polymer particles was 160 nm.

(Synthesis Example 5)
[Dye polymer aqueous dispersion (5)]
Exemplary compound (B-1-2) was synthesized according to the following scheme.

In a three-necked flask, 8 parts of MEK and 8 parts of THF were placed, and kept at 65 ° C. under nitrogen. Separately, dye monomer BM-1 (synthesized by the method described in JP-A-2016-75845) 6.0 parts, methoxypolyethylene glycol methacrylate MPG-2 (product name: BLEMMER PME-1000, manufactured by NOF Corporation) , Average molecular weight 1000) 2.0 parts, butyl acrylate 2.0 parts, V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 0.1 part), MEK 12 parts, THF 12 parts, and the mixed solution for 2 hours Over the flask. After dropping, the mixture was stirred for 2 hours, 0.1 part of V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 2 hours. Thereafter, 0.1 part of V-65 was further added and stirred for 2 hours. Thereafter, the mixture was stirred at 65 ° C. for 4 hours and then cooled to room temperature to obtain a MEK / THF solution of Exemplified Compound (B-1-2). The weight average molecular weight (Mw) of the exemplified compound (B-1-2) as measured by GPC was 22,000. Further, the glass transition temperature of Exemplified Compound (B-1-2) was measured by DSC (Differential Scanning Calorimetry), and as a result, it was confirmed to be about 90 ° C.
20 parts of MEK / THF solution of the above exemplified compound (B-1-2), 10 parts of MEK, and 35 parts of ultrapure water were mixed and further stirred at 14000 rpm for 12 minutes, and then the organic solvent was distilled off at 50 ° C. and 100 mbar. . The coarse particles were removed with a filter to obtain a dye polymer aqueous dispersion (5). The average particle diameter (Mv) of the polymer particles was 150 nm.

(Synthesis Example 6)
[Dye polymer aqueous dispersion (6)]
Exemplary compound (R-2-1) was synthesized according to the following scheme.

16 parts of NMP was added to a three-necked flask and kept at 85 ° C. under nitrogen. Separately, 8.5 parts of dye monomer RM-1 (synthesized as described in Chemical Abstract 84, page 19172), 1.5 parts of methoxypolyethylene glycol methacrylate MPG-1 (Aldrich, average molecular weight 2000), V -601 (product name, manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 part and NMP 24 part were mixed, and the mixture was added dropwise to the flask over 3 hours. After dropping, the mixture was further stirred for 2 hours. Thereafter, 0.1 part of V-601 was added and further stirred for 2 hours. Thereafter, the temperature was raised to 95 ° C., stirred for 2 hours, and then cooled to room temperature. 500 parts of distilled water was added to the reaction solution to precipitate the polymer, and the polymer was then taken out and dried at 60 ° C. for 24 hours with an air dryer to obtain 8.1 parts of exemplary compound (R-2-1). The absorption maximum wavelength of the ultraviolet-visible absorption spectrum of the exemplified compound (R-2-1) in a dilute THF solution was 542 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 12,000. The glass transition temperature of Exemplified Compound (R-2-1) by DSC (Differential Scanning Calorimetry) was about 170 ° C.

Illustrative compound (R-2-1) 0.25 parts, zirconia beads (made by Nikkato, trade name YTZ ball, diameter 0.1 μm) 10 parts, sodium oleate 0.05 parts, glycerin 0.5 parts, ultrapure water 4.2 parts were added, and the mixture was dispersed for 10 hours at a rotation speed of 400 rpm using a planetary fine pulverizer (Pulversette 7 manufactured by Fritsch). From the obtained dispersion, zirconia beads were removed using a filter cloth, and coarse particles were further removed using a filter to obtain an aqueous dye polymer dispersion (6). The average particle diameter (Mv) of the polymer particles was 130 nm.

(Synthesis Example 7)
[Dye polymer aqueous dispersion (7)]
Exemplary compound (D-1-2) was synthesized according to the following scheme.

16 parts of NMP was added to a three-necked flask and kept at 85 ° C. under nitrogen. Separately, 7.0 parts of dye monomer D-1 (synthesized by the method described in US2011 / 0149128), methoxypolyethylene glycol methacrylate MPG-2 (product name: Blemmer PME-1000, manufactured by NOF Corporation, average molecular weight 1000) ) 3.0 parts, V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 0.15 parts and NMP 24 parts were mixed, and the mixture was added dropwise to the flask over 3 hours. After dropping, the mixture was further stirred for 2 hours. Thereafter, 0.15 part of V-601 was added and further stirred for 2 hours. Thereafter, the temperature was raised to 95 ° C., stirred for 2 hours, and then cooled to room temperature. 500 parts of distilled water was added to the reaction solution to precipitate the polymer, which was then taken out by an air dryer at 60 ° C. for 24 hours to obtain 8.0 parts of exemplary compound (D-1-2). The absorption maximum wavelength of the ultraviolet-visible absorption spectrum of the exemplified compound (D-1-2) in a dilute NMP solution was 671 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 9,000. The glass transition temperature of Exemplified Compound (D-1-2) by DSC (Differential Scanning Calorimetry) was about 150 ° C.

Illustrative compound (D-1-2) 0.25 parts, zirconia beads (manufactured by Nikkato, trade name YTZ ball, diameter 0.1 μm) 10 parts, sodium oleate 0.05 parts, glycerin 0.5 parts, ultrapure water 4.2 parts were added, and the mixture was dispersed for 10 hours at a rotation speed of 400 rpm using a planetary fine pulverizer (Pulversette 7 manufactured by Fritsch). From the obtained dispersion, zirconia beads were removed using a filter cloth, and coarse particles were further removed using a filter to obtain an aqueous dye polymer dispersion (7). The average particle diameter (Mv) of the polymer particles was 120 nm.

Example 1
[Preparation of ink liquid for ink jet textile printing (A1)]
The following components were mixed at room temperature, stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare ink for inkjet printing (A1).
Dye polymer aqueous dispersion (1) 3.0 parts Trimethylolpropane 0.058 parts Ultrapure water 0.899 parts 1,2-hexanediol 0.118 parts Glycerin 0.580 parts Triethylene glycol monobutyl ether 0.121 parts 2-Pyrrolidone 0.159 parts Propylene glycol 0.042 parts Surfinol 465 (trade name, manufactured by Nissin Chemical Industry) 0.056 parts

[Inkjet printing method]
Ink for ink-jet textile printing (A1) is loaded into an ink cartridge, and an ink-jet printer (Calario PX-045A manufactured by Epson, product name) is used to make a polyester fabric (polyester tropical (manufactured by Teijin), manufactured by Color & Color Co., Ltd., product code A02. -01019), cotton fabric (with cotton broad sill, manufactured by Color Dyeing Co., Ltd., product code A02-01002), and polyester 65% cotton 35% mixed spinning (Blend Polyester 65 / Cotton 35 Broad, manufactured by Color Dyeing Co., Ltd., product code A02-) Each image was printed on 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 180 ° C., pressure 0.20 N / cm ² for 60 seconds. A clear image without blurring was obtained.

(Examples 2 to 7)
Inkjet textile printing inks (A2) to (A7) were prepared in the same manner as inkjet textile printing ink (A1) except that dye polymer aqueous dispersion (1) was changed to dye polymer aqueous dispersions (2) to (7). Prepared.

(Comparative Example 1) Sublimation transfer printing After printing an image on transfer paper using a sublimation transfer printing printer SureColor F6000 (trade name, manufactured by Seiko Epson Corporation), a polyester fabric (polyester tropical (made by Teijin), manufactured by Color dyeing company) , Product code A02-01019), cotton fabric (with cotton broad sill, manufactured by Color Dye Co., product code A02-01002), and 65% polyester 35% cotton blend (mixed-spun polyester 65/35 cotton broad, manufactured by Color Dye Co., Ltd.) An image was printed on each of product codes 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 parts of a styrene-acrylic acid copolymer (Johncrill 678, manufactured by BASF, trade name), 1.3 parts of dimethylaminoethanol, and 80.7 parts of ion-exchanged water were stirred and mixed at 70 ° C. Next, C.I. I. 15 parts of Pigment Blue 15: 3 and 50% by volume of zirconia beads having a particle diameter of 0.5 mm were filled by 50% and dispersed using a sand grinder mill to obtain a pigment dispersion having a cyan pigment content of 15%. .

(Preparation of aqueous binder)
50 parts of MEK was placed in a three-necked flask and kept at 75 ° C. under nitrogen. Separately, a mixture of 80 parts of butyl methacrylate, 20 parts of acrylic acid, 50 parts of MEK, and 0.5 part of azoisobutyronitrile was dropped into the flask over 3 hours. 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. Thereto was added 350 parts of ion-exchanged water and 1.05 moles of sodium hydroxide of acrylic acid added as a monomer and dissolved therein. Dilution with ion-exchanged water was performed so that the total amount became 500 parts to obtain a 20% aqueous solution of an aqueous binder.

(Preparation of pigment ink and coloring by inkjet method)
46.6 parts of the above pigment dispersion, 15 parts of the above aqueous binder, 2.9 parts of PDX-7664A (trade name, manufactured by BASF), 10 parts of triethylene glycol monobutyl ether, 5 parts of 1,2-hexanediol, 11 of diethylene glycol 11 .2 parts, Olfin 465 (manufactured by Nissin Chemical Industry Co., Ltd., 0.6 part) is mixed, and ion-exchanged water is added thereto to prepare a total amount of 100 parts, followed by filtration through a 0.8 μm filter for comparison. Pigment ink was obtained.
The obtained pigment ink is loaded into an ink cartridge, and an ink-jet printer (Calario PX-045A manufactured by Epson, product name) is used to fabricate a polyester fabric (polyester tropical (manufactured by Teijin), manufactured by Color & Color Co., Ltd., product code A02-01019. ), Cotton fabric (with cotton broad sill, manufactured by Color Dyeing Co., Ltd., product code A02-01002), and polyester 65% cotton 35% blended yarn (blended polyester 65 / cotton 35 broad, manufactured by Color Dyeing Co., Ltd., product code A02-01030) Images were printed on each 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 colored cloth printed with the pigment ink was obtained.

The evaluation results of Examples 1 to 7 and Comparative Examples 1 and 2 are shown in Table 1. The evaluation of the colored fabric is the result of the following method. Of the three types of fabrics, cotton fabrics were used in the evaluation of the texture and fastness to wet friction.
(Image clarity)
Visual sensory evaluation was performed. The three types of fabrics were evaluated in four stages: A for the case of clearness, B for the case of clearness with two types, C for the case of only one type, and D for no clear image.
(Texture)
The untreated cloth before dyeing and the colored cloth after dyeing were touched by hand, and the texture of the colored cloth was subjected to sensory evaluation. 10 points were assigned to the fabrics with the texture of the colored fabric that was close to that of the untreated fabrics, and 0 points were assigned to the other. The total score was shown in Table 1 below. A larger numerical value indicates an excellent texture close to the untreated cloth (100 (points)).
(Wet friction fastness)
JIS L-0849 (revised in 2013) The evaluation was made based on the Gakushin type friction test (class 5 method). Larger values indicate better robustness.

(Example 8)
5 parts of Wacker Finish CT-14 (manufactured by Wacker, trade name) and 3 parts of Matsuminsol MR50 (manufactured by Matsui Dye Co., Ltd., trade name) were stirred and mixed in 92 parts of water to obtain a post-treatment agent.
After printing an image by the inkjet method in the same manner as in Example 2, the post-treatment agent was padded, immediately squeezed with a mangle at a pickup rate of 70%, dried at 100 ° C. with a dryer, and then dried. By performing heat treatment using a heat press (product name: desktop automatic flat press machine AF-54TEN type, manufactured by Asahi Textile Machinery Co., Ltd.) at a temperature of 150 ° C., a pressure of 0.20 N / cm ² , and a time of 60 seconds, A clear image without blur was obtained.
As a result of the evaluation, the image sharpness A, the texture 90, and the fastness to wet friction were grades 3 to 4.

As is apparent from the above results, dyed fabrics having fabric versatility (giving clear images on various fabrics), good texture and fastness to wet friction are obtained by the inkjet printing method according to the embodiments of the present invention. I know you give it. In addition, in the inkjet printing method according to the embodiment of the present invention, waste water and waste materials are not generated, so that the environmental load is excellent and there is no problem in workability.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on Feb. 24, 2017 (Japanese Patent Application No. 2017-34065), the contents of which are incorporated herein by reference.

Claims

Inkjet printing method comprising a step of directly printing an ink-jet ink comprising a water dispersion of a polymer having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group on a fabric by an inkjet method .
The inkjet printing method according to claim 1, further comprising a heat treatment step.
The inkjet printing method according to claim 1 or 2, wherein the inkjet ink further contains an aqueous organic solvent.
The inkjet printing method according to any one of claims 1 to 3, wherein the nonionic hydrophilic group is a group represented by the following general formula (A).

In general formula (A), n1 represents an integer of 5 to 150.
The inkjet printing method according to any one of claims 1 to 4, wherein the repeating unit containing a structure derived from the dye is a repeating unit represented by the following general formula (1).

In General Formula (1), X 1 represents a linking group, L 1 represents a single bond or a divalent linking group, and D 1 represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye.
6. D 1 in the general formula (1) represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye represented by any one of the following general formulas (M1) to (M8). Inkjet printing method.

In general formula (M1), R 101 to R 110 each independently represents a hydrogen atom or a substituent.
In general formula (M2), R 201 to R 215 each independently represent a hydrogen atom or a substituent, X 201 represents a monovalent anion, and n201 represents 0 or 1.
In general formula (M3), R 301 to R 317 each independently represent a hydrogen atom or a substituent, X 301 represents a monovalent anion, and n301 represents 0 or 1.
In general formula (M4), R 402 to R 407 each independently represent a hydrogen atom or a substituent, Ar 401 represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M5), R 501 to R 508 each independently represent a hydrogen atom or a substituent.
In general formula (M6), R 601 to R 603 each independently represents a hydrogen atom or a substituent, Ar 601 represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M7), R 701 to R 706 each independently represent a hydrogen atom or a substituent.
In general formula (M8), R 811 to R 818 and R 821 to R 828 each independently represent a hydrogen atom or a substituent.
The inkjet printing method according to any one of claims 1 to 6, wherein the polymer has a glass transition temperature of 100 ° C or lower.
An inkjet ink for textile printing comprising a polymer aqueous dispersion having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group.
The inkjet ink according to claim 8, wherein the nonionic hydrophilic group is a group represented by the following general formula (A).

In general formula (A), n1 represents an integer of 5 to 150.
The inkjet ink according to claim 8 or 9, wherein the repeating unit including a structure derived from the dye is a repeating unit represented by the following general formula (1).

In General Formula (1), X 1 represents a linking group, L 1 represents a single bond or a divalent linking group, and D 1 represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye.
The D 1 in the general formula (1) represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye represented by any one of the following general formulas (M1) to (M8). Inkjet ink.

In general formula (M1), R 101 to R 110 each independently represents a hydrogen atom or a substituent.
In general formula (M2), R 201 to R 215 each independently represent a hydrogen atom or a substituent, X 201 represents a monovalent anion, and n201 represents 0 or 1.
In general formula (M3), R 301 to R 317 each independently represent a hydrogen atom or a substituent, X 301 represents a monovalent anion, and n301 represents 0 or 1.
In general formula (M4), R 402 to R 407 each independently represent a hydrogen atom or a substituent, Ar 401 represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M5), R 501 to R 508 each independently represent a hydrogen atom or a substituent.
In general formula (M6), R 601 to R 603 each independently represents a hydrogen atom or a substituent, Ar 601 represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M7), R 701 to R 706 each independently represent a hydrogen atom or a substituent.
In general formula (M8), R 811 to R 818 and R 821 to R 828 each independently represent a hydrogen atom or a substituent.
The inkjet ink according to any one of claims 8 to 11, wherein the glass transition temperature of the polymer is 100 ° C or lower.
The inkjet ink according to any one of claims 8 to 12, further comprising an aqueous organic solvent.
The inkjet ink according to any one of claims 8 to 13, wherein the polymer in the aqueous dispersion of the polymer is a particulate polymer, and the average particle diameter of the particulate polymer is 50 to 500 nm.
The inkjet ink according to any one of claims 8 to 13, wherein the polymer has a weight average molecular weight of 3,000 to 2,000,000.
An ink cartridge filled with the inkjet ink according to any one of claims 8 to 15.
A colored fabric comprising a fabric and a polymer having a repeating unit containing a structure derived from a dye and a repeating unit containing a nonionic hydrophilic group.