JP2018145399A - Ink set, inkjet textile printing method, ink cartridge, and inkjet printer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set capable of providing colored textiles excellent in texture, image sharpness and fastness to wet rubbing, an inkjet textile printing method based on the ink set, an ink cartridge having the ink set, and an inkjet printer.SOLUTION: The invention provides: an ink set that includes an inkjet ink including a water dispersion of a polymer having a structure derived from a dye and an inkjet ink including a water dispersion of a pigment; an inkjet textile printing method based on the ink set; an ink cartridge having the ink set; and an inkjet printer.SELECTED DRAWING: None

Description

  The present invention relates to an ink set, an ink jet textile printing method, an ink cartridge, and an ink jet printer.

  Ink-jet printing does not require the production of a plate, can quickly form an image with excellent gradation, and uses only a necessary amount of ink as a formed image, so it has environmental advantages such as less waste liquid. It can be said that this is an excellent printing method.

  For example, Patent Document 1 describes an ink jet textile printing method using a pigment. In this method, a pigment and a surfactant as a dispersant are mixed in water and then finely dispersed with an attritor or a mill machine together with glass beads, zirconia beads, titania beads, or stainless steel balls, etc., are used as a colorant. It has been. Then, this colorant is diluted with a reducer containing an emulsion resin for fixing the pigment, a pigment ink is prepared, adhered to the fiber by an ink jet method, and the resin is fused by a heating roller to fix the pigment. .

  Patent Document 2 describes an ink set for inkjet textile printing that includes an ink containing a pigment. Further, Patent Documents 3 and 4 describe ink-jet inks containing a polymer linked with a dye.

JP 2010-37700 A JP 2012-7148 A Special table 2004-534106 gazette Special table 2002-509957 gazette

However, the inkjet printing using the ink containing the pigment described in Patent Documents 1 and 2 must use a large amount of emulsion resin as a fixing agent in order to fix the pigment to the fabric, and the texture of the colored fabric is firm. Become. There is also room for improvement in image sharpness and wet friction fastness.
Patent Documents 3 and 4 do not specifically disclose textile printing and do not describe any of the above problems.

  An object of the present invention is to provide an ink set capable of providing a colored fabric excellent in texture, image sharpness and fastness to wet friction, an ink jet printing method using the ink set, an ink cartridge having the ink set, and an ink jet To provide a printer.

  The object of the present invention has been achieved by the following means. Although the details of the reason why the above problems have been solved by the ink set of the present invention have not been clarified, it is considered that a polymer having a structure derived from a dye corrects a color that cannot be colored only with a pigment.

<1>
An ink set comprising an inkjet ink comprising an aqueous dispersion of a polymer having a structure derived from a dye, and an inkjet ink comprising an aqueous dispersion of a pigment.
<2>
The ink set according to <1>, which is for inkjet textile printing.
<3>
The pigment is
Carbon black,
Aniline black,
C. I. Pigment Yellow 3, 12, 53, 55, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 155, 180, 185,
C. I. Pigment Red 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 209, 219,
C. I. Pigment violet 19, 23,
C. I. Pigment orange 36, 43, 64,
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 56, 60, 63,
C. I. Pigment Green 36
The ink set according to <1> or <2>, which is at least one selected from the group consisting of:
<4>
The structure derived from the dye is a structure derived from any dye selected from an azo compound, stilbene, triarylmethane, xanthene, indoaniline, indophenol, nigrosine, anthraquinone, quinophthalone, dicyanostyryl compound, and phthalocyanine. The ink set according to any one of <1> to <3>.
<5>
The ink set according to any one of <1> to <4>, wherein the polymer having a structure derived from the dye is polyurethane.
<6>
The ink set according to any one of <1> to <5>, wherein the polymer having a structure derived from the dye is a polymer having a crosslinked structure.
<7>
The ink set according to any one of <1> to <6>, wherein the polymer having a structure derived from the dye melts at 200 ° C.
<8>
The inkjet ink containing an aqueous dispersion of a polymer having a structure derived from the dye is at least one of a magenta ink, a yellow ink, a cyan ink, and a black ink,
The ink set according to any one of <1> to <7>, wherein the inkjet ink containing the pigment aqueous dispersion is at least one of a yellow ink, a cyan ink, and a black ink.
<9>
<1>-<8> The inkjet textile printing method which has the process of printing directly on a fabric with an inkjet system using the ink set of any one of <8>.
<10>
An ink jet method using an aqueous pretreatment liquid containing a flocculant to a fabric to obtain a pretreated fabric, and the ink set according to any one of <1> to <8> And an ink jet printing method comprising a step of printing on the pretreated fabric.
<11>
Furthermore, the inkjet textile printing method as described in <9> or <10> including a heat processing process.
<12>
The inkjet printing method according to <11>, wherein the polymer having a structure derived from the dye is melted in the heat treatment step.
<13>
An ink cartridge having the ink set according to any one of <1> to <8>.
<14>
<1>-<8> The inkjet printer which has an ink set of any one of <8>.

  ADVANTAGE OF THE INVENTION According to this invention, the ink set which can provide the colored cloth excellent in texture, image clarity, and wet-fastness fastness, the inkjet textile printing method using the said ink set, the ink cartridge which has the said ink set, and an inkjet A printer can be provided.

It is a figure which shows UV (ultraviolet) absorption spectrum in chloroform / methanol = 1/1 solution about (M-1-1).

Hereinafter, the present invention will be described in detail.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

In the present specification, the “substituent selected from substituent group A” refers to the substituents described in [0012] to [0051] of International Publication No. 2015/199135.
In the present specification, the substituent group A1 includes the following substituents.

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

  In the present invention, the ionic group such as a sulfo group or a carboxyl 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).

[Inkjet ink containing aqueous dispersion of polymer having structure derived from dye]
An inkjet ink containing an aqueous dispersion of a polymer having a structure derived from a dye is also referred to as “inkjet ink (P)”. Hereinafter, the inkjet ink (P) will be described.

(Polymer having structure derived from dye)
The inkjet ink (P) includes an aqueous dispersion of a polymer having a structure derived from a dye.
In the polymer having a structure derived from a dye (hereinafter, also referred to as “dye polymer”) used in the present invention, the structure derived from a dye means one or more arbitrary hydrogen atoms from an organic compound used as a dye. A group formed by removing (dye residue), preferably a group formed by removing one or two arbitrary hydrogen atoms from an organic compound used as a dye.
The dye polymer is a pigment multimer including a structure derived from a dye, and may be a linear polymer or a network polymer. In the case of a linear polymer, the structure derived from the dye may be included in the main chain of the polymer, or may be included in the side chain.
The dye polymer is preferably a polymer having a repeating unit containing a structure derived from a dye.
The method for obtaining the dye polymer is arbitrary, but a method for obtaining a dye polymer by polymerizing or copolymerizing a monomer containing a structure derived from a dye, or a polymer that does not have a structure derived from a dye in advance. Is prepared, and then a structure derived from a dye is introduced by a polymer reaction or the like to obtain a dye polymer. The method for producing the dye polymer or the polymer having no structure derived from the dye is not particularly limited, but those synthesized by radical polymerization, addition polymerization or condensation polymerization are preferably used.

As a structure derived from a dye, a structure derived from a dye as classified by a color index (abbreviation “CI”), or an arbitrary substituent within the scope of the effect of the present invention in the structure A structure in which is substituted, or a structure in which an arbitrary substituent is removed from the structure within a range where the effects of the present invention are obtained is preferable.
Examples of structures derived from dyes include azo compounds (monoazo compounds, disazo compounds, trisazo compounds, polyazo compounds), stilbenes, carotenoids, diarylmethanes, triarylmethanes, xanthenes, acridines, quinolines, methines (monomethine, polymethine), Examples include structures derived from any dye selected from azomethine, aniline, indoaniline, indamine, indophenol, azine, oxazine, thiazine, anthraquinone, indigo, quinophthalone, digrosine, porphyrin, cyanine, and phthalocyanine. It is done.
The structure derived from the dye is azo compound, stilbene, diarylmethane, triarylmethane, xanthene, acridine, quinoline, polymethine, monomethine, azomethine, indoaniline, indophenol, nigrosine, oxazine, thiazine, anthraquinone, indigo, quinophthalone, porphyrin , A dicyanostyryl compound, a structure derived from any dye selected from cyanine and phthalocyanine, and from the viewpoint of coloring power, an azo compound, stilbene, triarylmethane, xanthene, indoaniline, indophenol, nigrosine It is more preferable to include a structure derived from any dye selected from among an anthraquinone, a quinophthalone, a dicyanostyryl compound, and a phthalocyanine.

  The dye may be a water-soluble dye or a water-insoluble dye, but it may be a water-insoluble dye from the viewpoint of water resistance and washing resistance of the dye polymer. preferable. Moreover, it is preferable that it is a dye which does not have ionic groups, such as a carboxyl group, a sulfo group, a phosphoric acid group, these salts, and an ammonium group. Such a dye is not particularly limited, and for example, a water-insoluble dye such as a disperse dye may be used, or a water-soluble dye obtained by removing an ionic group may be used.

As the dye polymer, a polymer containing a structure derived from a dye in the main chain or side chain is preferably used. The polymer constituting the main chain in the polymer containing a structure derived from a dye in the main chain or side chain is not particularly limited, but an acrylic polymer, urethane polymer (polyurethane), urea polymer (polyurea), or styrene polymer is preferably used. In particular, an acrylic polymer or a urethane polymer is preferable, and a urethane polymer is most 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. In this specification, “(meth) acrylic acid” represents at least one of acrylic acid and methacrylic acid, and “(meth) acrylic acid ester” represents at least one of acrylic acid ester and methacrylic acid ester. In addition, the urethane polymer in the present invention is a polymer having a urethane bond in the main chain, and includes a compound having two or more hydroxyl groups (polyol compound) and a compound having two or more isocyanate groups (polyisocyanate compound). Formed by reaction. The urethane polymer may be referred to as polyurethane. The urethane polymer in the present invention may further be a polymer having a urea bond. A polymer having a urethane bond and a urea bond is also referred to as “polyurethane / urea”. As one type of preferred form of the dye polymer in the present invention, there is a polyurethane / urea in which a structure derived from a dye and a first partial structure including a urethane bond and a second partial structure including a urethane bond are bonded by a urea bond. Can be mentioned. The urea polymer in the present invention is a polymer having a urea bond in the main chain, and is formed by a reaction between a compound having two or more amino groups (polyamine compound) and a polyisocyanate compound. The urea polymer is sometimes referred to as polyurea. Moreover, the styrene polymer in this invention means the polymer which has a repeating unit derived from styrene.
It is preferable that the dye polymer is polyurethane from the viewpoint of improving color developability. When the dye polymer is polyurethane, since the structure derived from the dye is not introduced into the side chain of the polymer but introduced into the main chain, the structure derived from the dye is less likely to aggregate and the color developability is improved. I guess.

  The structure derived from the dye in the dye polymer is not limited as long as the effect of the present invention is achieved, but any hydrogen atom from the dye represented by any one of the following general formulas (M1) to (M9) is 1 The dye residue is preferably removed by one or more (preferably one or two), and is represented by any one of the following general formulas (M1) to (M3), (M5), (M7) to (M9). More preferably, it is a dye residue obtained by removing one or more (preferably one or two) arbitrary hydrogen atoms from the dye. In addition, general formula (M2) and (M3) shall also include each resonance structure.

In General Formula (M1), R ^{101 to} R ¹¹⁰ each independently represent a hydrogen atom or a substituent.
In General Formula (M2), R ^{201 to} R ²¹⁵ each independently represent a hydrogen atom or a substituent, X ²⁰¹ represents a monovalent anion, and n ²⁰¹ represents 0 or 1.
In General Formula (M3), R ^{301 to} R ³¹⁷ each independently represent a hydrogen atom or a substituent, X ³⁰¹ represents a monovalent anion, and n301 represents 0 or 1.
In General Formula (M4), R ^{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 ⁶⁰² each independently represent a hydrogen atom or a substituent, R ⁶⁰³ represents a hydrogen atom or a substituent, and Ar ⁶⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group. And the phenyl group, the naphthyl group, or the heterocyclic group may further have a substituent.
In 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.
In General Formula (M9), R ^{1 to} R ¹⁸ each independently represents a hydrogen atom or a substituent. R ¹⁹ and R ²⁰ each independently represents an alkyl group or a hydroxyalkyl group.

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 , R ^{501 to} R ⁵⁰⁸ in general formula (M5), R ^{601 to} R ⁶⁰³ in general formula (M6), R ^{701 to} R ⁷⁰⁶ in general formula (M7), R ⁸¹¹ in general formula (M8) To R ⁸¹⁸ and R ^{821 to} R ⁸²⁸ , and when R ^{1 to} R ¹⁸ in General Formula (M9) represent a substituent, the substituent is selected from the above substituent group A (preferably the above substituent) Substituents selected from group A1).

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, at least two of the substituents are bonded to each other, and It may form a 6-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. (Preferably a substituent selected from the above substituent group A1).

The substituent in the case where Ar ⁴⁰¹ in the general formula (M4) further has a substituent and the substituent in the case where Ar ⁶⁰¹ in the general formula (M6) further has a substituent are selected from the above substituent group A. And a substituent (preferably a substituent selected from the substituent group A1).

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

  Some of the dyes represented by the above general formulas (M1) to (M9) are classified by color index, and can be synthesized by a conventionally known method (for example, Japanese Patent Publication No. 7-49583, patent) No. 5715380, International Publication No. 2010/110199, Japanese Translation of PCT International Publication No. 2002-509957, etc.).

  Specific examples of the dyes represented by the general formulas (M1) to (M9) are those described in [0126] to [0132] of International Publication No. 2017/131107, and [0092] of Japanese Patent Application No. 2017-034066. ] To [0100], and those described in [0068] of JP 2013-535558 A, in particular, the specific examples of the dye represented by the general formula (M9) An example is Solvent Black 3.

(Molecular weight of dye polymer)
When the dye polymer does not have a crosslinked structure, the weight average molecular weight (Mw) of the dye polymer is preferably 3,000 to 2,000,000, more preferably 3,000 to 1,000,000, and 3,000 to 200,000 is particularly preferred. The weight average molecular weight of the dye polymer can be measured by gel permeation chromatography (GPC).

(Structure of dye polymer)
The dye polymer may have a structure derived from a dye as an essential structure, but it is preferable to introduce a dispersing group from the viewpoint of dispersibility in water. The dispersing group may be ionic or nonionic. At least one of a hydrophobic group (an electrically neutral non-polar group having low affinity with water) and an ionic group (an electrically ionic polar group having high affinity with water) Repeating units containing may be introduced.
The molecular structure of the dye polymer may be linear or branched, may be random, alternating, periodic, or block, and may be a graft polymer designed with a trunk and branch structure.

The dye polymer may have a structure having an ionic group as a dispersing group. The introduction amount of the structure having an ionic group in the dye polymer is preferably introduced so that the acid value or amine value of the dye polymer is 1 to 60 mgKOH / g, and is introduced so as to be 1 to 30 mgKOH / g. More preferably. Within the above range, the dispersion stability and wash fastness of the aqueous dispersion of the dye polymer are excellent. The acid value or amine value can be determined by a neutralization titration method such as JIS (Japanese Industrial Standard) K 0070.
The dye polymer may have a structure having a nonionic group as a dispersing group. The introduction amount of the structure (monomer unit) having a nonionic group as a dispersing group is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass. Within the above range, the dispersion stability and wash fastness of the aqueous dispersion of the dye polymer are excellent.
The dye polymer preferably has an anionic group.
The anionic group is preferably an acid group.

The dye polymer preferably has a crosslinked structure. By having a crosslinked structure, the strength of the film formed by fusing the dye polymer is improved, and a colored cloth having excellent durability can be obtained. The crosslinked structure represents a structure obtained by using a compound having a total of three or more hydroxyl groups and isocyanate groups in the molecule as at least one monomer. Examples of the compound having three or more hydroxyl groups in the molecule include glycerin, polyglycerin, trimethylolpropane, pentaerythritol and the like. Examples of the compound having three or more isocyanate groups in the molecule include polymeric MDI (manufactured by Wako Pure Chemical Industries, Aldrich or Tosoh Corporation), duranate (manufactured by Asahi Kasei Corporation, trade name), and the like.
In general, since a polymer having a crosslinked structure is hardly soluble in an organic solvent, when a dye polymer is mixed with dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), or tetrahydrofuran (THF), it is insoluble in any solvent. If the minute remains, it can be considered that the dye polymer is a polymer having a crosslinked structure.

As will be described later, in the inkjet printing method of the present invention, it is preferable to perform a heat treatment step after printing an aqueous dispersion of a dye polymer. In the heat treatment step, since the dye polymer is melt-dyed, the dye polymer is preferably melted at a heat treatment temperature or lower. Since the heat treatment step is preferably performed at 100 to 200 ° C, the dye polymer is preferably melted at 200 ° C or lower, and more preferably at 180 ° C or lower.
The Tg (glass transition temperature) of the dye polymer is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and even more preferably 150 ° C. or lower.
The Tg of the dye polymer can be measured by DSC (differential scanning calorimetry).
The dye polymer has a higher Tg by having a structure derived from a dye as compared with a polymer not having a structure derived from a dye. In the acrylic polymer in which the structure derived from the dye is introduced into the side chain of the (meth) acrylate ester, it may not melt at 200 ° C. depending on the structure or composition, but the main chain is polyurethane, and the main chain or side chain A polymer having a structure derived from a dye often melts at 200 ° C. or lower.

(Aqueous dispersion of dye polymer)
The aqueous dispersion of dye polymer (dye polymer aqueous dispersion) contains at least water and the dye polymer, and may further contain an aqueous organic solvent. Further, depending on the method for producing the aqueous dispersion of the dye polymer, either a low molecular surfactant or a high molecular dispersant may be used together or not (so-called self-dispersing).
The dye polymer can be used alone or in admixture of two or more.

In the present invention, the above-described dye polymer is used not in a state dissolved in water but in a state dispersed in water (water dispersion).
In the state where the dye polymer is dispersed in water, unlike the state in which the dye polymer is dissolved in water, the polymer is substantially insoluble in water, and thus is excellent in terms of water resistance such as washing resistance and sweat resistance. In the ink-jet printing method of the present invention, a step of washing with water after printing is unnecessary, and therefore the dye polymer is a polymer that is substantially insoluble in water. In the aqueous dispersion of the dye polymer, the dye polymer that is insoluble in water is dispersed as particles, and the average particle diameter is preferably 50 to 500 nm. When the dye polymer is dissolved in water, the dye polymer is not present as particles in water.
It is preferable to use ultrapure water as water.

  When dispersed in water, the dye polymer is easily compatible with water (easy to get wet) and electrostatic repulsion (repulsive force) as a property of the dye polymer itself or by adsorption with the low molecular surfactant or polymer dispersant used in combination. ) Or steric repulsion prevents re-aggregation of the fine particles of the dye polymer, and has a function of suppressing sedimentation.

The dye polymer is particulate in the aqueous dispersion. The average particle diameter of the particulate dye polymer in the aqueous dispersion of the dye polymer is preferably 50 to 500 nm, more preferably 50 to 300 nm, and particularly preferably 50 to 200 nm. Within this range, the fabric can be printed by the ink jet method.
As the average particle size in the present specification, the value of the volume average size (MV) measured using a particle size distribution measuring device (Nanotrack UPA EX150, trade name, manufactured by Nikkiso Co., Ltd.) was used.

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

(Low molecular surfactant or polymer dispersant)
The low molecular surfactant or the high molecular dispersant is preferably a low molecular surfactant or a high molecular dispersant having a hydrophobic group and an ionic group, and is added when the dye polymer is dispersed. The low molecular surfactant or polymer dispersant adsorbs to the surface of the dye polymer and blends (wet) it with water, and the dye polymer fine particles ground by mechanical action are electrostatically repulsive (repulsive) or steric repulsive. This prevents the re-aggregation of fine particles and has a function of suppressing sedimentation.

  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 dye polymer aqueous dispersion, and the surface tension of the aqueous dispersion is within this range. Is preferably adjusted arbitrarily.

  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 dye polymer aqueous dispersion, and the surface tension of the aqueous dispersion can be arbitrarily set within such a range. It is preferable to adjust to.

The method for producing an aqueous dispersion of a dye polymer is as follows:
(I) After mixing a dye polymer powder or paste and, if necessary, a low molecular surfactant or a high molecular dispersant in water or an aqueous organic solvent, glass beads, zirconia beads, titania beads, Or a method of finely dispersing with an attritor or a mill with a stainless steel ball,
(Ii) a method of obtaining an aqueous dispersion of a dye polymer by synthesizing a dye polymer in an organic solvent and then adding water, optionally a surfactant or a solvent, and removing a solvent other than water;
(Iii) An organic solvent, a compound having a structure derived from a dye and having a group that reacts with a polyisocyanate compound, a polyisocyanate compound, and other monomers and a polymerization initiator as necessary are added. In addition, a compound having a structure derived from a dye in an organic solvent and having a group that reacts with a polyisocyanate compound is polymerized, and water, optionally a neutralizer, an emulsifier (surfactant), and a chain extender are added. Emulsifying and chain-extending the polymer, and then appropriately removing the organic solvent to obtain an aqueous dispersion of the dye polymer,
(Iv) An organic solvent solution of a first prepolymer having an isocyanate group at the terminal, obtained by reacting a compound having a structure derived from a dye and having a group that reacts with a polyisocyanate compound and the polyisocyanate compound An organic solvent solution of a second prepolymer having a dispersible structure and having an isocyanate group at the terminal, optionally mixed with an emulsifier (surfactant) and an organic solvent, water, optionally an emulsifier (surfactant) ) Is added and emulsified, and the organic solvent is appropriately removed to obtain an aqueous dispersion of the dye polymer.
These can be suitably used.

(Aqueous organic solvent)
The aqueous organic solvent preferably has a water solubility at 25 ° C. of 10 g / 100 g-H ₂ O or more, more preferably 20 g / 100 g-H ₂ O or more, and is miscible with water at an arbitrary ratio. Is particularly preferred. Examples of the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents.
The content of the aqueous organic solvent in the dye polymer aqueous dispersion is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. This range is preferable because the stability of the aqueous dispersion and the ejection stability as an inkjet ink can be imparted.

(Crosslinking agent)
The inkjet ink (P) may contain a cross-linking agent for the purpose of improving the friction resistance or the fastness to washing of the colored fabric. 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).

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

(Aqueous dispersion of water-insoluble polymer without structure derived from dye)
The inkjet ink (P) may contain an aqueous dispersion of a water-insoluble polymer having no structure derived from a dye, in addition to the aqueous dispersion of a polymer having a structure derived from the dye and the pigment.
By further including an aqueous dispersion of a water-insoluble polymer not having a structure derived from a dye in the ink-jet ink (P), the dye polymer and / or the pigment can be firmly fixed to the fabric in the ink-jet printing.
In the present invention, the water-insoluble polymer is a polymer that is dispersed as particles in water at 25 ° C. The average particle size (MV) of the water dispersion of the water-insoluble polymer is preferably 20 to 500 nm, and more preferably 30 to 300 nm. If the polymer is dissolved in water, the polymer is not present as particles in water.
The water-insoluble polymer that does not have a structure derived from a dye is a polymer that does not have a structure derived from a dye in the molecule, and the “structure derived from a dye” is as described above.
The water-insoluble polymer having no structure derived from a dye is preferably a colorless polymer.

An aqueous dispersion of a water-insoluble polymer not having a structure derived from a dye contains at least water and a water-insoluble polymer not having a structure derived from a dye, and water having no structure derived from a dye. The insoluble polymer is dispersed in water. In addition, the water-insoluble polymer which does not have the structure derived from a dye is a component different from the polymer dispersing agent which can be used as a dispersing agent. A water-insoluble polymer that does not have a structure derived from a dye exists by being dispersed alone in the ink, while a polymer dispersant is dispersed in a mixture with an aqueous dispersion of a dye polymer in the ink. Exist.
The water-insoluble polymer having no structure derived from a dye is preferably polyurethane, polyester, acrylic polymer, styrene-butadiene copolymer, or polyvinyl chloride. The water-insoluble polymer having no structure derived from the dye may be used alone or in combination of two or more.
A water-insoluble polymer having no structure derived from a dye may be synthesized by a known method, or a commercially available product may be used.
Specific examples of polyurethane that can be used as a water-insoluble polymer that does not have a structure derived from a dye include Takelac manufactured by Mitsui Chemicals, Inc., Elastron manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Taisei Fine Chemical Co., Ltd. The WBR series, Meisei Chemical Industry Co., Ltd. pass call, Enomoto Kasei Co., Ltd. Neorez series, etc. are mentioned.
Specific examples of the polyester that can be used as a water-insoluble polymer that does not have a structure derived from a dye include Toyobo Co., Ltd. vylonal, Takamatsu Yushi Co., Ltd. pesresin, and the like.
Specific examples of the acrylic polymer that can be used as a water-insoluble polymer that does not have a structure derived from a dye include styrene / acrylic resin from Nippon Synthetic Chemical Co., Ltd., Movinyl series, and Lovene series from Mallard Creek Polymers. Styrene / acrylic resin, acrylic resin, and urethane / acrylic resin.
Examples of the styrene-butadiene copolymer that can be used as a water-insoluble polymer that does not have a structure derived from a dye include Lovene series manufactured by Mallard Creek Polymers and Nipol Lx421 manufactured by Nippon Zeon Co., Ltd.
Specific examples of polyvinyl chloride that can be used as a water-insoluble polymer that does not have a structure derived from a dye include vinibran manufactured by Nissin Chemical Industry Co., Ltd.

As will be described later, in the inkjet printing method of the present invention, it is preferable to perform a heat treatment step after printing the ink. In the heat treatment step, the water-insoluble polymer that does not have a structure derived from a dye is preferably melted at a heat treatment temperature or lower as in the above-described dye polymer. A water dispersion of a water-insoluble polymer having no structure derived from a dye melts at a temperature lower than the heat treatment temperature, whereby the dye polymer and / or the pigment can be firmly fixed on the fabric. Since the heat treatment step is preferably performed at 100 to 200 ° C., the water-insoluble polymer having no structure derived from the dye is preferably melted at 200 ° C. or less, more preferably 180 ° C. or less.
The Tg (glass transition temperature) of the water-insoluble polymer having no structure derived from the dye is preferably 200 ° C. or less, more preferably 180 ° C. or less, and further preferably 150 ° C. or less.
The Tg of a water-insoluble polymer having no structure derived from a dye can be measured by DSC (differential scanning calorimetry).
From the reason of maintaining a good texture of the colored fabric when the ink of the present invention is used for inkjet printing, it is even more preferable that the Tg of the water-insoluble polymer having no structure derived from the dye is 150 ° C. or less. It is particularly preferably 120 ° C. or less, and most preferably less than 100 ° C. The lower the Tg of the water-insoluble polymer that does not have a structure derived from a dye, the softer the resulting film, the better the texture of the colored cloth.

The content of the water-insoluble polymer having no structure derived from the dye in the aqueous dispersion of the water-insoluble polymer having no structure derived from the dye is preferably 0.1 to 40% by mass, and more preferably. It is 1-30 mass%, Most preferably, it is 1-25 mass%.
The water content in the aqueous dispersion of the water-insoluble polymer having no structure derived from the dye is preferably 40 to 95% by mass, more preferably 50 to 90% by mass.

  When the inkjet ink (P) includes an aqueous dispersion of a water-insoluble polymer that does not have a structure derived from a dye, the aqueous dispersion of a water-insoluble polymer that does not have a structure derived from a dye in the inkjet ink (P) The content of is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass.

For matters other than those mentioned above,
A water-insoluble polymer that does not have a structure derived from a dye and a water that does not have a structure derived from a dye, except that it does not have a structure derived from a dye and the preferable range of Tg is the above range. The detailed description of the aqueous dispersion of the insoluble polymer is the same as that described above for the dye polymer and the aqueous dispersion of the dye polymer.

(Other ingredients)
The inkjet ink (P) may contain other components other than those described above. Other components include, for example, colorants other than the above dye polymers, organic solvents, surfactants, optical brighteners, surface tension modifiers, antifoaming agents, anti-drying agents, lubricants, thickeners, UV absorption Agents, anti-fading agents, antistatic agents, matting agents, antioxidants, specific resistance adjusting agents, rust inhibitors, inorganic pigments, anti-reducing agents, antiseptics, antifungal agents, chelating agents, and the like.

The inkjet ink (P) contains at least a water dispersion of a dye polymer, that is, the ink jet ink (P) is a dispersion in which a dye polymer is dispersed in a liquid containing water. In addition, the dye polymer is in the form of particles in the inkjet ink (P), and the preferable average particle diameter of the particulate dye polymer is the same as that described above.
The content of the dye polymer in the inkjet ink (P) is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 3 to 12% by mass. .
The water content in the inkjet ink (P) is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and still more preferably 50 to 80% by mass.
The method for preparing the inkjet ink (P) is not particularly limited. For example, the inkjet ink (P) can be prepared by mixing an aqueous dispersion of a dye polymer with water or other components as necessary.

[Inkjet ink containing aqueous dispersion of pigment]
An inkjet ink containing an aqueous dispersion of pigment is also referred to as “inkjet ink (Q)”. The inkjet ink (Q) will be described.

(Aqueous dispersion of pigment)
The inkjet ink (Q) contains an aqueous dispersion of pigment.
As the pigment aqueous dispersion (also referred to as “pigment aqueous dispersion”), the pigment dispersion described in JP2012-7148A can be used.
The pigment of the pigment aqueous dispersion in the present invention is
Carbon black,
Aniline black,
C. I. Pigment Yellow 3, 12, 53, 55, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 155, 180, 185,
C. I. Pigment Red 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 209, 219,
C. I. Pigment violet 19, 23,
C. I. Pigment orange 36, 43, 64,
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 56, 60, 63,
C. I. Pigment Green 36
It is preferably at least one selected from

0.5-30 mass% is preferable and, as for the addition amount of the pigment in the pigment aqueous dispersion in this invention, 1.0-15 mass% is more preferable. If the addition amount of the pigment is 0.5% by mass or more, the printing density is preferably increased, and if it is 30% by mass or less, the viscosity of the ink is increased or the structural property is hardly generated in the viscosity characteristic. This is preferable because of excellent discharge stability.
As the pigment, a self-dispersing pigment can also be used. Self-dispersing pigments that can be used include self-dispersing carbon black CAB-O-JET 200, 300 (above, manufactured by Cabot Corporation), BONJET CW-1 (500 μmol / g as a carboxy group), CW-2 ( Commercial products such as carboxy group (470 μmol / g) (manufactured by Orient Chemical Co., Ltd.) and Tokai Carbon Co., Ltd. Aqua-Black 162 (carboxyl group, about 800 μmol / g) can be used.
A pigment can be used individually or in mixture of 2 or more types in arbitrary ratios.
In the present invention, the dye polymer can also be used as a dispersant for dispersing the pigment in water. However, when a dye polymer is used as a pigment dispersant, the dye polymer present as a dispersant around the pigment is not the “aqueous dispersion of dye polymer” in the present invention. That is, the “dye polymer aqueous dispersion” in the present invention does not contain a pigment. Therefore, the ink set of the present invention includes an inkjet ink including a pigment dispersion containing a pigment and a dye polymer present as a dispersant around the pigment, even when a dye polymer is used as a pigment dispersant. Apart from that, it is necessary to include an inkjet ink containing an aqueous dispersion of a dye polymer. An ink set comprising an ink-jet ink comprising an ink-jet ink comprising an aqueous dispersion of a dye polymer and not including an ink-jet ink and comprising a pigment polymer containing a dye polymer present as a dispersant around the pigment is a heat treatment step in ink-jet printing. Due to the melting of the polymer, the dye polymer may be peeled off from the pigment and the pigment may bleed out.

(Other ingredients)
The inkjet ink (Q) may contain polymer fine particles. As the polymer fine particles, polymer fine particles described in JP2012-7148A can be used. As the polymer fine particles, crosslinkable polyurethane and / or crosslinkable polyurethane-polyurea are preferably used.
The inkjet ink (Q) may contain 1,2-alkylene glycol, glycol ether, or a water-soluble organic solvent. The preferable form about these is the form described in Unexamined-Japanese-Patent No. 2012-7148.
The inkjet ink (Q) may contain other components other than those described above. Other components include, for example, colorants other than the above pigments, crosslinking agents, organic solvents, surfactants, penetration inhibitors, pH adjusters, fluorescent brighteners, surface tension adjusters, antifoaming agents, and drying inhibitors. , Lubricants, thickeners, UV absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, resistivity regulators, rust inhibitors, inorganic pigments, anti-reduction agents, antiseptics, antifungal agents, And chelating agents.
Examples of the crosslinking agent that the inkjet ink (Q) may include are the same as those described as the crosslinking agent that the inkjet ink (P) may include.

The inkjet ink (Q) contains at least an aqueous dispersion of a pigment, that is, the inkjet ink (Q) is a dispersion in which a pigment is dispersed in a liquid containing water.
The content of the pigment in the inkjet ink (Q) is preferably 0.5 to 30% by mass, and more preferably 1 to 15% by mass.
The water content in the inkjet ink (Q) is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass.
Although the preparation method of inkjet ink (Q) is not specifically limited, For example, it can prepare by mixing the water dispersion of a pigment, and water or another component as needed.

The surface tension of the inkjet ink (P) and the inkjet ink (Q) is preferably adjusted to 20 mN / m to 70 mN / m, and more preferably adjusted to 25 mN / m to 60 mN / m. The viscosity of the inkjet ink (P) and the inkjet ink (Q) is preferably adjusted to 40 mPa · s or less, more preferably adjusted to 30 mPa · s or less, and particularly preferably adjusted to 20 mPa · s or less. preferable. Viscosity is measured using an E-type rotational viscometer, controlled at 25 ° C.
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.

[Ink set]
The ink set of the present invention includes inkjet ink (P) and inkjet ink (Q).
The ink set of the present invention may contain two or more ink-jet inks (P), and may contain two or more ink-jet inks (Q). That is, the ink set of the present invention only needs to include at least one ink-jet ink (P) and at least one ink-jet ink (Q).
The ink set of the present invention preferably contains at least two colored inks, and for example, preferably contains at least two colored inks selected from magenta ink, yellow ink, cyan ink, and black ink.
More specific embodiments include those shown in the following (1), but the present invention is not limited to these.
(1) The inkjet ink (P) is at least one of magenta ink, yellow ink, cyan ink, and black ink, and the inkjet ink (Q) is any of yellow ink, cyan ink, and black ink. At least one.

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

[Inkjet printing method]
The ink jet textile printing method of the present invention is an ink jet textile printing method having a step of printing on a fabric by an ink jet method using the ink set of the present invention, and there are the following two preferred embodiments.
1st aspect: The inkjet textile printing method which has the process of printing directly on a fabric by the inkjet system using the ink set of this invention.
Second aspect: A pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to a fabric to obtain a pretreated fabric, and directly using the ink set of the present invention to a fabric pretreated by an inkjet method An ink-jet printing method comprising a printing step.
In the present invention, “direct printing” on a fabric by an ink jet method does not require a transfer step, and does not require a step of printing ink jet ink directly on a fabric and a step of applying printing paste. Both ink jet inks are printed directly on the fabric.
The ink jet textile printing method of the present invention produces an effect of being excellent in the quality (texture), image sharpness and fastness to wet friction of a colored cloth with simple workability without producing waste materials such as waste water and transfer paper.

(Pretreatment process)
The pretreatment step in the second aspect is a step of obtaining a pretreated fabric by applying an aqueous pretreatment liquid containing a flocculant to the fabric. The method for applying the aqueous pretreatment liquid to the fabric is not particularly limited, and examples thereof include a coating method, a padding method, an ink jet method, a spray method, and a screen printing method.
The flocculant contained in the aqueous pretreatment liquid is not particularly limited as long as it has an action of aggregating the dye polymer, but is at least one selected from organic acids, polyvalent metal salts, and cationic compounds. It is preferable.
In particular, when the flocculant is a cationic compound or a polyvalent metal salt and the dye polymer has an anionic group (preferably an acid group), a high-concentration colored cloth is obtained by printing with the ink jet printing method. be able to. This is because the pre-treated cationic compound or polyvalent metal salt stays on the fabric surface as a result of agglomeration at the moment of contact with the ink containing the dye polymer having an anionic group, resulting in the surface. It is thought that the amount of the dye polymer present increases and the concentration can be increased. More preferably, the flocculant is a cationic compound.

≪Polyvalent metal salt≫
The polyvalent metal salt is a compound composed of a divalent or higher valent metal ion and an anion. Specifically, calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium hydroxide, calcium carbonate, magnesium chloride, magnesium acetate, magnesium sulfate, magnesium carbonate, barium sulfate, barium chloride, zinc sulfide, zinc carbonate, copper nitrate Etc.

≪Cationic compound≫
The cationic compound is not particularly limited, and may be a low molecular compound or a high molecular compound.
Examples of the low molecular weight cationic compound include (2-hydroxyethyl) trimethylammonium chloride, benzoylcholine chloride, benzyltriethylammonium chloride, trimethylacetohydrazide ammonium chloride, 1-butyl-1-methylpyrrolidinium chloride, 3- Examples thereof include hydroxy-4- (trimethylammonio) butyrate hydrochloride, glycidyltrimethylammonium chloride, L-carnitine hydrochloride and the like.
Examples of the high molecular weight cationic compound include water-soluble and positively active in water such as polyallylamine or a derivative thereof, an amine-epihalohydrin copolymer, or other quaternary ammonium salt type cationic polymer. Examples include charged cationic polymers. In some cases, a water-dispersible cationic polymer can be used.

A flocculant may be used individually by 1 type and may be used together 2 or more types.
The aqueous pretreatment liquid may contain, for example, a surfactant, a resin and the like in addition to water and an aqueous organic solvent.

  The ink-jet printing method of the present invention is further integrated with the fiber by fusing the dye polymer to the fiber of the fabric by adding a heating step, and further improving the friction resistance without impairing the texture. There is an advantage that it can be granted.

(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). Is possible). The colored fabric is preferably dried and then subjected to heat treatment for the purpose of melting and dyeing, usually at 100 to 250 ° C., more preferably 100 to 200 ° C., particularly preferably 120 to 200 ° C. The heat treatment time is preferably 30 seconds to 3 minutes. In addition, when a reactive group (for example, a blocked isocyanate group) is introduced into the dye polymer, or when a crosslinking agent (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent) is used as an additive, From the viewpoint of friction resistance, it is possible to cause a crosslinking reaction using a reactive group introduced into the polymer (for example, a blocked isocyanate group) or a crosslinking agent used in combination as an additive (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent). preferable.

(Post-processing)
The fabric colored by the inkjet printing method of the present invention (colored fabric) is excellent in the flexibility and fastness (friction resistance) of the texture, but if necessary, the entire surface is padded with a post-treatment agent. Thus, it is possible to obtain a colored fabric with improved texture flexibility and fastness (particularly friction resistance).

(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.
As the fabric, a pretreated fabric can also be used. The pretreatment liquid can be applied by a coating method, a padding method, an ink jet method, a spray method, a screen printing method, or the like. The pretreatment liquid contains an aggregating agent that aggregates the dye polymer, and is preferably an aqueous solution. Examples of the flocculant include organic acids, polyvalent metal salts, and cationic compounds.
Apparel includes T-shirts, trainers, jerseys, pants, sweatsuits, dresses, blouses and the like. It is also suitable for bedding, handkerchiefs, cushion covers, curtains and the like.

[Ink cartridge and inkjet printer]
The present invention also relates to an ink cartridge having the ink set of the present invention and an ink jet printer having the ink set of the present invention.

[Synthesis of Dye Polymer (R-2-1)]
The dye polymer (R-2-1) was synthesized according to the following scheme. The unit of the ratio of the following repeating units is% by mass. Me represents a methyl group, and Et represents an ethyl group.

  To a 100 mL three-necked flask, 10 mL of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) was added, and the internal temperature was raised to 85 ° C. To the PGMEA, 9.0 g of polymerizable monomer RDW R-13 (manufactured by Wako Pure Chemicals, trade name), 1.0 g of polymerizable monomer 2-ethylhexyl methacrylate (EHMA), V-601 (Wako Pure Chemical) (Product name) 0.057 g and a solution prepared by dissolving 0.20 g of 1-dodecanethiol in 13.24 g of PGMEA was added dropwise over 3 hours. After completion of dropping, the reaction solution A was obtained by reacting at 85 ° C. for 1 hour. Then, V-601 (0.057g) was added to the reaction liquid A, and also it was made to react at 85 degreeC for 2 hours, and the reaction liquid B was obtained. The reaction solution B is allowed to cool to room temperature (20 ° C.), poured into 300 mL of water / 200 mL of methanol, crystals are precipitated, and the crystals are separated by filtration. It was dried for a day to obtain a red powder of a dye polymer (R-2-1). The yield of the dye polymer (R-2-1) was 8.0 g. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of the dye polymer (R-2-1) in tetrahydrofuran (THF) was 562 nm. Moreover, the weight average molecular weight (Mw) in gel permeation chromatography (GPC) measurement was 8,900 (polystyrene conversion), and dispersion degree (Mw / Mn) was 1.7. Mn represents a number average molecular weight. As GPC, HLC-8220 GPC (manufactured by Tosoh Corporation) was used.

[Synthesis of Dye Polymer (B-4-3)]
The dye polymer (B-4-3) was synthesized according to the following scheme. The unit of the ratio of the following repeating units is% by mass.

(Synthesis of Intermediate (BM-1))
C. I. 67.65 g of Acid Blue 1 (manufactured by Tokyo Chemical Industry) is stirred in 1.2 L of chloroform, and the internal temperature is cooled to 0 ° C. While maintaining the internal temperature at 0 ° C., 69.5 mL of oxalyl chloride was added dropwise, then 6 mL of DMF (N, N-dimethylformamide) was added dropwise, and then reacted at room temperature for 24 hours. Reaction was performed at 0 ° C. for 2 hours to obtain a reaction solution C. After concentrating the reaction liquid C using a rotary evaporator, 400 mL of acetonitrile was added, 29.8 g of 2-aminoethyl methacrylate hydrochloride was added, and then the internal temperature was cooled to 10 ° C. Triethylamine 58.2mL was dripped here slowly, and it was made to react at room temperature after that for 2 hours, and the reaction liquid D was obtained. The reaction solution D was poured into 1200 mL of water, and the precipitated crystals were separated by filtration. The obtained crystals were heated and washed with methanol to obtain an intermediate (BM-1) powder (yield 65.6 g).
Intermediate (BM-1) 3.0 g, 2-ethylhexyl methacrylate 2.0 g, 1-dodecanethiol 0.237 g, N-methylpyrrolidone (NMP) 27.8 g were added to a 100 mL three-necked flask, and the internal temperature was 85 ° C. The temperature was raised to. 0.3 g of V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added 4 times every 2 hours. After the completion of the reaction, the reaction solution is allowed to cool to room temperature, poured into 500 mL of water, crystals are precipitated, the crystals are filtered off, and dried for 1 day in a 60 ° C. blower dryer, and the dye polymer (B- 4-3) blue-yellow powder was obtained. The yield of the dye polymer (B-4-3) was 4.2 g. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of the dye polymer (B-4-3) in tetrahydrofuran (THF) was 610 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement of the dye polymer (B-4-3) was 9,100 (polystyrene conversion), and dispersity (Mw / Mn) was 2.3. As GPC, HLC-8220 GPC (manufactured by Tosoh Corporation) was used.

(Synthesis of dye polymer (Br-1))
A polyurethane compound (Br-1), which is a dye polymer, was synthesized according to Example 1 of JP-T-2002-509957.

(Synthesis of dye polymer (B-5))
According to Example 11 of JP-T-2002-509957, a polyurethane compound (B-5) as a dye polymer was synthesized.

[Preparation of dye polymer aqueous dispersion (1)]
0.4 g of dye polymer (R-2-1), 10 g of zirconia beads (manufactured by Nikkato, trade name YTZ ball, diameter 0.1 μm), 0.8 g of 10% by weight aqueous solution of sodium oleate, 0.5 g of glycerin, and ultrapure 4.2 g of water was added, and the mixture was dispersed for 10 hours at a rotation speed of 400 rpm (revolution per minute) using a planetary granulator (Pulverset 7 manufactured by Fritsch). From the obtained dispersion, zirconia beads were removed using a filter cloth to obtain a dye polymer aqueous dispersion (1). The average particle diameter (MV) of the particulate dye polymer in the dye polymer aqueous dispersion (1) was 98 nm.

[Preparation of dye polymer aqueous dispersion (2)]
Except for using the dye polymer (B-4-3) instead of the dye polymer (R-2-1), the dye polymer aqueous dispersion (2) was prepared in the same manner as in the preparation of the dye polymer aqueous dispersion (1). It was created. The average particle diameter (MV) of the particulate dye polymer in the dye polymer aqueous dispersion (2) was 81 nm.

[Preparation of dye polymer aqueous dispersion (3)]
Add 2.0 g of dye polymer (Br-1), 20 g of zirconia beads (manufactured by Nikkato, trade name YTZ ball, diameter 0.1 μm), and 8.0 g of ultrapure water, and add a planetary fine pulverizer (Pulversette 7 manufactured by Fritsch) The sample was dispersed at a rotation speed of 400 rpm (revolution per minute) for 5 hours. From the obtained dispersion, zirconia beads were removed using a filter cloth to obtain an aqueous dye polymer dispersion (3). The average particle diameter (MV) of the particulate dye polymer in the dye polymer aqueous dispersion (3) was 130 nm.

[Preparation of dye polymer aqueous dispersion (4)]
A dye polymer aqueous dispersion (4) was prepared in the same manner as the dye polymer aqueous dispersion (3) except that the dye polymer (B-5) was used instead of the dye polymer (Br-1). The average particle diameter (MV) of the particulate dye polymer in the dye polymer aqueous dispersion (4) was 150 nm.

[Creation of inkjet ink (Pm)]
The following components were mixed at room temperature, stirred for 15 minutes, and then filtered through a membrane filter (average pore size 0.8 μm) to prepare an inkjet ink (Pm). The inkjet ink (Pm) is magenta ink.
Dye polymer aqueous dispersion (1) 3.0 g
Trimethylolpropane 0.056g
0.913g of ultrapure water
1,12-hexanediol 0.112g
Glycerin 0.560g
Triethylene glycol monobutyl ether 0.112 g
2-pyrrolidone 0.168g
Propylene glycol 0.028g
Surfynol 465 (trade name, manufactured by Nissin Chemical Industry) 0.056g

[Creation of inkjet ink (Pc)]
An inkjet ink (Pc) was prepared in the same manner as the inkjet ink (Pm) except that the dye polymer aqueous dispersion (2) was used instead of the dye polymer aqueous dispersion (1). The inkjet ink (Pc) is a cyan ink.

[Preparation of inkjet ink (Pb)]
Instead of 3.0 g of the dye polymer aqueous dispersion (1), 1.5 g of the dye polymer aqueous dispersion (3) and 1.5 g of the dye polymer aqueous dispersion (4) were used. Inkjet ink (Pb) was prepared in the same manner as the preparation. The inkjet ink (Pb) is a black ink.

[Creation of inkjet ink (Qm)]
(Preparation of pigment dispersion)
3 g of a styrene-acrylic acid copolymer (Johncrill 678, manufactured by BASF, trade name), 1.3 g of dimethylaminoethanol, and 80.7 g of ion-exchanged water were stirred and mixed at 70 ° C. Next, C.I. I. 15 g of Pigment Red 112 and 50% by volume of zirconia beads having a particle diameter of 0.5 mm were filled by volume and dispersed using a sand grinder mill to obtain a pigment dispersion having a pigment content of 15% by mass.

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

(Preparation of pigment ink)
46.6 g of the pigment dispersion, 15 g of a 20% by weight aqueous solution of the aqueous binder, 2.9 g of PDX-7664A (trade name, manufactured by BASF), 10 g of triethylene glycol monobutyl ether, 5 g of 1,2-hexanediol, diethylene glycol 11 .2 g and Olfin 465 (manufactured by Nissin Chemical Industry, 0.6 g) are mixed, and ion-exchanged water is added thereto to prepare a total amount of 100 g, followed by filtration with a 0.8 μm filter, and inkjet ink (Qm ) The inkjet ink (Qm) is magenta ink.

[Preparation of inkjet ink (Qc)]
C. I. In place of Pigment Red 112, C.I. I. An inkjet ink (Qc) was prepared in the same manner as the inkjet ink (Qm) except that CI Pigment Blue 15: 4 was used. The inkjet ink (Qc) is a cyan ink.

[Creation of inkjet ink (Qy)]
C. I. In place of Pigment Red 112, C.I. I. An inkjet ink (Qy) was prepared in the same manner as the inkjet ink (Qm) except that CI Pigment Yellow 180 was used. The inkjet ink (Qy) is a yellow ink.

[Creation of inkjet ink (Qb)]
C. I. An inkjet ink (Qb) was prepared in the same manner as the inkjet ink (Qm) except that carbon black was used instead of the pigment red 112. The inkjet ink (Qb) is a black ink.

[Create ink set for inkjet textile printing]
Ink sets for ink jet textile printing 1 to 3 were prepared using the ink jet ink combinations shown in Table 1 below.

Example 1
Ink set 1 for ink jet textile printing is loaded into an ink cartridge, and using an ink jet printer (Calario PX-045A, trade name, manufactured by Seiko Epson Corporation), polyester fabric (polyester tropical (manufactured by Teijin Limited), color dye, Inc. Co., Ltd., product code A02-01019), cotton fabric (with cotton broad sill, color dye, product code A02-01002), polyester 65% cotton 35% blend (blend polyester 65 / cotton 35 broad, stock) Each image was printed on a product code A02-01030), manufactured by Color Co., Ltd., and dried at room temperature for 12 hours. After drying, using a heat press (Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type), heat treatment is performed at a temperature of 200 ° C., a pressure of 0.20 N / cm ² , for 60 seconds, A colored fabric was obtained.

(Example 2)
Ink-jet printing was performed in the same manner as in Example 1 except that the ink-jet printing ink set 2 was used in place of the ink-jet printing ink set 1 to obtain a colored fabric.

(Example 3)
[Preparation of aqueous pretreatment liquid A (1) containing flocculant]
An aqueous pretreatment liquid A (1) was prepared by mixing and stirring the following components. Cathiomaster PD-7 contains a cationic compound as a flocculant.
Cachio Master PD-7 (manufactured by Yokkaichi Synthesis Co., Ltd., solid content 50% by mass) 50 g
BYK348 (by Big Chemie Japan) 5g
Glycerin 100g
845g of water

[Pretreatment process]
Polyester fabric (polyester tropical (manufactured by Teijin Ltd.), Color Dyeing Co., Ltd., product code A02-01019), cotton fabric (with cotton broad sill, Co., Ltd., product dyeing A02-01002), and polyester 65% cotton 35% blend (mixed polyester 65 / cotton 35 broad, manufactured by Color Dyeing Co., Ltd., product code A02-01030) was applied with the prepared aqueous pretreatment liquid A (1) by a padding method, It was squeezed at a squeezing rate of 70% and dried for 24 hours. The squeezing rate (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid relative to the fabric after the cloth containing the aqueous treatment liquid is squeezed.

[Inkjet printing process]
Ink-jet printing was carried out in the same manner as in Example 1 except that a pretreated fabric was used as a fabric to obtain a colored fabric.

(Example 4)
Ink-jet printing was performed in the same manner as in Example 2 except that a pretreated fabric was used as a fabric, and a colored fabric was obtained.

(Comparative Example 1)
Ink-jet printing was performed in the same manner as in Example 1 except that the ink-jet printing ink set 3 was used in place of the ink-jet printing ink set 1 to obtain a colored fabric.

(Comparative Example 2)
Ink-jet printing was performed in the same manner as in Comparative Example 1 except that a pretreated fabric was used as a fabric to obtain a colored fabric.

The colored cloths obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated as follows.
In the evaluation of texture and fastness to wet friction, cotton cloth was used among the three kinds of cloth. Moreover, about the texture, Example 1 and 2 and the comparative example 1 were evaluated.
-Image clarity: The sensory evaluation was performed visually. AA when 3 types of fabric are clear and dark, A when 3 types of fabric are clear, B when 2 types are clear, C when only 1 type is clear, and 4 when there is no clear image D Rated by stage. The results are shown in Table 2.
-Texture: The untreated cloth before dyeing and the colored cloth after dyeing were touched by hand, and the texture of the colored cloth was subjected to sensory evaluation. 10 points were given for the excellent texture of the colored fabric close to that of the untreated fabric, and 0 for the others, and this evaluation was performed by 10 people. The numerical values of the total points are shown in Table 2 below. A larger numerical value indicates an excellent texture close to the untreated cloth (100 (points)).
-Wet friction fastness: JIS (Japanese Industrial Standards) L-0849 (revised in 2013) Evaluated based on the Gakushin type friction test (grade 5 method). The results are shown in Table 2.
The evaluation result of wet friction fastness shows that the larger the value, the better the fastness.

  As is clear from the above results, the ink set for ink jet textile printing according to the examples of the present invention has a fabric versatility (giving clear images with various fabrics), a good texture, and a fastness to wet friction. It turns out to give a cloth. In addition, the ink jet textile printing method according to the embodiment of the present invention does not require a pretreatment process, and does not generate waste water and waste materials.

[Synthesis of Dye Polymer (D-3-2)]
The dye polymer (D-3-2) was synthesized according to the following scheme. The unit of the ratio of the following repeating units is% by mass.

  To a 200 mL three-necked flask, 5.0 g of D-3, 0.79 g of 2,2-bis (hydroxymethyl) propionic acid and 45.8 g of N-methylpyrrolidone (NMP) were added, and the internal temperature was raised to 90 ° C. . To this, 81 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei) and 2.46 g of isophorone diisocyanate were added. After completion of the dropwise addition, the mixture was reacted at 90 ° C. for 4 hours. The reaction solution was allowed to cool to 20 ° C., poured into 1 L of a 0.1 mol / L aqueous sodium hydroxide solution, 110 mL of 1 mol / L aqueous hydrochloric acid was added, and the mixture was filtered. The obtained residue was added to 1 L of a 0.1 mol / L aqueous sodium hydroxide solution and stirred for 10 minutes. Then, 1 mol / L aqueous hydrochloric acid was added to adjust the pH to 5.2, followed by filtration. The obtained residue was poured into 500 mL of water, stirred for 10 minutes, and then filtered. The obtained residue was dried with a vacuum dryer at 60 ° C. for 3 hours to obtain a dye polymer (D-3-2). Yield 23.2 g. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum of the dye polymer (D-3-2) in a dilute solution of methanol / chloroform = 1/1 was 555 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement was 13,100 (polymethylmethacrylate conversion), and dispersion degree (Mw / Mn) was 4.3. As GPC, HLC-8220GPC (manufactured by Tosoh Corporation) was used.

(Preparation of aqueous dye polymer dispersion (ULx-1))
0.5 g of the obtained solid state dye polymer (D-3-2) was dissolved in 4.5 g of trifluoroethanol, and adjusted to pH 7.5 with 0.1 mol / L aqueous sodium hydroxide solution, Further, water was added so that the total amount of water was 4.5 g, stirred well, and concentrated to obtain 4.7 g of an aqueous dispersion. Coarse particles were removed with a filter, and water was added so that the final solid content concentration was 10% by mass to obtain a dye polymer aqueous dispersion (ULx-1). The average particle diameter (MV) of the dye polymer in the dye polymer aqueous dispersion (ULx-1) was 86 nm.

[Preparation of inkjet ink (Pm2)]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare an inkjet ink (Pm2). The inkjet ink (Pm2) is magenta ink.

<Composition of inkjet ink (Pm2)>
Dye polymer aqueous dispersion (ULx-1) 6.7 parts by mass Glycerin 0.4 parts by mass Diethylene glycol 0.3 parts by mass Surfynol 465 (manufactured by Nissin Chemical Industry) 0.1 parts by mass Water 2.5 parts by mass

[Synthesis of (M-1-1)]
Referring to US Pat. No. 6,348,592, 2,2-bis (hydroxymethyl) 2,3-dihydroperimidine, which is a raw material of (M-1-1), was synthesized. Further, 4-phenylazo-1-naphthylamine was synthesized with reference to International Publication No. 2016/096085.

  In a three-necked flask, 24.7 g of 4-phenylazo-1-naphthylamine, 510 mL of acetic acid and 110 mL of propionic acid were added and stirred at 20 ° C. to dissolve. The concentrated hydrochloric acid 7.3mL was thrown into there and it cooled so that it might become 0-5 degreeC. While maintaining at 0 to 5 ° C., an 8.5% by mass aqueous solution of sodium nitrite was added dropwise and reacted for 1 hour after the addition to obtain a diazonium salt solution. In a three-necked flask, 23 g of 2,2-bis (hydroxymethyl) 2,3-dihydroperimidine and 150 mL of tetrahydrofuran (THF) were added and stirred at 20 ° C. to dissolve. This was cooled to 5 ° C. or lower, and the diazonium salt solution was added dropwise while maintaining the reaction temperature at 5 ° C. or lower, followed by stirring for 30 minutes to obtain a reaction solution. The reaction solution was filtered and the solid was collected by filtration, washed with pure water until acetic acid ceased, and dried to obtain 40 g of (M-1-1) solid. Analysis of (M-1-1) revealed LC (Liquid Chromatography) -MS (Mass Spectrometry) (Nega) 487.2, (Posi) 489.1. FIG. 1 shows a UV (ultraviolet) absorption spectrum of (M-1-1) in a chloroform / methanol = 1/1 solution. “Abs.” In FIG. 1 represents “absorbance”.

(Preparation of THF solution of Prepolymer 1)
In a three-necked flask, 4.4 g of isophorone diisocyanate, 6.5 g of (M-1-1), 25.5 g of THF, 0.03 g of Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) and put at 65 ° C. Stir for 6 hours. The disappearance of (M-1-1) was confirmed by high performance liquid chromatography. THF was added so that the final solid content concentration was 30% by mass to obtain a THF solution of Prepolymer 1.

(High-performance liquid chromatography measurement conditions)
Apparatus: SHIMADZU Nexera X2 (manufactured by Shimadzu Corporation)
Column: TSKgel ODS-120H (manufactured by Tosoh Corporation)
Eluent: Liquid A) 1 L of water, 1 mL of trifluoroacetic acid B liquid) 1 L of tetrahydrofuran, 1 mL of trifluoroacetic acid
Changed from A solution concentration 60% and B solution concentration 40% to A solution concentration 0% and B solution concentration 100% over 6 minutes, and then kept A solution concentration 0% and B solution concentration 100% for 2 minutes. .

(Preparation of Prepolymer 2 in THF)
In a three-necked flask, 13.1 g of isophorone diisocyanate, 4.0 g of dimethylolbutanoic acid, 6.4 g of polycaprolactone diol (manufactured by Aldrich, average molecular weight 530), 0.5 g of trimethylolpropane, 56.0 g of THF, Neostan U-600 ( Nitto Kasei Kogyo Co., Ltd., trade name) 0.7 g was added and stirred at 75 ° C. for 4 hours. THF was added so that the final solid content concentration was 30% by mass, and a THF solution of prepolymer 2 was obtained.

(Preparation of aqueous dye polymer dispersion (ULx-2))
In a container, 17.6 g of the THF solution of prepolymer 1 obtained above as the first prepolymer, 3.2 g of 30% by weight THF solution of prepolymer 2 as the second prepolymer, 10.4 g of ethyl acetate, triethylamine 0.1 g was added. Furthermore, a mixed liquid of 35.6 g of pure water and 11.7 g of 4 mass% sodium dodecyl sulfate aqueous solution was added, stirred for 12 minutes at 16000 rpm, and emulsified to obtain an emulsion. Thereafter, the obtained emulsion was distilled off under reduced pressure to remove the organic solvent. Thereafter, 1.8 g of a 10% by mass aqueous solution of UCAT SA102 (trade name, manufactured by San Apro Co., Ltd.) was added to the emulsion, and pure water was added so that the solid content concentration was 15% by mass. The reaction was held for a day. Thereafter, coarse particles were removed by filtration to obtain 40 g of a black dye polymer aqueous dispersion (ULx-2). The final solid content concentration of the dye polymer aqueous dispersion (ULx-2) was 15% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-2) was polyurethane / urea, and the average particle size (MV) was 115 nm. Further, the above dye polymer was found to be a polymer having a crosslinked structure because insoluble matter remained in any of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and tetrahydrofuran (THF). It was.

[Preparation of inkjet ink (Pb2)]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare an inkjet ink (Pb2). The inkjet ink (Pb2) is a black ink.

<Composition of inkjet ink (Pb2)>
Dye polymer aqueous dispersion (ULx-2) 6.7 parts by mass Glycerin 0.4 parts by mass Diethylene glycol 0.3 parts by mass Surfynol 465 (manufactured by Nissin Chemical Industry) 0.1 parts by mass Water 2.5 parts by mass

[Create ink set for inkjet textile printing]
Ink sets for ink jet textile printing 4 to 11 were prepared using the ink jet ink combinations shown in Table 3 below.

(Examples 5 to 12)
Ink-jet printing was performed in the same manner as in Example 1 except that ink-jet printing ink sets 4 to 11 were used in place of the ink-jet printing ink set 1 to obtain a colored fabric.
The image sharpness was evaluated by the method described above, and the results are shown in Table 4 below.

(Examples 13 to 20)
Except that the above-mentioned pretreated fabric was used as the fabric, inkjet printing was performed in the same manner as in Examples 5 to 12 to obtain a colored fabric.
Image sharpness was evaluated by the method described above.
In addition, dry cleaning resistance was evaluated by the following method.
The results are shown in Table 5 below.

<Dry cleaning resistance>
Evaluation was performed based on the JIS L-1096 A method in accordance with “JIS Handbook 31 Fiber” edited by Japanese Standards Association, published in 2015. Larger values indicate better dry cleaning resistance.

  In addition, for all the dye polymers used in the examples, using a melting point measuring machine, the temperature was raised to 200 ° C. at 10 ° C./min, and it was confirmed whether or not it was melted at 200 ° C. The dye polymer melted at 200 ° C.

Claims (14)

  An ink set comprising an inkjet ink comprising an aqueous dispersion of a polymer having a structure derived from a dye, and an inkjet ink comprising an aqueous dispersion of a pigment.   The ink set according to claim 1, which is for inkjet printing. The pigment is
Carbon black,
Aniline black,
C. I. Pigment Yellow 3, 12, 53, 55, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 155, 180, 185,
C. I. Pigment Red 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 209, 219,
C. I. Pigment violet 19, 23,
C. I. Pigment orange 36, 43, 64,
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 56, 60, 63,
C. I. Pigment Green 36
The ink set according to claim 1, wherein the ink set is at least one selected from the group consisting of:   The structure derived from the dye is a structure derived from any dye selected from an azo compound, stilbene, triarylmethane, xanthene, indoaniline, indophenol, nigrosine, anthraquinone, quinophthalone, dicyanostyryl compound, and phthalocyanine. The ink set according to any one of claims 1 to 3, further comprising:   The ink set according to any one of claims 1 to 4, wherein the polymer having a structure derived from the dye is polyurethane.   The ink set according to claim 1, wherein the polymer having a structure derived from the dye is a polymer having a crosslinked structure.   The ink set according to any one of claims 1 to 6, wherein the polymer having a structure derived from the dye melts at 200 ° C. An inkjet ink containing an aqueous dispersion of a polymer having a structure derived from the dye is at least one of a magenta ink, a yellow ink, a cyan ink, and a black ink,
The ink set according to any one of claims 1 to 7, wherein the inkjet ink containing the pigment aqueous dispersion is at least one of a yellow ink, a cyan ink, and a black ink.   An ink-jet printing method comprising a step of directly printing on a fabric by an ink-jet method using the ink set according to any one of claims 1 to 8.   An aqueous pretreatment liquid containing an aggregating agent is applied to a fabric to obtain a pretreated fabric, and the ink set according to any one of claims 1 to 8 is used in an ink jet method. An inkjet printing method comprising a step of printing on a pretreated fabric.   The inkjet printing method according to claim 9 or 10, further comprising a heat treatment step.   The inkjet printing method according to claim 11, wherein in the heat treatment step, a polymer having a structure derived from the dye is melted.   An ink cartridge comprising the ink set according to claim 1. An ink jet printer having the ink set according to claim 1.

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