JP2018177876A - Ink set, inkjet textile printing method, ink cartridge, and inkjet printer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an ink set that can form an image with excellent clarity on various types of textile and can provide colored textile with excellent texture; an inkjet textile printing method using the ink set; an ink cartridge having the ink set; and an inkjet printer.SOLUTION: The invention provides: an ink set which 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 water-insoluble dye; an inkjet textile printing method using 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 printing method, an ink cartridge, and an ink jet printer.

  Ink-jet textile printing does not have to make a plate, can quickly form an image with excellent gradation, and uses only the amount of ink necessary for forming an image, so it has environmental advantages such as little waste liquid. It can be said that it is an excellent textile printing method.

  For example, Patent Document 1 describes an ink jet printing method using an ink containing an aqueous dispersion containing a water-insoluble dye.

  Further, Patent Documents 2 and 3 describe an inkjet ink containing a polymer in which a dye is linked.

JP, 2015-91907, A Japanese Patent Application Publication No. 2004-534106 Japanese Patent Application Publication No. 2002-509957

However, inkjet printing using an ink containing a non-water-soluble dye described in Patent Document 1 mainly corresponds to the coloring of a polyester fabric, and since a resin is used, the texture of a colored cloth (colored cloth) There is also room for improvement.
Further, Patent Documents 2 and 3 have no specific disclosure on textile printing, and none of the above problems has been described.

  An object of the present invention is an ink set capable of forming an image excellent in sharpness on various types of fabrics and providing a colored cloth excellent in texture, an ink jet printing method using the above ink set, An ink cartridge having the above ink set, and an inkjet printer are provided.

  The object of the present invention is achieved by the following means. Although the ink set of the present invention does not reveal the details of the reason why the above problems are solved, polymers having a structure derived from dyes are capable of coloring various types of fabrics, and water-insoluble dyes are It is believed that the diffusion to the polymer having a structure derived from the dye is effectively working.

<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 water-insoluble dye.
<2>
The ink set as described in <1> which is for inkjet textile printing.
<3>
The above water-insoluble dyes are
C. I. Disperse yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86,
C. I. Solvent Yellow 2, 14, 16, 21, 33, 34, 43, 45, 62, 85, 93, 98, 114, 131, 157, 160, 163, 167, 176, 179, 185, 189,
C. I. Disperse Red 11, 50, 53, 55, 55: 51, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240,
C. I. Solvent Red 8, 23, 24, 25, 49, 52, 109, 111, 119, 122, 135, 146, 149, 150, 168, 169, 172, 179, 195, 197, 207, 222, 227, 312, 313,
C. I. Disperse Blue 3, 5, 19, 26, 26: 1, 35, 55, 56, 64, 64: 1, 72, 72: 1, 79, 81, 81: 1, 91, 95, 108, 131, 141, 145, 359, 360,
C. I. Solvent Blue 3, 4, 5, 35, 36, 38, 45, 59, 63, 67, 68, 70, 78, 83, 97, 101, 102, 104, 105, 111, 122,
C. I. Disperse Orange 1, 1: 1, 5, 7, 20, 23, 25, 25: 1, 33, 56, 76,
C. I. Solvent Orange 3, 14, 54, 60, 62, 63, 67, 86, 107,
C. I. Disperse Violet 8, 11, 17, 23, 26, 27, 28, 29, 36, 57,
C. I. Solvent Violet 8, 9, 11, 13, 14, 26, 28, 31, 36, 59,
C. I. Solvent Green 3,5,7,28,
C. I. Disperse Brown 2,4,
C. I. Solvent Brown 53,
C. I. Solvent Black 3, 5, 7, 27, 29, 34
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 above 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 of any one of <1>-<3> containing.
<5>
An inkjet ink containing an aqueous dispersion of a polymer having a structure derived from the above dye is at least one of a magenta ink, a yellow ink, a cyan ink, and a black ink.
The inkjet ink containing the water dispersion of the said water-insoluble dye is any one of <1>-<4> which is any one of a magenta ink, a yellow ink, a cyan ink, and a black ink. Ink set.
<6>
The inkjet textile printing method which has the process of printing on a fabric directly by inkjet method using the ink set of any one of <1>-<5>.
<7>
Applying an aqueous pretreatment liquid containing an aggregating agent to the fabric to obtain a pretreated fabric, and using the ink set according to any one of <1> to <5>, an inkjet method An ink jet printing method comprising the step of printing on the pretreated fabric.
<8>
Furthermore, the inkjet textile-printing method as described in <6> or <7> including the heat treatment process.
<9>
The ink cartridge which has an ink set of any one of <1>-<5>.
<10>
The inkjet printer which has an ink set of any one of <1>-<5>.

  According to the present invention, an ink set capable of forming an image excellent in sharpness on various types of fabrics and providing a colored cloth excellent in texture, an ink jet printing method using the above ink set, An ink cartridge having the above ink set and an ink jet printer can be provided.

[Ink jet ink containing water 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) contains 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 It is a group to be removed (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 dye multimer including a structure derived from a dye, and may be a linear polymer or a reticulated polymer. When it is a linear polymer, the structure derived from the dye may be in the main chain of the polymer or in the side chain.
The dye polymer is preferably a polymer having a repeating unit containing a structure derived from a dye.
A method for obtaining a dye polymer is optional, but a method of polymerizing or copolymerizing a monomer containing a structure derived from a dye to obtain a dye polymer, or a polymer having no structure derived from a dye in advance And preparing a structure derived from the dye by 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.

The structure derived from the dye may be any structure derived from the dye as classified by the color index (abbreviated as "CI"), or any substituent within the range that exerts the effect of the present invention on the structure. It is preferable that it is the structure which substituted, or the structure which remove | eliminated the arbitrary substituent in the range from which the effect of this invention is show | played from the structure.
Examples of structures derived from dyes include azo compounds (monoazo compounds, disazo compounds, trisazo compounds, polyazo compounds), stilbenes, carotenoids, diarylmethanes, triarylmethanes, xanthenes, acridines, quinolines, quinolines, methines (monomethines, polymethines), Those containing a structure derived from any dye selected from azomethine, aniline, indoaniline, indamine, indophenol, azine, oxazine, thiazine, anthraquinone, indigo, quinophthalone, diglosin, porphyrin, cyanine, and phthalocyanine Be
The structure derived from the dye is azo compound, stilbene, diarylmethane, triarylmethane, xanthene, acridine, quinoline, polymethine, monomethine, azomethine, indoaniline, indophenol, nigrosine, 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, azo compounds, stilbene, triarylmethane, xanthene, indoaniline, indophenol, nigrosine It is more preferable to include a structure derived from any dye selected from anthraquinone, quinophthalone, dicyanostyryl compound, and phthalocyanine.

  The dye may be a dye that is soluble in water or a dye that is insoluble in water, but is a dye that is insoluble in water from the viewpoint of the water resistance and the wash 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, but, for example, a dye insoluble in water such as a disperse dye may be used, or a dye in which an ionic group is removed from a water-soluble dye may be used.

As the dye polymer, a polymer containing a structure derived from the dye in the main chain or side chain is preferably used. The polymer constituting the main chain of the polymer containing the structure derived from the dye in the main chain or side chain is not particularly limited, but acrylic polymer, urethane polymer or styrene polymer is preferably used, and in particular, acrylic polymer and urethane polymer preferable.
The acrylic polymer in the present invention is a polymer having at least one repeating unit from the group consisting of repeating units derived from (meth) acrylic acid and repeating units derived from (meth) acrylic acid ester. In the present 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. The urethane polymer in the present invention is a polymer having a urethane bond in its main chain, and is formed by the reaction of a polyol compound and a polyisocyanate compound. Sometimes called polyurethane. Further, the styrene polymer in the present invention refers to a polymer having a repeating unit derived from styrene.

(Molecular weight of dye polymer)
3,000-2,000,000 are preferable, as for the weight average molecular weight (Mw) of a dye polymer, 3,000-1,000,000 are more preferable, and 3,000-200,000 are especially preferable. 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 the dye as an essential structure, but from the viewpoint of dispersibility in water, a hydrophobic group (an electrically neutral nonpolar group having low affinity with water It is more preferable to introduce a repeating unit containing at least one of a group) and an ionic group (an electrically ionic polar group having a high affinity to water). The molecular structure of the dye polymer may be linear or branched, may be random, alternating, periodic or block, or may be a graft polymer in which the structure of stem and branch is designed.

(Water dispersion of dye polymer)
The water dispersion of the dye polymer (dye polymer water dispersion) contains at least water and the dye polymer, and preferably contains an aqueous organic solvent. Further, depending on the method of producing the aqueous dispersion of the dye polymer, the low molecular weight surfactant or the high molecular weight dispersing agent may be used in combination or may not be used in combination (so-called self-dispersion).
Only one type of dye polymer can be used, or two or more types can be mixed and used in any ratio.

In the present invention, the above-mentioned dye polymer is used not in a state of being dissolved in water but in a state of being dispersed in water (water dispersion).
In a state where the dye polymer is dispersed in water, it is a polymer substantially insoluble in water, unlike a state in which it is dissolved in water, so that it is excellent in water resistance such as washing resistance and sweat resistance. In the ink jet printing method of the present invention, the dye polymer is a substantially water-insoluble polymer because the step of washing with water after printing is unnecessary. In the water dispersion of the dye polymer, the dye polymer insoluble in water is dispersed as particles, and the average particle size is preferably 50 to 500 nm. When the dye polymer is soluble in water, the dye polymer is not present as particles in water. In order for the dye polymer to be a water dispersion, it is preferable that the dye polymer does not have a sulfo group.
It is preferable to use ultrapure water as water.

  The dye polymer, when dispersed in water, is easy to be compatible with water (wettable) or electrostatic repulsion (repulsive force) as a property of the dye polymer itself or by adsorption with a low molecular type surfactant or a polymer type dispersant used in combination. Or steric repulsion to prevent reaggregation of the fine particles of the dye polymer, and has the function of suppressing sedimentation.

The dye polymer is in the form of particles in the aqueous dispersion. The average particle diameter of the particulate dye polymer in the water 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 inkjet method.
The average particle diameter in this specification used the value measured using the particle size distribution measuring apparatus (Nanotrac UPA EX150, the Nikkiso Co., Ltd. make, brand name).

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. If it is in this range, it is possible to obtain a colored cloth with high density in printing while securing the storage stability as an inkjet ink.
The content of water in the dye-polymer water dispersion is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and particularly preferably 60 to 90% by mass. Within this range, the stability of the aqueous dispersion and the ejection stability as an inkjet ink can be imparted, which is preferable. The stability of the aqueous dispersion indicates that sedimentation and the like are less likely to occur.

(Aqueous organic solvent)
The aqueous organic solvent is preferably one having 10 g / 100 g H ₂ O or more as water solubility at 25 ° C., more preferably 20 g / 100 g H ₂ O or more, and 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 water 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, which is preferable.

(Low-molecular-weight surfactant or polymeric dispersant)
The low molecular weight surfactant or the high molecular weight dispersant is preferably a low molecular weight surfactant or a high molecular weight dispersant having a hydrophobic group and an ionic group, and is added when the dye polymer is dispersed. Low-molecular-weight surfactant or high-molecular-weight dispersant adsorbs to the surface of the dye polymer and makes it wet (is wet) with water, and electrostatic repulsion (repulsion) or steric repulsion of dye polymer fine particles milled by mechanical action It prevents the reaggregation of fine particles and has the function of suppressing the formation of sedimentation.

  The content of the low molecular weight 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 water dispersion, and the surface tension of the water dispersion in such a range It is preferable to adjust the

  The content of the polymer-type 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 water dispersion, and the surface tension of the water dispersion is arbitrary in such a range It is preferable to adjust to

The method of producing the aqueous dispersion of dye polymer is
(I) Glass beads, zirconia beads, titania beads after mixing powder or paste of dye polymer and, if necessary, low molecular weight surfactant or high molecular weight dispersant in water or an aqueous organic solvent Or a method of finely dispersing with an attritor or mill together with stainless steel balls etc.
(Ii) After synthesizing the dye polymer in an organic solvent, there is a method of adding water, optionally a surfactant or a solvent, removing the solvent other than water to obtain an aqueous dispersion of the dye polymer, etc. Can be suitably used.

(Other ingredients)
The inkjet ink (P) may contain other components other than those described above. As other components, for example, coloring agents other than the above dye polymers, crosslinking agents, organic solvents, surfactants, pH adjusters, optical brighteners, surface tension adjusters, antifoaming agents, anti-drying agents, lubricants Thickener, UV absorber, antifading agent, antistatic agent, matting agent, antioxidant, specific resistance regulator, rust inhibitor, inorganic pigment, reduction inhibitor, preservative, fungicide, and chelating agent Etc.

(Crosslinking agent)
The inkjet ink (P) may contain a crosslinking agent in order to improve the abrasion resistance or the washing fastness of the colored cloth. As a crosslinking agent, blocked isocyanate crosslinking agents (for example, Maycanate CX, TP-10, DM-35 HC, SU-268A, etc., all manufactured by Meisei Kogyo Co., Ltd., trade names), polyfunctional epoxy crosslinking agents (for example, And Denacol EX-313, 314, 322, 411, etc., all of which are manufactured by Nagase ChemteX Co., Ltd. (trade names).

The inkjet ink (P) contains at least an aqueous dispersion of the dye polymer, that is, the inkjet ink (P) is a dispersion in which the dye polymer is dispersed in a liquid containing water. In the inkjet ink (P), the dye polymer is in the form of particles, and the preferable average particle diameter of the dye polymer in the form of particles 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 still more preferably 3 to 12% by mass. .
The content of water 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.
Although the preparation method of inkjet ink (P) is not specifically limited, For example, it can prepare by mixing the water dispersion of dye polymer, and water or other components as needed.

[Ink jet ink containing water dispersion of water-insoluble dye]
An inkjet ink containing a water dispersion of a water-insoluble dye is also referred to as "inkjet ink (Q)". The inkjet ink (Q) will be described.

(Water dispersion of water-insoluble dyes)
The inkjet ink (Q) contains a water dispersion of a water-insoluble dye.
A water-insoluble dye is a dye that is insoluble in water (water-insoluble). Here, water insoluble means that the solubility in water at 25 ° C. is 1 g / l or less, preferably 500 mg / l or less, more preferably 100 mg / l or less.
The water-insoluble dye is preferably a disperse dye or an oil-soluble dye.

  The water dispersion of the water-insoluble dye (also referred to as "water-insoluble dye water dispersion") will be described.

The water-insoluble dye of the water-insoluble dye water dispersion in the present invention is
C. I. Disperse yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86,
C. I. Solvent Yellow 2, 14, 16, 21, 33, 34, 43, 45, 62, 85, 93, 98, 114, 131, 157, 160, 163, 167, 176, 179, 185, 189,
C. I. Disperse Red 11, 50, 53, 55, 55: 51, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240,
C. I. Solvent Red 8, 23, 24, 25, 49, 52, 109, 111, 119, 122, 135, 146, 149, 150, 168, 169, 172, 179, 195, 197, 207, 222, 227, 312, 313,
C. I. Disperse Blue 3, 5, 19, 26, 26: 1, 35, 55, 56, 64, 64: 1, 72, 72: 1, 79, 81, 81: 1, 91, 95, 108, 131, 141, 145, 359, 360,
C. I. Solvent Blue 3, 4, 5, 35, 36, 38, 45, 59, 63, 67, 68, 70, 78, 83, 97, 101, 102, 104, 105, 111, 122,
C. I. Disperse Orange 1, 1: 1, 5, 7, 20, 23, 25, 25: 1, 33, 56, 76,
C. I. Solvent Orange 3, 14, 54, 60, 62, 63, 67, 86, 107,
C. I. Disperse Violet 8, 11, 17, 23, 26, 27, 28, 29, 36, 57,
C. I. Solvent Violet 8, 9, 11, 13, 14, 26, 28, 31, 36, 59,
C. I. Solvent Green 3,5,7,28,
C. I. Disperse Brown 2,4,
C. I. Solvent Brown 53,
C. I. Solvent Black 3, 5, 7, 27, 29, 34
It is preferable that it is at least one selected from

In the water-insoluble dye water dispersion in the present invention, the water-insoluble dye is present dispersed in water.
The non-water-soluble dye becomes compatible with water (wettable) preferably by adsorption with a dispersing agent at the time of dispersion, and prevents reaggregation of the non-water-soluble dye particles by electrostatic repulsion (repulsion) or steric repulsion. , Has the function of suppressing sedimentation.
A known method can be used as a method of dispersing the water-insoluble dye.

The dispersed water-insoluble dye is preferably in the form of particles. The dispersed non-water-soluble dye is preferably in the form of particles having an average particle diameter of 200 nm or less, more preferably in the form of particles of 20 to 200 nm, and still more preferably in the form of particles of 40 to 150 nm. It becomes easy to print on a fabric by the inkjet method as the average particle diameter of the water-insoluble dye currently disperse | distributed is 200 nm or less.
The average particle diameter of the water-insoluble dye was a value measured using a particle size distribution measuring apparatus (Nanotrac UPA EX150, manufactured by Nikkiso Co., Ltd., trade name).

1.0-30 mass% is preferable, and, as for content of the non-water-soluble pigment in the water-insoluble dye water dispersion in this invention, 3.0-15 mass% is more preferable. If the content of the water-insoluble dye is 1.0% by mass or more, the printing density is preferably high, and if it is 30% by mass or less, structural viscosity does not easily occur in the viscosity increase or the viscosity characteristics of the ink. It is preferable because it has excellent ink ejection stability.
The water-insoluble dyes may be used alone or in combination of two or more in any proportion.
It is preferable that it is 40-90 mass%, and, as for content of the water in the water-insoluble dye water dispersion in this invention, it is more preferable that it is 50-80 mass%.

(Dispersant)
The water-insoluble dye water dispersion preferably contains a dispersant.
By using the dispersant, the dispersion stability of the water-insoluble dye is excellent, and the storage stability of the ink jet ink (Q), the ejection stability over a long period, and the like can be enhanced.
The dispersant is not particularly limited, and may be a low molecular weight dispersant or a high molecular weight dispersant.
The low molecular weight dispersant is not particularly limited, and examples thereof include anionic dispersants and nonionic dispersants.
The anionic dispersant is not particularly limited. For example, formalin condensates of aromatic sulfonic acids, formalin condensates of β-naphthalenesulfonic acids, formalin condensates of alkyl naphthalene sulfonic acids, and creosote oil sulfonic acids There may be mentioned formalin condensates.
The aromatic sulfonic acid is not particularly limited, and examples thereof include alkyl naphthalene sulfonic acids such as creosote oil sulfonic acid, cresol sulfonic acid, phenol sulfonic acid, β-naphthol sulfonic acid, methyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid, etc. A mixture of β-naphthalenesulfonic acid and β-naphtholsulfonic acid, a mixture of cresol sulfonic acid and 2-naphthol-6-sulfonic acid, lignin sulfonic acid and the like can be mentioned.
The nonionic dispersant is not particularly limited, and examples thereof include ethylene oxide adducts of phytosterols, ethylene oxide adducts of cholestanol, and the like.
The polymer type dispersant is not particularly limited, and examples thereof include polyacrylic acid partial alkyl esters, polyalkylene polyamines, polyacrylates, styrene-acrylic acid copolymers, and vinyl naphthalene-maleic acid copolymers. Be
When the water-insoluble dye water dispersion contains a dispersant, the content of the dispersant in the water-insoluble dye water dispersion is preferably 0.1 to 10% by mass, and 0.2 to 5% by mass More preferable.

  Further, as the water-insoluble dye water dispersion, an aqueous dispersion containing a water-insoluble colorant (in particular, a disperse dye or an oil-soluble dye) described in JP-A-2015-91907 can also be used.

  The preparation method of the water-insoluble dye water dispersion is not particularly limited. For example, a non-water-soluble dye and water, and if necessary, a dispersing agent are mixed and finely dispersed in an attritor or mill together with glass beads, zirconia beads, titania beads, or stainless steel balls, glass beads, zirconia beads, There is a method of removing titania beads or stainless steel balls to obtain a water-insoluble dye water dispersion.

(resin)
The inkjet ink (Q) can contain a resin in a dispersed state in the ink.
In addition, the said resin is a component different from the polymeric type dispersing agent which can be used as a dispersing agent.
When the inkjet ink (Q) contains a resin and a polymer-type dispersant, the resin is dispersed alone in the inkjet ink (Q), but the polymer-type dispersant is present in the inkjet ink (Q) It is present dispersed in a mixture with a water-insoluble dye.

  When the inkjet ink (Q) contains a resin, the resin forms a film on the fabric, and the water-insoluble dye can diffuse into the film to form a colored image. In this case, the fabric and the resin are used. A crosslinking agent can be used to further strengthen the adhesion of the toner and improve the fastness of the image. Therefore, it is preferable that the resin has a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group or the like as a group capable of reacting with the crosslinkable group of the crosslinking agent.

The resin is preferably a urethane resin, a polyester resin, or a vinyl chloride resin, and may be used alone or in combination.
The resin may be synthesized by a known method or a commercially available product may be used.
The Tg (glass transition temperature) of the resin is preferably 150 ° C. or less, more preferably 120 ° C. or less, and still more preferably less than 100 ° C., for the purpose of maintaining good texture of the dyed product. The molecular weight of the resin is preferably 150,000 or less, more preferably 100,000 or less, and still more preferably 70,000 or less. If the molecular weight is 150,000 or less, discharge stability can be secured in the long run.

In the inkjet ink (Q), it is preferable that the resin is present in a dispersed manner.
At the time of dispersion, the resin is easy to conform to water (wettable) as a property of the resin itself or by using a dispersing agent in combination, and prevents reaggregation of the fine particles of the resin by electrostatic repulsion (repulsive force) or steric repulsion. , Has the function of suppressing sedimentation.
A known method can be used as a method of dispersing the resin.

The dispersed resin is preferably in the form of particles. The dispersed resin is preferably in the form of particles having an average particle diameter of 200 nm or less, more preferably in the form of particles of 20 to 200 nm, and still more preferably in the form of particles of 40 to 150 nm. It becomes easy to print on a fabric by the inkjet method as the average particle diameter of the resin currently disperse | distributed is 200 nm or less.
The average particle size of the resin can be measured using a particle size distribution measuring apparatus (Nanotrac UPA EX150, manufactured by Nikkiso Co., Ltd., trade name).

  When the ink-jet ink (Q) contains a resin, the content of the resin in the ink-jet ink (Q) causes the non-water-soluble dye to be uniformly diffused and dissolved in the resin, and does not impair the texture of the dyed material. 1-20 mass% is preferable, 2-15 mass% is more preferable, 3-10 mass% is further more preferable.

  In the inkjet ink (Q), the ratio of the content of the resin to the content of the non-water-soluble dye (the content of the resin, because the non-water-soluble dye is uniformly diffused and dissolved in the resin to realize high colorability. Amount / content of water-insoluble dye) is preferably 1/1 to 5/1, more preferably 1/1 to 4/1, and 1/1 to 3/1 based on mass Is more preferred.

(Other ingredients)
The inkjet ink (Q) may contain polymer particles. As the polymer particles, polymer particles described in JP-A-2012-7148 can be used. As the polymer fine particles, a crosslinkable polyurethane and / or a crosslinkable polyurethane-polyurea is preferably used.
The inkjet ink (Q) may contain a 1,2-alkylene glycol, a glycol ether, or an aqueous organic solvent. Preferred forms of 1,2-alkylene glycol and glycol ether are the forms described in JP-A-2012-7148. As the aqueous organic solvent, water-soluble organic solvents described in JP 2012-7148 A can be preferably used in addition to those described above.
The inkjet ink (Q) may contain other components other than those described above. As other components, for example, colorants other than the above-mentioned water-insoluble dyes, crosslinking agents, organic solvents, surfactants, permeation inhibitors, pH adjusters, optical brighteners, surface tension adjusters, antifoaming agents, Anti-drying agents, lubricants, thickeners, UV absorbers, anti-fading agents, anti-static agents, matting agents, anti-oxidants, specific resistance modifiers, anti-rust agents, inorganic pigments, anti-reductive agents, preservatives, anti-corrosion agents There may be mentioned lozenges, chelating agents and the like.
As a crosslinking agent which inkjet ink (Q) may contain, it is the same as that of what was described as a crosslinking agent which the above-mentioned inkjet ink (P) may contain.

The inkjet ink (Q) contains at least an aqueous dispersion of a water-insoluble dye, that is, the inkjet ink (Q) is a dispersion in which the water-insoluble dye is dispersed in a liquid containing water.
The content of the water-insoluble dye in the inkjet ink (Q) is preferably 1.0 to 30% by mass, and more preferably 3.0 to 15% by mass.
The content of water in the ink jet 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 water-insoluble dye, and water or other components as needed.

[Ink set]
The ink set of the present invention comprises an inkjet ink (P) and an 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 contain at least one inkjet ink (P) and at least one inkjet ink (Q).
The ink set of the present invention preferably contains at least two colored inks, and preferably contains at least two colored inks selected from, for example, 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 thereto.
(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 magenta ink, yellow ink, cyan ink, and black ink Or at least one of them.

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

[Ink jet 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 modes as preferable embodiments.
1st aspect: The inkjet textile printing method which has the process of printing on fabric directly by 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 pretreatment fabric, and using the ink set of the present invention to mark a fabric pretreated by an inkjet method An ink jet printing method comprising the step of chewing.
In the present invention, “directly printing on the fabric” by the inkjet method does not require a transfer step, the inkjet ink is directly printed on the fabric, and the pretreatment step is unnecessary, and the inkjet ink is It refers to both being directly printed on the fabric.
The ink jet textile printing method of the present invention does not produce waste materials such as waste water and transfer paper, and has an effect of being excellent in the quality (texture) of the colored cloth, the image sharpness and the wet rub fastness with simple workability.

(Pretreatment process)
The pretreatment step in the second aspect is a step of applying an aqueous pretreatment liquid containing a coagulant to the fabric to obtain a pretreated 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 inkjet method, a spray method, a screen printing method, and the like.
The aggregating agent contained in the aqueous pretreatment solution is not particularly limited as long as it has an effect of aggregating the dye polymer, and is at least one selected from organic acids, polyvalent metal salts, and cationic compounds. Is preferred.

  In the ink jet printing method of the present invention, the dye polymer is further fused to the fibers of the fabric by adding the heating step, whereby the fibers are more integrated with the fibers and the texture is not impaired, and the abrasion resistance and the like are further reduced. It has the advantage of being able to be granted.

(Heat treatment process)
The ink jet printing method of the present invention preferably further includes a heat treatment step. In particular, after printing on the fabric, the dye polymer particles can be melted (or softened) by the heat treatment step to improve the adhesion with the fibers (that is, melt dyeing by heat treatment) Can) After drying, the colored cloth is preferably subjected to a heat treatment for the purpose of causing the above-mentioned melt dyeing to be performed, and usually it is preferably carried out at 100 to 250 ° C, more preferably 100 to 200 ° C, particularly preferably 120 to It is 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 together as an additive, The crosslinking reaction is carried out using a reactive group (for example, a blocked isocyanate group) introduced into the polymer, or a crosslinking agent (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent) used in combination as an additive preferable.

(Post-processing)
The cloth (colored cloth) colored by the inkjet textile printing method of the present invention is excellent in the softness and fastness (abrasion resistance) of the texture, but if necessary, the colored cloth may be subjected to a padding treatment over the entire surface. Thus, it is possible to obtain a colored cloth with further improved texture softness and fastness (especially abrasion resistance).

(Fabric)
Examples of the fabric 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 hair, and mixed fibers thereof, woven fabrics, knitted fabrics, non-woven fabrics, etc. Can be mentioned.
A pretreated fabric can also be used as the fabric. The pretreatment liquid can be applied by a coating method, a padding method, an inkjet method, a spray method, a screen printing method or the like. The pretreatment liquid contains an aggregating agent for aggregating the dye polymer, and is preferably an aqueous solution. Examples of the aggregating agent include organic acids, polyvalent metal salts, and cationic compounds.
Clothing items include T-shirts, trainers, jerseys, pants, sweat suits, 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)]
Dye polymer (R-2-1) was synthesized by the following scheme. The unit of the ratio of the following repeating unit is mass%. Me represents a methyl group, Et represents an ethyl group.

  10 mL of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) was added to a 100 mL three-necked flask, and the internal temperature was raised to 85 ° C. In the above PGMEA, 9.0 g of RDW R-13 (trade name, made by Wako Pure Chemical Industries, Ltd.) which is a polymerizable monomer, 1.0 g of 2-ethylhexyl methacrylate (EHMA) which is a polymerizable monomer, V-601 (Wako Pure Chemical Industries, Ltd.) A solution prepared by dissolving 0.057 g of P. C., and 0.20 g of 1-dodecanethiol in 13.24 g of PGMEA was dropped over 3 hours. After completion of the dropwise addition, reaction was carried out at 85 ° C. for 1 hour to obtain a reaction solution A. Thereafter, V-601 (0.057 g) was added to the reaction solution A, and reaction was further performed at 85 ° C. for 2 hours to obtain a reaction solution B. The reaction solution B is allowed to cool to room temperature (20 ° C.), poured into 300 mL of water / 200 mL of methanol to precipitate crystals, and the crystals are filtered off by filtration, and then the filtered crystals are separated by a blower dryer at 60 ° C. 1 After drying for a day, a red powder of dye polymer (R-2-1) was obtained. The yield of the dye polymer (R-2-1) was 8.0 g. The absorption maximum wavelength of UV-visible absorption spectrum of the dye polymer (R-2-1) in a dilute solution of tetrahydrofuran (THF) was 562 nm. Moreover, the weight average molecular weight (Mw) in gel permeation chromatography (GPC) measurement was 8,900 (in terms of polystyrene), and the degree of dispersion (Mw / Mn) was 1.7. Mn represents a number average molecular weight. GPC used HLC-8220GPC (made by Tosoh Co., Ltd.).

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

(Synthesis of Intermediate (BM-1))
C. I. 67.65 g of Acid Blue 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) 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 is added dropwise, then 6 mL of DMF (N, N-dimethylformamide) is added dropwise, and then allowed to react at room temperature for 24 hours. The reaction was allowed to proceed for 2 hours at ° C. The reaction liquid C was concentrated 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. 58.2 mL of triethylamines was dripped here slowly, then it was made to react at room temperature 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 crystals obtained were washed with heating under heating and stirring to obtain a powder of an intermediate (BM-1) (yield 65.6 g).
In a 100 mL three-necked flask, 3.0 g of intermediate (BM-1), 2.0 g of 2-ethylhexyl methacrylate, 0.237 g of 1-dodecanethiol, 27.8 g of N-methylpyrrolidone (NMP) are added, and the internal temperature is 85 ° C. The temperature rose to 0.3 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd., trade name) was added four times every two hours. After completion of the reaction, the reaction solution is allowed to cool to room temperature, poured into 500 mL of water to precipitate crystals, and the crystals are filtered off by filtration and then dried with a blower dryer at 60 ° C. for 1 day to obtain dye polymer (B- A pale yellow powder of 4-3) was obtained. The yield of the dye polymer (B-4-3) was 4.2 g. The absorption maximum wavelength of UV-visible absorption spectrum of the dye polymer (B-4-3) in a dilute solution of tetrahydrofuran (THF) was 610 nm. Moreover, the weight average molecular weight (Mw) in GPC measurement of dye polymer (B-4-3) was 9,100 (polystyrene conversion), and dispersion degree (Mw / Mn) was 2.3. GPC used HLC-8220GPC (made by Tosoh Co., Ltd.).

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

(Synthesis of Dye Polymer (B-5))
The polyurethane compound (B-5) which is a dye polymer was synthesized according to Example 11 of JP-A-2002-509957.

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

[Preparation of Dye-Polymer Water Dispersion (2)]
Dye polymer water dispersion (2) in the same manner as in the preparation of dye polymer water dispersion (1) except that dye polymer (B-4-3) is used instead of dye polymer (R-2-1) It was created. The average particle size of the particulate dye polymer in the dye polymer water dispersion (2) was 81 nm.

[Preparation of Dye-Polymer Water 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 particle grinder (Pulverlsette 7 made by Fritsch) It was dispersed for 5 hours at a revolution of 400 rpm (revolution per minute). From the obtained dispersion, the zirconia beads were removed using a filter cloth to obtain a dye polymer aqueous dispersion (3). The average particle size of the particulate dye polymer in the dye polymer water dispersion (3) was 130 nm.

[Preparation of Dye-Polymer Water Dispersion (4)]
A dye polymer water dispersion (4) was prepared in the same manner as the preparation of the dye polymer water dispersion (3) except that the dye polymer (B-5) was used in place of the dye polymer (Br-1). The average particle size of the particulate dye polymer in the dye polymer water dispersion (4) was 150 nm.

[Preparation 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 diameter: 0.8 μm) to prepare an inkjet ink (Pm). The inkjet ink (Pm) is a magenta ink.
Dye polymer water dispersion (1) 3.0 g
Trimethylolpropane 0.056 g
Ultra pure water 0.913 g
1,2-hexanediol 0.112 g
Glycerin 0.560 g
Triethylene glycol monobutyl ether 0.112 g
2-pyrrolidone 0.168 g
Propylene glycol 0.028 g
Surfynol 465 (Nisshin Chemical Industries, trade name) 0.056 g

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

[Preparation of inkjet ink (Pb)]
Example of inkjet ink (Pm) except that 1.5 g of dye polymer water dispersion (3) and 1.5 g of dye polymer water dispersion (4) were used instead of 3.0 g of dye polymer water dispersion (1) An inkjet ink (Pb) was prepared in the same manner as the preparation. The inkjet ink (Pb) is a black ink.

[Preparation of inkjet ink (Qm)]
(Preparation of water-insoluble dye water dispersion 1)
Water-insoluble dyes C.I. I. Disperse Red 60 (10 parts by mass), Demol NL (manufactured by Kao Corporation) (6 parts by mass), water (84 parts by mass), and zirconia beads having a diameter of 0.1 mm, and mixing them with a planetary fine particle crusher (Fritsch The dispersion was obtained by dispersing for 10 hours at a rotational speed of 400 rpm (revolution per minute), using Pulverlsette 7). The zirconia beads were removed from the obtained dispersion using a filter cloth to obtain a water-insoluble dye water dispersion 1. The average particle size of the water-insoluble dye in the water-insoluble dye water dispersion 1 was 90 nm.
Demol NL is a dispersant.

Non-water-soluble dye water dispersion 1 (30 parts by mass) obtained above, glycerin (10 parts by mass), propylene glycol (20 parts by mass), BYK-348 (manufactured by Bick Chemie Japan) (0.4 parts by mass) ), Polyester resin Vylonal MD-1480 (also described as “MD1480”) (Toyobo Co., Ltd., solid content 30 mass% (water except solid content), volume average particle size (Mv): 110 nm) (30 mass parts) And water (9.6 parts by mass), and filtered with a membrane filter (pore diameter: 0.8 μm) to prepare an inkjet ink (Qm).
Glycerin and propylene glycol are aqueous organic solvents, and BYK-348 is a surfactant.
The inkjet ink (Qm) is a magenta ink.

[Preparation of inkjet ink (Qc)]
As water-insoluble dyes, C.I. I. In place of disperse red 60, C.I. I. An inkjet ink (Qc) was prepared in the same manner as the preparation of the inkjet ink (Qm) except that disperse blue 359 was used. The average particle size of the water-insoluble dye in the ink was 115 nm. The inkjet ink (Qc) is a cyan ink.

[Preparation of inkjet ink (Qy)]
As water-insoluble dyes, C.I. I. In place of Disperse Blue 359, C.I. I. An inkjet ink (Qy) was prepared in the same manner as the preparation of the inkjet ink (Qc) except that disperse yellow 54 was used. The average particle size of the water-insoluble dye in the ink was 103 nm. The inkjet ink (Qy) is a yellow ink.

[Preparation of inkjet ink (Qb)]
As water-insoluble dyes, C.I. I. C.I instead of Disperse Red 60 (15 parts by mass); I. Disperse Brown 4 (7.5 parts by mass) and C.I. I. An inkjet ink (Qb) was prepared in the same manner as the preparation of the inkjet ink (Qm) except using disperse blue 79 (7.5 parts by mass). The average particle size of the water-insoluble dye in the ink was 122 nm. The inkjet ink (Qb) is a black ink.

[Preparation of ink set for inkjet textile printing]
The ink sets 1-6 for inkjet textile printing were created by the combination of the inkjet ink shown to following Table 1. FIG.

Example 1
An ink set 1 for ink jet printing is loaded into an ink cartridge, and a polyester fabric (Polyester Tropical (manufactured by Teijin Ltd.), Color Dyeing Co., Ltd.) is used using an ink jet printer (Carrio PX-045A manufactured by Seiko Epson Corporation). Co., Inc., product code A02-01019), cotton fabric (with cotton broadsil, product code A02-01002), and polyester 65% cotton 35% blend (blend polyester 65 / cotton 35 broad, stock The image was printed on company company Color Dye Co., Ltd., product code A02-01030), and dried at room temperature for 12 hours. After drying, heat treatment is performed for 60 seconds at a temperature of 200 ° C. and a pressure of 0.20 N / cm ² using a heat press (made by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press AF-54 TEN). I got a colored cloth.

(Examples 2 to 5)
An inkjet textile printing was performed in the same manner as in Example 1 except that the inkjet textile printing ink sets 2 to 5 were used instead of the inkjet textile printing ink set 1 to obtain a colored cloth.

(Comparative example 1)
Inkjet textile printing was performed in the same manner as in Example 1 except that the ink set for inkjet textile printing 6 was used in place of the ink set for inkjet textile printing 1, to obtain a colored cloth.

(Example 6)
[Preparation of aqueous pretreatment liquid A (1) containing flocculant]
The following components were mixed and stirred to prepare an aqueous pretreatment liquid A (1).
Casio Master PD-7 (Flocculant-containing; made by Yokkaichi Synthetic, solid content 50% by mass)
50g
BYK 348 (made by Big Chemie Japan) 5g
100 g of glycerin
Water 845g

[Pretreatment process]
Polyester fabric (Polyester Tropical (made by Teijin Ltd., product name A02-01019), manufactured by Teijin Ltd.), cotton fabric (with cotton broadsil, product name A02-01002), and polyester The aqueous pretreatment solution A (1) prepared above is applied to a 65% cotton 35% blend (blended polyester 65 / cotton 35 broad, product code A02-01030) manufactured by Color Dyes Co., Ltd. by padding method, It squeezed by 70% of squeezing rates, and allowed to dry for 24 hours. In addition, a squeeze rate (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid A (1) to the fabric after squeezing the fabric containing the aqueous treatment liquid A (1).

[Ink jet printing process]
Inkjet printing was performed in the same manner as in Example 1 using the ink set 1 of Example 1 except that a pre-treated cloth was used as the cloth, to obtain a colored cloth.

(Comparative example 2)
Inkjet printing was performed in the same manner as in Comparative Example 1 using the ink set 6 of Comparative Example 1 except that the above-described pretreated fabric was used as the fabric, to obtain a colored cloth.

The following evaluations were performed on the colored cloths obtained in Examples 1 to 6 and Comparative Examples 1 and 2.
In the evaluation of texture, a cotton fabric was used among the three types of fabrics.
Image sharpness: Visual sensory evaluation was performed. All three types of fabrics were evaluated in the following four grades: A, two types, B, one type, C, and no image, D. The results are listed in Table 1 below.
-Texture: The untreated cloth before dyeing and the colored cloth after dyeing were touched by hand, and the feeling of the colored cloth was evaluated sensoryally. The evaluation was performed by 10 people, with 10 points being excellent, with the texture of the colored cloth close to the untreated cloth being 0, and the other points being 0, and the numerical values of the total points are shown in Table 1 below. The larger the value, the better the texture close to the untreated cloth (100 (point)).

  As is clear from the above results, the ink set for ink jet textile printing according to the embodiment of the present invention is to provide a colored cloth having fabric versatility (performance to give clear images with various fabrics) and having a good feeling. I understand. In addition, the ink jet printing method according to the embodiment of the present invention does not require a pretreatment process, has no waste water and no waste material, has excellent environmental load, and has no problem in workability.

Claims (10)

  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 water-insoluble dye.   The ink set according to claim 1, which is for inkjet printing. The water-insoluble dye is
C. I. Disperse yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86,
C. I. Solvent Yellow 2, 14, 16, 21, 33, 34, 43, 45, 62, 85, 93, 98, 114, 131, 157, 160, 163, 167, 176, 179, 185, 189,
C. I. Disperse Red 11, 50, 53, 55, 55: 51, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240,
C. I. Solvent Red 8, 23, 24, 25, 49, 52, 109, 111, 119, 122, 135, 146, 149, 150, 168, 169, 172, 179, 195, 197, 207, 222, 227, 312, 313,
C. I. Disperse Blue 3, 5, 19, 26, 26: 1, 35, 55, 56, 64, 64: 1, 72, 72: 1, 79, 81, 81: 1, 91, 95, 108, 131, 141, 145, 359, 360,
C. I. Solvent Blue 3, 4, 5, 35, 36, 38, 45, 59, 63, 67, 68, 70, 78, 83, 97, 101, 102, 104, 105, 111, 122,
C. I. Disperse Orange 1, 1: 1, 5, 7, 20, 23, 25, 25: 1, 33, 56, 76,
C. I. Solvent Orange 3, 14, 54, 60, 62, 63, 67, 86, 107,
C. I. Disperse Violet 8, 11, 17, 23, 26, 27, 28, 29, 36, 57,
C. I. Solvent Violet 8, 9, 11, 13, 14, 26, 28, 31, 36, 59,
C. I. Solvent Green 3,5,7,28,
C. I. Disperse Brown 2,4,
C. I. Solvent Brown 53,
C. I. Solvent Black 3, 5, 7, 27, 29, 34
The ink set according to claim 1 or 2, which 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, comprising. 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 according to any one of claims 1 to 4, wherein the inkjet ink containing the water dispersion of the water-insoluble dye is at least one of a magenta ink, a yellow ink, a cyan ink, and a black ink. set.   The inkjet textile printing method which has the process of printing a fabric directly by inkjet method using the ink set of any one of Claims 1-5.   An aqueous pretreatment liquid containing a flocculant is applied to a fabric to obtain a pretreated fabric, and the ink set according to any one of claims 1 to 5 is applied by an inkjet method. An ink jet printing method comprising the step of printing on a pretreated fabric.   The ink jet printing method according to claim 6, further comprising a heat treatment step.   The ink cartridge which has an ink set of any one of Claims 1-5.   An ink jet printer having the ink set according to any one of claims 1 to 5.