JP2020002218A - Ink, inkjet textile printing method, ink cartridge, and inkjet printer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink or the like which can obtain a colored cloth excellent in color density and is excellent in continuous ejection property. An ink containing water, colored resin particles, and a water-soluble organic solvent, wherein the colored resin particles are at least one polymer selected from the group of acrylic polymers, polyurethanes, and polyureas, and an oil-soluble dye. , A disperse dye, and at least one dye selected from the group consisting of vat dyes, the acid value of the polymer is 5 to 90 mgKOH / g, and the solubility of the polymer in the water-soluble organic solvent is 0. 0.05% by mass or more, the water-soluble organic solvent is ether or amide, the boiling point of the water-soluble organic solvent is 287 ° C. or more, an inkjet printing method using the ink, an ink cartridge having the ink And inkjet printer. [Selection diagram] None

Description

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

  An inkjet ink is an ink applicable to an inkjet method, and is widely used for various uses. For example, ink-jet printing does not require the production of a printing plate, can quickly form an image with excellent gradation, and furthermore uses only a necessary amount of ink as a formed image, thereby reducing the amount of waste liquid. It can be said that this is an excellent printing method having advantages.

  Patent Literature 1 describes an ink for inkjet recording having an aqueous fine particle dispersion containing water, a water-soluble organic solvent, a disperse dye, and a dispersant. As a dispersant, a water-soluble ink having a sulfonic acid value of 100 to 250 is used. A water-soluble addition polymer is disclosed.

JP-A-10-114866

  However, when the ink described in Patent Literature 1 is applied to ink-jet printing, the coloring density of the obtained colored cloth is low, and the continuous discharge property of the ink is also poor.

  An object of the present invention is to provide an ink capable of obtaining a colored cloth having an excellent color density and excellent in a continuous discharge property, an ink jet printing method using the ink, an ink cartridge having the ink, and an ink jet printer. It is in.

  The present inventors have conducted intensive studies and found that the above-mentioned problems can be solved by the following means.

<1>
Water, colored resin particles, and an ink containing a water-soluble organic solvent,
The colored resin particles include at least one polymer selected from the group consisting of (meth) acrylic polymers, polyurethanes and polyureas, and at least one dye selected from the group consisting of oil-soluble dyes and disperse dyes. ,
The acid value of the polymer is 5 to 90 mgKOH / g,
The solubility of the polymer in the water-soluble organic solvent is 0.05% by mass or more,
The water-soluble organic solvent is an ether or an amide,
Ink, wherein the water-soluble organic solvent has a boiling point of 287 ° C. or higher.
<2>
The ink according to <1>, comprising a self-dispersing pigment.
<3>
The ink according to <1> or <2>, wherein the content of the water-soluble organic solvent is 25 to 45% by mass based on the total mass of the ink.
<4>
The ink according to any one of <1> to <3>, wherein the dye is a compound represented by the following general formula (MA).

In Formula (MA), R ^{1 to} R ²⁰ each independently represent a hydrogen atom or a substituent.
<5>
The dye is C.I. I. The ink according to any one of <1> to <4>, which is Solvent Black 3.
<6>
The ink according to any one of <1> to <5>, wherein the acid value of the polymer is 10 to 80 mgKOH / g.
<7>
The ink according to any one of <1> to <6>, wherein the polymer is a polyurethane.
<8>
The ink according to any one of <1> to <7>, containing a crosslinking agent.
<9>
The ink according to any one of <1> to <8>, which is used for inkjet.
<10>
The ink according to any one of <1> to <9> for printing.
<11>
An ink-jet printing method comprising a step of printing the ink according to any one of <1> to <10> on a fabric by an ink-jet method.
<12>
The inkjet printing method according to <11>, further comprising a heat treatment step.
<13>
An ink cartridge containing the ink according to any one of <1> to <10>.
<14>
An inkjet printer including the ink according to any one of <1> to <10>.

The present inventors have found that the above problem can be solved by using an ink containing water, specific colored resin particles, and a specific water-soluble organic solvent. Although the details of the mechanism for solving the above problems according to the present invention are not completely clear, the present inventors consider as follows.
It is already known to use a dispersion of colored resin particles containing a dye and a polymer in an ink, but the problem is that the dyes are easily associated with each other in the colored resin particles, and it is difficult to obtain a sufficient color density. was there.
In the ink of the present invention, by using a water-soluble organic solvent having a high solubility of the polymer, the polymer in the colored resin particles is easily dissolved, and the association of the dyes originally associated with each other is easily released. Further, by using a water-soluble organic solvent having a high boiling point (boiling point of 287 ° C. or higher), the volatilization rate of the water-soluble organic solvent at the time of thermal fixing to a fabric in ink jet printing decreases. Therefore, since the time for the polymer in the colored resin particles and the water-soluble organic solvent to adapt increases, the polymer and the water-soluble organic solvent coexist until immediately before heat fixing to the fabric, and the association of the dye is increased. It is considered that the dye is easily disintegrated, and it is possible to sufficiently express the original coloring density of the dye in the heat fixing to the fabric.
In the ink of the present invention, the compatibility between the polymer and the water-soluble organic solvent in the ink is good, and the dispersibility of the colored resin particles is good. Can be improved.
Further, in the present invention, at least one polymer selected from the group consisting of (meth) acrylic polymer, polyurethane and polyurea is used as the polymer, and these polymers are more compatible with the dye than other polymers. It is considered that the association of the dyes dissolved by the water-soluble organic solvent does not easily return to the original state even after the heat fixing, which is effective for improving the color density.
The acid value of the polymer used in the present invention is 5 to 90 mgKOH / g. When the acid value of the polymer is higher than 90 mgKOH / g, dispersibility in an ink in which a large amount of water-soluble organic solvent coexists is lowered, and continuous dischargeability is considered to be lowered. In addition, a cationic compound is used as a pretreatment agent for fabric. It is considered that the use of a compound containing the compound strongly interacts with the cationic compound on the fabric, hinders dissociation of the dyes, and lowers the color density. On the other hand, when the acid value of the polymer is lower than 5 mgKOH / g, the dispersibility of the dispersion of the colored resin particles is considered to be low.

  According to the present invention, it is possible to provide an ink capable of obtaining a colored cloth having excellent color density and excellent continuous dischargeability, an ink jet printing method using the ink, an ink cartridge having the ink, and an ink jet printer. Can be.

Hereinafter, the present invention will be described in detail.
In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the present specification, “(meth) acrylate” represents at least one of acrylate and methacrylate, “(meth) acryl” represents at least one of acryl and methacryl, and “(meth) acryloyl” is at least one of acryloyl and methacryloyl. Represents a kind.
In the present specification, the “substituent group A” refers to a substituent described in [0117] of WO 2017/131107.
In this specification, the substituent group A1 includes the following substituents.

(Substituent group A1)
Halogen atom, alkyl group (preferably having 1 to 30 carbon atoms), cycloalkyl group (preferably having 3 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), heterocyclic group (preferably having 3 to 30 carbon atoms) 30), an acyl group (preferably having 2 to 30 carbon atoms), a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an alkoxy group (preferably having 1 to 30 carbon atoms), and an aryloxy group (preferably having 2 to 30 carbon atoms) 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, Amino group (preferably having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably having 1 to 30 carbon atoms), arylsulfonylamino group (preferably having 6 to 30 carbon atoms), and substitution obtained by combining two or more of these. Base.

[ink]
The ink of the present invention is
Water, colored resin particles, and an ink containing a water-soluble organic solvent,
The colored resin particles include at least one polymer selected from the group consisting of (meth) acrylic polymers, polyurethanes and polyureas, and at least one dye selected from the group consisting of oil-soluble dyes and disperse dyes. ,
The acid value of the polymer is 5 to 90 mgKOH / g,
The solubility of the polymer in the water-soluble organic solvent is 0.05% by mass or more,
The water-soluble organic solvent is an ether or an amide,
An ink in which the water-soluble organic solvent has a boiling point of 287 ° C. or higher.

<(A) Water>
The ink of the present invention contains water. The water is not particularly limited, and ion-exchanged water, ultrafiltration water, reverse osmosis water, pure water such as distilled water, or ultrapure water can be used. More preferred.
The content of water in the ink is preferably 40 to 80% by mass, more preferably 45 to 75% by mass, and particularly preferably 50 to 75% by mass. When the water content is within the above range, the stability of the ink is excellent (the sedimentation or the like is unlikely to occur), and the ejection stability as an inkjet ink is also excellent.

<(B) Colored resin particles>
The ink of the present invention contains colored resin particles.
The average particle diameter of the colored resin particles is preferably 200 nm or less, more preferably 20 to 200 nm, and still more preferably 40 to 150 nm. When the average particle diameter of the colored resin particles is 200 nm or less, it becomes easy to print on the fabric by the ink jet method.
As the average particle diameter of the colored resin particles, a value of a volume average particle diameter (MV) measured using a particle size distribution analyzer (Nanotrack UPA EX150, manufactured by Nikkiso Co., Ltd.) was used.

In the ink of the present invention, the colored resin particles are present in a dispersed state.
When dispersed, the colored resin particles are easily mixed with water (easy to wet) as a property of the colored resin particles themselves or by using a dispersant in combination, and are regenerated by electrostatic repulsion (repulsive force) or steric repulsion. It has the function of preventing aggregation and suppressing sedimentation.
As a method for dispersing the colored resin particles, a known method can be used.

(polymer)
The colored resin particles used in the present invention contain at least one polymer selected from the group consisting of (meth) acrylic polymers, polyurethanes and polyureas.

-Polyurethane Polyurethane is a polymer having a urethane bond, and can typically be synthesized by reacting a compound having two or more isocyanate groups with a compound having two or more hydroxyl groups.
Polyurethane may be synthesized by a known method, or a commercially available product may be used.

The polyurethane may have a crosslinked structure.
The crosslinked structure represents a structure obtained by using a compound having three or more hydroxyl groups or isocyanate groups in the molecule as at least one monomer.
Examples of the compound having three or more hydroxyl groups or isocyanate groups in the molecule include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, hexamethylene diisocyanate, biuret of toluene diisocyanate, isocyanurate, adduct and the like. No.

The polyurethane may further have a urea bond. A resin having a urethane bond and a urea bond is also called “polyurethane / polyurea”.
As one kind of a preferable form of the polyurethane in the present invention, there is a polyurethane / polyurea in which a first partial structure containing a urethane bond and a second partial structure containing a urethane bond are bonded by a urea bond.

The weight average molecular weight (Mw) of the polyurethane is preferably at least 1,000, more preferably at least 5,000, even more preferably at least 10,000. When the molecular weight is 10,000 or more, it is preferable from the viewpoint of securing fixability after heating and securing color fastness. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyurethane can be measured by gel permeation chromatography (GPC).
In the present specification, GPC was measured using HLC-8220GPC (manufactured by Tosoh Corporation), columns were measured using TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation) unless otherwise specified. The average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated in terms of polystyrene.

-Polyurea Polyurea is a polymer having a urea bond, and can be typically synthesized by reacting a compound having two or more isocyanate groups with a compound having two or more amino groups.
Polyurea may be synthesized by a known method, or a commercially available product may be used.

Polyurea may have a crosslinked structure.
The crosslinked structure represents a structure obtained by using a compound having three or more hydroxyl groups or isocyanate groups in the molecule as at least one monomer.
Examples of the compound having three or more hydroxyl groups or isocyanate groups in the molecule include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, hexamethylene diisocyanate, biuret of toluene diisocyanate, isocyanurate, adduct and the like. No.

  The polyurea may further have a urethane bond. As described above, a resin having a urethane bond and a urea bond is also referred to as “polyurethane / polyurea”.

  Further, the weight average molecular weight (Mw) of the polyurea is preferably at least 1,000, more preferably at least 5,000, further preferably at least 10,000, and particularly preferably at least 30,000. When the molecular weight is 30,000 or more, it is preferable from the viewpoints of fixing property after heating and securing color fastness. The number average molecular weight (Mn) and weight average molecular weight (Mw) of polyurea can be measured by gel permeation chromatography (GPC).

-(Meth) acrylic polymer In the present invention, "(meth) acrylic polymer" represents at least one of an acrylic polymer and a methacrylic polymer.
In the present invention, a commercially available product or a synthetic product may be used as the (meth) acrylic polymer, and the synthetic product can be synthesized by a known radical polymerization method using a known monomer.
Further, the weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably at least 1,000, more preferably at least 5,000, further preferably at least 10,000, and particularly preferably at least 30,000. . When the molecular weight is 30,000 or more, it is preferable from the viewpoints of fixing property after heating and securing color fastness. The number average molecular weight (Mn) and weight average molecular weight (Mw) of polyurea can be measured by gel permeation chromatography (GPC).

  The polymer contained in the colored resin particles in the present invention is preferably at least one selected from the group consisting of polyurethane and polyurea from the viewpoint of improving the color density, improving the fastness, and the like, and is more preferably polyurethane.

The acid value of the polymer is between 5 and 90 mg KOH / g.
When the acid value is 5 mgKOH / g or more, when the colored resin particles are used as a dispersion, the dispersibility of the dispersion can be maintained, and the stability of the ink is not reduced. On the other hand, when the acid value is 90 mgKOH / g or less, the association of the dye by the water-soluble organic solvent is easily released, the dispersibility can be maintained, and the color density and the continuous ejection property of the ink are not reduced.
The acid value of the polymer is preferably from 5 to 90 mgKOH / g, more preferably from 10 to 90 mgKOH / g, particularly preferably from 10 to 80 mgKOH / g.

In consideration of the accuracy of the measurement, the acid value of the polymer was measured for the polymer particles prepared without adding a dye in the preparation of the colored resin particles.
The acid value can be measured according to the indicator titration method of JIS (Japanese Industrial Standard) K1557. However, the measurement is performed after removing the neutralizing agent used to neutralize the acidic group. For example, when an organic amine is used as a neutralizing agent, a colored resin particle dispersion or a polymer is applied to a glass plate and dried at a temperature of 60 ° C. under a reduced pressure of 20 mmHg for 24 hours to remove the organic amine. After volatilization, the obtained coating film is dissolved in N-methylpyrrolidone, and the acid value can be measured according to the indicator titration method of JIS K1557.
Note that 760 mmHg is 101325 Pa.

In the ink of the present invention, in the ink jet printing method using the ink, a crosslinking agent described below can be used in order to further increase the adhesion between the fabric and the polymer and improve the image fastness. Therefore, the polymer preferably 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.
In the ink of the present invention, it is preferable not to use a crosslinking agent. It is also preferable that the colored resin particles of the ink of the present invention do not contain a crosslinking agent. Furthermore, it is also preferred that the polymer has no groups that can react with the crosslinkable groups of the crosslinking agent.

  The polymer in the colored resin particles is preferably contained in an amount of 5 to 80% by mass, more preferably 5 to 60% by mass, based on the total mass of the entire colored resin particles, from the viewpoints of dispersibility, color development, and color fastness. Preferably, it is particularly preferably from 10 to 60% by mass.

(dye)
The colored resin particles in the ink of the present invention contain at least one dye (also simply referred to as “dye”) selected from the group consisting of oil-soluble dyes and disperse dyes.

The dye in the present invention is not particularly limited, but the following dyes are particularly preferred. Note that “CI” is an abbreviation for “color index”. Those described as "Disperse" are disperse dyes, and those described as "Solvent" are oil-soluble dyes.
C. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86,
C. I. Solvent Yellow 2, 14, 16, 21, 33, 43, 44, 56, 82, 85, 93, 98, 114, 131, 135, 157, 160, 163, 167, 176, 179, 185, 189,
C. I. Disperse Red 11,50,53,55,55: 1,59,60,65,70,75,93,146,158,190,190: 1,207,239,240,
C. I. Solvent Red 8, 23, 24, 25, 49, 52, 109, 111, 119, 122, 124, 135, 146, 149, 150, 168, 169, 172, 179, 195, 196, 197, 207, 222, 227, 312, 313,
C. I. Disperse Blue 3,5,19,26,26: 1,35,55,56,58,60,64,64: 1,72,72: 1,81,81: 1,91,95,108,131, 141, 145, 359, 360,
C. I. Solvent Blue 3, 4, 5, 35, 36, 38, 44, 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,
C. I. Solvent Brown 53,
C. I. Solvent Black 3,5,7,27,29,34

  Among the above dyes, oil-soluble dyes are preferred.

  The dye is preferably a compound represented by the following formula (MA).

In Formula (MA), R ^{1 to} R ²⁰ each independently represent a hydrogen atom or a substituent.
Examples of the substituent include a substituent selected from the substituent group A (preferably, a substituent selected from the substituent group A1).
In the general formula (MA), R ¹ and R ² preferably represent a hydrogen atom.
R ^{3 to} R ¹⁸ preferably represent a hydrogen atom.
R ¹⁹ and R ²⁰ each independently preferably represent an alkyl group, more preferably represent an alkyl group having 1 to 30 carbon atoms, still more preferably represent an alkyl group having 1 to 10 carbon atoms, Particularly preferably, it represents 1 to 6 alkyl groups, most preferably a methyl group.

  Examples of the dye include C.I. I. Solvent Black 3 is most preferred.

  The content of the dye in the colored resin particles is preferably from 10 to 90% by mass, more preferably from 15 to 80% by mass, still more preferably from 20 to 75% by mass, from the viewpoint of ensuring color developability and color fastness. -70% by mass is particularly preferred.

  In the colored resin particles of the ink of the present invention, the dye exists in a form coated with the polymer. Preferably, the polymer and the dye are not covalently linked. Since the polymer and the dye are not bound by a covalent bond, the mobility of the dye is enhanced, and a high color density can be exhibited.

  The content of the colored resin particles in the ink of the invention is preferably from 0.5 to 30% by mass, more preferably from 1.0 to 25% by mass, and more preferably from 2.0 to 25% by mass, from the viewpoint of ensuring ejection stability and color development. To 20% by mass is more preferable, and 3.0 to 20% by mass is particularly preferable.

The colored resin particles are preferably used as a dispersion.
The method for producing the colored resin particle dispersion is not particularly limited. When the polymer is polyurethane, for example, the following method may be used. In the presence or absence of an organic solvent containing no active hydrogen-containing group in the molecule (eg, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, etc.), a polymer having two or more isocyanate groups in one molecule A polyurethane is synthesized by subjecting an isocyanate, a polyol having two or more hydroxyl groups in one molecule, a polyol having an acidic group or a salt thereof to a urethanization reaction by a one-shot method or a multi-stage method to synthesize a polyurethane, and if necessary, the polyurethane After neutralization with a wetting agent, a dye is added, water is dropped into the reaction solution where the reaction solution is vigorously stirred, and the solvent is removed as necessary to obtain a colored resin particle dispersion.

  The method for producing the colored resin particle dispersion includes, in advance, a polyisocyanate having two or more isocyanate groups in one molecule, a polyol having two or more hydroxyl groups in one molecule, an acidic group-containing polyol or a salt thereof. , A prepolymer is synthesized under the condition of an excess of isocyanate, a dye is added, and the mixture is dispersed in water. Then, a chain extender is added to obtain a colored resin particle dispersion.

(Polyisocyanate)
The polyisocyanate that can be used in the method for producing a colored resin particle dispersion is not particularly limited as long as it is a polyisocyanate containing two or more isocyanate groups in one molecule. Examples of the polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, and 2,6-diisocyanate methyl isocyanate. Aromatic, aliphatic and alicyclic organic diisocyanates such as proate, isophorone diisocyanate (IPDI), methylcyclohexane-2,4- (or 2,6-) diisocyanate, and 4,4′-methylenebis (cyclohexyl isocyanate); Or a multimer containing a polyfunctional isocyanate group such as a burette or isocyanurate thereof, or a polymer of these isocyanates Alone or a mixture may be mentioned.
In particular, from the viewpoint of weather resistance, an aliphatic and / or alicyclic organic diisocyanate compound is preferable. Specifically, aliphatic and alicyclic organic diisocyanates such as HDI, IPDI, dodecane diisocyanate, cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate are preferable. Diisocyanates or mixtures of these isocyanates are more preferred.

(Polyol)
The polyol that can be used in the method for producing the colored resin particle dispersion is not particularly limited as long as the polyol contains two or more hydroxyl groups in one molecule. For example, a polymer polyol or a low molecular weight polyol is used. Can be. Examples of polym-polyols include polyether polyols, polyester polyols, polycarbonate polyols and the like.
The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a random copolymer of ethylene oxide and propylene oxide, a random copolymer of ethylene oxide and butylene oxide, and a block copolymer. Further, a polyether polyester polyol having an ether bond and an ester bond can be used.
The polyester polyol is not particularly limited, for example, polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol, polybutylene succinate polyol, polyethylene seba Kate polyol, polybutylene sebacate polyol, poly-ε-caprolactone polyol, poly (3-methyl-1,5-pentylene adipate) polyol and the like can be mentioned.
Examples of the polycarbonate polyol include a linear aliphatic polycarbonate polyol, a branched aliphatic polycarbonate polyol, a polycarbonate polyol having an alicyclic structure in a main chain, and a polycarbonate polyol having an aromatic ring in a main chain.
The low-molecular-weight polyol is not particularly limited, but a low-molecular-weight diol can be used. For example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl- 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6 Aliphatic diols having 2 to 9 carbon atoms such as -hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol , 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis ( Hydroxyethyl) cyclohexane, 2,7-norbornanediol, tetrahydrofuranmethanol, diols having an alicyclic structure having 6 to 12 carbon atoms such as 2,5-bis (hydroxymethyl) -1,4-dioxane, and the like. Can be. Further, as the low molecular weight polyol, a low molecular weight polyhydric alcohol such as trimethylolpropane, pentaerythritol, and sorbitol may be used.

  The polyol is a compound containing two or more hydroxyl groups, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol , 1,2-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol Linear aliphatic glycols such as polyethylene glycol, polypropylene glycol, 1,8-octanediol, 1,2-octanediol and 1,9-nonanediol; neopentyl glycol, 3-methyl-1,5-pentanediol, 2 Methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, Aliphatic branched glycols such as 2-methyl-1,8-octanediol; alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; glycerin, trimethylolethane, trimethylolpropane, tributy And polyfunctional glycols such as roll propane, pentaerythritol, and sorbitol; and these can be used alone or in combination of two or more, and can also be used as a copolymer of two or more.

(Acid-containing polyol or salt thereof)
The acidic group-containing polyol that can be used in the method for producing the colored resin particle dispersion is a compound having two or more hydroxyl groups and one or more acidic groups in one molecule. It is used for introducing a carboxylate group or a sulfonate group for the purpose of emulsifying a polymer in water and imparting dispersion stability of a colored resin particle dispersion. The carboxyl group-containing polyol is not particularly limited. For example, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctane Acids and the like. Examples of the sulfone group-containing polyol include sulfonic acid diol {3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid} and sulfamic acid diol {N, N-bis (2-hydroxylalkyl) sulfamic acid. And an alkylene oxide adduct thereof. The salt of the polyol containing a carboxyl group and / or a sulfone group is not particularly limited, and examples thereof include ammonium salts, amine salts [primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propyl Amines and octylamine) salts, secondary monoamines (dimethylamine, diethylamine and dibutylamine) salts, tertiary monoamines (trimethylamine, triethylamine triethanolamine, N-methyldiethanolamine and aliphatic tertiary such as N, N-dimethylethanolamine) Monoamines; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; tertiary monoamines containing aromatic rings such as benzyldimethylamine, α-methylbenzyldimethylamine; and N-dimethylaniline ) Salts, alkali metal (sodium, potassium and lithium cations) salts, as well as combinations of two or more of these.

  When the polyol is not a salt but a carboxyl group and / or sulfone group-containing polyol, a neutralizing agent may be used to neutralize the carboxyl group and / or sulfone group to form a carboxylate group and / or sulfonate group. it can.

(Neutralizer)
The neutralizing agent is not particularly limited, and examples thereof include an alkaline compound capable of neutralizing the carboxyl group and / or the sulfone group. For example, ammonia, amine [a primary amine having 1 to 12 carbon atoms (primary monoamine such as methylamine, ethylamine, propylamine and octylamine), a secondary monoamine (dimethylamine, diethylamine and dibutylamine), and a tertiary monoamine ( Aliphatic tertiary monoamines such as trimethylamine, triethylamine, triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; benzyldimethylamine; α-methylbenzyldimethylamine; and tertiary monoamines containing an aromatic ring such as N-dimethylaniline)], alkali metals (sodium, potassium and lithium cations), alkali metal hydroxides, and Combinations of two or more of the like.

(Chain extender)
Examples of the chain extender include, but are not limited to, water, short-chain diols such as ethylene glycol, 1,3-propanediol, and 1,4-butanediol, hydrazine, ethylenediamine, diethyltriamine, triethylenetetramine, and tetraethylene. Examples thereof include polyamines such as pentamine, pentaethylenehexamine, propylenediamine, hexamethylenediamine, and cyclohexylenediamine. These may be used alone or in combination of two or more.

  As a method for producing a colored resin particle dispersion, when the polymer is polyurea, for example, an organic solvent containing no active hydrogen-containing group in the molecule (for example, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, etc.) A polyisocyanate having two or more isocyanate groups in one molecule, a polyamine having two or more amino groups in a molecule, an acidic group-containing polyol or a salt thereof in the presence or absence of Polyurea was synthesized by a urethanation reaction by a multi-stage method, and if necessary, after neutralizing the polyurea with a neutralizing agent, a dye was added, and water was added dropwise while the reaction solution was vigorously stirred. Thereafter, the solvent is removed as necessary to obtain a colored resin particle dispersion.

  The method for producing the colored resin particle dispersion includes, in advance, a polyisocyanate having two or more isocyanate groups in one molecule, a polyamine having two or more amino groups in one molecule, an acidic group-containing polyol or a salt thereof. , A prepolymer is synthesized under the condition of an excess of isocyanate, a dye is added, and the mixture is dispersed in water. Then, a chain extender is added to obtain a colored resin particle dispersion.

(Polyamine)
The polyamine that can be used in the method for producing the colored resin particle dispersion is not particularly limited as long as it is a polyamine containing two or more amino groups in one molecule. For example, a polymer polyamine or a low molecular weight polyamine may be used. Can be.
The polymer polyamine is not particularly restricted but includes, for example, polyethyleneimine, polyethyleneoxy polymer terminal diamine, polyoxypropylene polymer terminal diamine, polyoxyethylene / oxypropylene copolymer terminal diamine, and the like.
The low molecular weight polyamine is not particularly limited, and examples thereof include ethylenediamine, propylenediamine, putrescine, hexamethylenediamine, spermidine, spermine, phenyldiamine, naphthalenediamine, xylenediamine, and isophoronediamine.

  As for the polyisocyanate, the acidic group-containing polyol or a salt thereof, the neutralizing agent, and the chain extender, the above-described polyisocyanate, the acidic group-containing polyol or a salt thereof, the neutralizing agent, and the chain extender can be used.

  When the polymer is a (meth) acrylic polymer, the colored resin particle dispersion can be synthesized by a known radical polymerization method using a known monomer. For example, it can be synthesized with reference to synthesis and reaction of a polymer (Kyoritsu Shuppan Co., Ltd.).

<(C) Water-soluble organic solvent>
The ink of the present invention contains a water-soluble organic solvent. The solubility of the polymer in the colored resin particles in the water-soluble organic solvent is 0.05% by mass or more.
The water-soluble organic solvent is an ether or an amide. The boiling point of the water-soluble organic solvent is 287 ° C. or higher.

The water-soluble organic solvent preferably has a solubility in water 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 has an arbitrary ratio with water. Those that are miscible are particularly preferred.

  It is preferable that the solubility of the polymer in the water-soluble organic solvent is 0.05% by mass or more, because the color density can be improved. When the solubility is 0.05% by mass or more, the color density can be dramatically improved in the heat fixing after printing on the fabric by the inkjet method.

  This is a phenomenon that cannot be seen with ordinary dye inks for dyeing and pigment inks.In the present invention, the polymer of the colored resin particles is easily dissolved in the water-soluble organic solvent, and further, the association between the dyes is increased. This is considered to be because the dye was easily released and the color development inherent in the dye was sufficiently exhibited.

  The solubility of the polymer in the water-soluble organic solvent is preferably 5% by mass or less, more preferably 1% by mass or less.

  The solubility can be measured by a general-purpose method, but in the present invention, the solubility can be measured by the following method. The measurement of the solubility of the polymer was performed on the polymer particles produced without adding a dye in the production of the colored resin particles. The aqueous dispersion of the polymer particles is allowed to stand on a Petri dish at 25 ° C., and dried until there is no loss in mass. 100 g of a water-soluble organic solvent is weighed in a glass vial, the solid of the polymer obtained above is added thereto, and ultrasonic waves are applied by an ultrasonic cleaner (1-6900-01, manufactured by AS ONE Corporation) for 30 minutes. The presence or absence of dissolution is visually evaluated. The weighed value of the polymer solid is appropriately changed, and the solubility (% by mass) is calculated from the weighed value of the maximum amount of the solid that completely dissolves and the mass of the water-soluble organic solvent.

  As described above, when the boiling point of the water-soluble organic solvent is 287 ° C. or higher, the coloring density can be improved. On the other hand, when the boiling point is lower than 287 ° C., a sufficient coloring density may not be obtained. is there. This is presumably because the higher the boiling point, the lower the volatilization rate of the water-soluble organic solvent at the time of heat fixing, and the longer the time required for the polymer and the water-soluble organic solvent to sufficiently adapt. Further, it is presumed that the higher the boiling point, the more the drying on the ink jet nozzle surface is suppressed, but the continuous dischargeability can be greatly improved.

In the present invention, the boiling point can be measured at atmospheric pressure by a general distillation method. The boiling point in the specification is a value of the boiling point under standard conditions (1 atm, 25 ° C.).
One atmosphere is 101.325 kPa.

  In the measurement of the boiling point of the water-soluble organic solvent, when the boiling point exceeds 350 ° C., decomposition of the water-soluble organic solvent may occur during the measurement, and it may be difficult to measure the accurate boiling point. In the present invention, a water-soluble organic solvent having a boiling point exceeding 350 ° C. can be used with the boiling point being “350 ° C. or higher”.

The content of the water-soluble organic solvent is preferably from 25 to 45% by mass, more preferably from 30 to 40% by mass, based on the total mass of the ink.
When the content of the water-soluble organic solvent is 25% by mass or more with respect to the total mass of the ink, the polymer is easily dissolved, and the ink jet nozzle surface is hardly dried. It is preferable that the properties are not easily deteriorated. Further, when the content of the water-soluble organic solvent is 45% by mass or less based on the total mass of the ink, the storage stability of the polymer in the ink hardly deteriorates, which is preferable. It is preferable that the content of the water-soluble organic solvent is appropriately selected in an appropriate range within the above range.

  The water-soluble organic solvent is not particularly limited as long as it satisfies the above. Specifically, triethylene glycol, tetraethylene glycol, polyethylene glycol (for example, having a molecular weight of 400 to 800), hydroxyethylpyrrolidone, hydroxy Propylpyrrolidone, valerolactam, caprolactam, heptalactam and the like. , Hydroxypropylpyrrolidone and the like are more preferable, and triethylene glycol, tetraethylene glycol and hydroxyethylpyrrolidone are particularly preferable, and triethylene glycol and tetraethylene glycol Le is most preferable.

<(D) Crosslinking agent>
The ink of the present invention may further contain a crosslinking agent.
The crosslinking agent is preferably a compound having at least two crosslinking groups.
As the crosslinkable group of the crosslinking agent, a carboxyl group, a hydroxyl group, a sulfo group, an amide group, and the like are preferable.
Examples of the crosslinking agent include a blocked isocyanate compound, an oxazoline compound, and a carbodiimide compound. Among them, HDI (hexamethylene diisocyanate), H6XDI (hydrogenated xylylene diisocyanate), IPDI (isophorone diisocyanate), or H12MDI ( A blocked isocyanate compound obtained by blocking a TMP (trimethylolpropane) adduct of dicyclohexylmethane diisocyanate) or an isocyanurate with a blocking agent is preferable, and the blocking agent may be DEM (diethyl malonate), DIPA (diisopropyl) based on its dissociation temperature. Amine), TRIA (1,2,4-triazole), DMP (3,5-dimethylpyrazole), and MEKO (butanone oxime). That. In addition, these blocked isocyanate compounds can also be used as oligomers in which a part of the isocyanate group is reacted with polyol, polycarbonate, polyester, polyether, or the like.
By including a crosslinking agent, dyeing fastness such as sweat resistance, washing resistance, and rub resistance can be improved.In particular, the crosslinking agent is a blocked isocyanate, and the water-soluble organic solvent in the present invention is an ether-based solvent. In some cases, it has a great effect.
This is presumably because the hydroxyl groups at both ends of the ether-based water-soluble organic solvent act on the cross-linking agent and participate in the cross-linking system, thereby improving the strength of the obtained ink film.
The cross-linking agent particles preferably have an average particle diameter of 200 nm or less from the viewpoint of improving the dischargeability in inkjet. As the average particle diameter, a value of a volume average particle diameter (MV) measured using a particle size distribution measuring device (Nanotrack UPA EX150, manufactured by Nikkiso Co., Ltd.) can be used.
The dissociation temperature of the crosslinking agent is preferably as low as possible from the viewpoint of crosslinking efficiency, and is preferably as high as possible from the viewpoint of storage stability. The dissociation temperature can be appropriately selected. The dissociation temperature is preferably in the range of 90C to 180C, more preferably in the range of 90C to 120C, and particularly preferably in the range of 110C to 120C.
The crosslinking agent is preferably added to the ink as a water-soluble or self-emulsifying agent by imparting a hydrophilic group. In this state, the viscosity of the compounded ink can be reduced, and excellent redispersibility can be obtained.
Examples of the crosslinking agent particles include, but are not particularly limited to, elastron BN-77 (block isocyanate, particle size 19 nm, dissociation temperature of 120 ° C. or higher, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), elastron BN-27 ( Block isocyanate, particle size 108 nm, dissociation temperature 180 ° C. or higher, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Duranate WM44-70G (block isocyanate, particle size 42 nm, dissociation temperature about 90 ° C., manufactured by Asahi Kasei Corporation), TRIXENE AQUA BI200 (block isocyanate) , A particle size of 94 nm, a dissociation temperature of 110 to 120 ° C, and manufactured by BAXENDEN).

  The content of the cross-linking agent in the ink is preferably 0.1 to 10% by mass, since it is necessary to incorporate a cross-linkable functional group sufficient to react the polymer and the fabric. The content is more preferably from 8 to 8% by mass, and still more preferably from 1 to 5% by mass.

<(E) Pigment>
The ink of the present invention may further contain a pigment. The pigment is preferably dispersed in the ink of the present invention.
In the ink jet printing method of the present invention, the polymer forms a film on the fabric, but depending on the color, the pigment may be further dispersed in the film to adjust the hue or to increase the color density. Is preferred because Only one pigment may be used, or two or more pigments may be used.

The pigment that can be used in the present invention is not particularly limited, for example,
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 is preferable.

  When the ink of the present invention contains a pigment, the content of the pigment in the ink is preferably 0.5 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 0.5 to 5% by mass. .

  In the present invention, at the time of preparing the ink, an aqueous dispersion of a pigment in which a pigment is dispersed in water using a dispersant (also referred to as an “aqueous pigment dispersion”) may be used. As the pigment aqueous dispersion, for example, a pigment dispersion described in JP-A-2012-7148 can be used.

(Self-dispersible pigment)
As the pigment, a self-dispersion pigment is preferably used.
The self-dispersion pigment is a pigment that can be dispersed in water without using a dispersant. Self-dispersible pigments include, for example, a carbonyl group, a hydroxyl group, a carboxyl group, a sulfo group, a hydrophilic group such as a phosphoric acid group, and at least one of their salts, which are directly or via other groups, on the surface of the pigment. Those introduced by bonding may be mentioned.
The self-dispersing pigment is preferably a self-dispersing carbon black.
In the ink of the present invention, by using the self-dispersible pigment together with the colored resin particles, it is possible to obtain a color density higher than the color density obtained only with the colored resin particles. This is because, when ink-jet printing is performed using ink using only colored resin particles, the ink film obtained after heat fixing is smooth, which may cause light reflection. It is considered that by using them together, a higher color density can be obtained by roughening the ink film after thermal fixing and suppressing reflection.
Further, the self-dispersion type pigment is preferable because the pigment surface is hydrophilic and can prevent the colored resin particles from being associated on the pigment surface when used together with the colored resin particles.
Examples of the self-dispersible pigments that can be used include self-dispersible carbon blacks CAB-O-JET 200, 300 (all manufactured by Cabot Corporation), BONJET CW-1 (500 μmol / g as a carboxy group), and CW-2 ( Commercially available products such as 470 μmol / g as a carboxy group (above, manufactured by Orient Chemical Industry Co., Ltd.) and Aqua-Black 162 (about 800 μmol / g as a carboxyl group) of Tokai Carbon Co., Ltd.
Further, the ratio of the content of the self-dispersing pigment to the content of the coloring resin particles (content of the self-dispersing pigment / content of the coloring resin particles) is 1/9 to 4/6 by mass ratio. And more preferably 2/8 to 3/7.

<Other ingredients>
The ink of the present invention may contain components other than those described above.
Other components include, for example, colorants other than the above dyes and pigments, organic solvents, surfactants, pH adjusters, fluorescent brighteners, surface tension adjusters, defoamers, anti-drying agents, lubricants, Viscosity agents, ultraviolet absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, resistivity adjusters, rust inhibitors, inorganic pigments, reduction inhibitors, preservatives, fungicides, chelating agents, etc. No. As these components, those described in WO 2017/131107 can be preferably used.

When the ink of the present invention is used for inkjet (inkjet ink), the surface tension of the ink is preferably adjusted to 20 mN / m to 70 mN / m, more preferably to 25 mN / m to 60 mN / m. preferable. When the ink is used for inkjet, the viscosity of the ink is preferably adjusted to 40 mPa · s or less, more preferably to 30 mPa · s or less, and particularly preferably to 20 mPa · s or less. preferable. The viscosity is measured at 25 ° C. using an E-type rotational viscometer.
The surface tension and the viscosity are determined by various additives such as a viscosity modifier, a surface tension regulator, a specific resistance regulator, a film regulator, an ultraviolet absorber, an antioxidant, a discoloration inhibitor, a fungicide, and a rust inhibitor. It can be adjusted by adding a dispersant, a surfactant and the like.

The ink of the present invention (preferably an inkjet ink) is preferably used for textile printing.
The ink of the present invention is more preferably an ink-jet ink for textile printing, which prints on a fabric by an ink-jet method.

  INDUSTRIAL APPLICABILITY The inkjet ink for textile printing of the present invention is useful from the viewpoint of workability because it can directly print on a fabric to which a pretreatment agent has not been applied, without bleeding.

<Ink preparation method>
The method for preparing the ink of the present invention is not particularly limited. For example, a method of first obtaining a dispersion of colored resin particles, and then mixing the dispersion of the colored resin particles with an aqueous organic solvent, water, and, if necessary, a surfactant, to prepare an ink. Is mentioned.

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

[Inkjet printing method]
The ink-jet printing method of the present invention is an ink-jet printing method including a step of printing the ink of the present invention (ink-jet ink for printing) directly on a fabric by an ink-jet method.
In the inkjet printing method of the present invention, the cloth may be a cloth pretreated with an aqueous pretreatment liquid containing a flocculant. That is, the inkjet printing method of the present invention may include a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to the fabric to obtain a pretreated fabric.
Note that, in the present invention, "directly printing" the textile ink jet ink on the fabric by the inkjet method means that the transfer step is unnecessary, the step of applying the printing paste is unnecessary, and the textile ink jet ink is directly applied to the fabric. Refers to being stamped.
The inkjet printing method of the present invention does not generate waste materials such as wastewater and transfer paper, is a simple method, and is useful.

(Pretreatment step)
The pretreatment step is a step of applying an aqueous pretreatment liquid containing a flocculant 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, and a screen printing method.
The coagulant contained in the aqueous pretreatment liquid is not particularly limited as long as it has an action of coagulating the colored resin particles, and is at least one selected from organic acids, polyvalent metal salts, and cationic compounds. Preferably, there is.
In particular, when the aggregating agent is a cationic compound or a polyvalent metal salt and the polymer in the colored resin particles has an anionic group (preferably an acid group, more preferably a carboxyl group), the above-mentioned inkjet printing method When the printing is performed in the above, a colored cloth having a high concentration can be obtained. This is because the pre-treated cationic compound or polyvalent metal salt stays on the fabric surface due to aggregation at the moment it comes into contact with the ink containing the polymer having an anionic group, and consequently exists on the surface. It is considered that the amount of the colored resin particles increased and the concentration was increased. More preferably, the flocculant is a cationic compound.

≪Polyvalent metal salt≫
A 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 And the like.

≪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, Hydroxy-4- (trimethylammonio) butyrate hydrochloride, glycidyltrimethylammonium chloride, L-carnitine hydrochloride and the like can be mentioned.
Examples of the high molecular weight cationic compound include, for example, polyallylamine or a derivative thereof, an amine-epihalohydrin copolymer, and other quaternary ammonium salt-type cationic polymers, which are soluble in water and positively formed in water. Chargeable cationic polymers can be mentioned. In some cases, a water-dispersible cationic polymer may be used.

The coagulants may be used alone or in combination of two or more.
The aqueous pretreatment liquid may contain, for example, a surfactant and a resin in addition to water and an aqueous organic solvent.

<Heat treatment process>
The inkjet 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 polymer can easily form a film.
The heat treatment step is preferably performed by heating the colored cloth.
The temperature of the heat treatment step is preferably from 100 to 220C, more preferably from 130 to 200C. The heating time in the heat treatment step is preferably from 20 seconds to 300 seconds, more preferably from 30 to 240 seconds, and still more preferably from 40 to 180 seconds.

<Post-processing>
Fabrics colored with the ink jet ink for textile printing of the present invention are further improved in texture flexibility and robustness (particularly rub resistance) by padding the entire surface of the colored fabric with a post-treatment agent, if necessary. A colored cloth can be obtained. Examples of post-treatment agents for softening include cationic surfactants, anionic surfactants, nonionic surfactants, dimethyl silicone oil, amino silicone oil, carboxy-modified silicone oil, hydroxy-modified silicone oil, and fatty acids. Amides, fatty acid amides, mineral oils, vegetable oils, animal oils, plasticizers and the like.
In addition, as post-treatment agents for the purpose of improving the slipperiness of the colored cloth surface, metal soap, paraffin wax, carnauba wax, microstalin wax, dimethyl silicone oil, amino silicone oil, carboxy-modified silicone oil, hydroxy-modified silicone oil, etc. Is mentioned.
In the padding treatment, a colored cloth is immersed in a product obtained by emulsifying, thermally emulsifying, or dispersing these post-treatment agents in a water solvent by stirring with a mixer, squeezed and dried with a mangle or the like, and subjected to heat treatment.
Further, by adding a small amount of a resin emulsion as a fixing agent in the post-treatment agent, the friction resistance of the colored cloth can be improved. The blending amount with respect to the post-treatment agent is preferably less than 5%, which is preferable because the softness of the texture of the colored cloth is not easily impaired.
The resin emulsion to be added as a fixing agent to the post-treatment agent is not particularly limited, but is an acrylate resin emulsion, a urethane resin emulsion, an ethylene / vinyl acetate copolymer resin (EVA resin) emulsion, a silicone / acryl resin emulsion. In order to soften the texture of the colored cloth, the glass transition point of these resin emulsions is preferably 0 ° C. or lower.

<Cloth>
The inkjet printing method of the present invention can be applied to various types of fabrics. For example, 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, fabrics, and knits thereof. Nonwoven fabrics and the like can be mentioned.
As the cloth, a pretreated cloth can be used. 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 polymer in the colored resin particles, and is preferably an aqueous solution. Examples of the coagulant include an organic acid, a polyvalent metal salt, and a cationic compound.
Clothing includes T-shirts, trainers, jerseys, pants, sweatsuits, dresses, blouses, and the like. It is also suitable for bedding and handkerchiefs.

<Example 1>
(Preparation of Colored Resin Particle Dispersion (A1))
In a reaction vessel equipped with a thermometer and a stirrer, 61.7 parts by mass of poly (3-methylpentyl adipate) diol (number average molecular weight 2000), 2.7 parts by mass of 2,2-dimethylolpropanoic acid (DMPA), After adding 60 parts by mass of hexamethylene diisocyanate (HDI) and 2 parts by mass of trimethylolpropane, ethyl acetate was added to the mixture to adjust the solid content to 30% by mass, and the reaction system was replaced with nitrogen gas. After stirring for 3 hours, 2.9 parts by mass of triethylamine (1.05 equivalent / carboxyl group) was added. Next, C.I. I. 100 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) was added with stirring. Next, a solution obtained by dissolving 9 parts by mass of sodium dodecyl sulfate in 650 parts by mass of water was added to the above ethyl acetate solution, and after emulsification and chain extension reaction, ethyl acetate was distilled off at 30 to 40 ° C. under reduced pressure. The concentration was adjusted with water to obtain a colored resin particle dispersion (A1) having a solid content of 20% by mass and a volume average particle diameter of 120 nm.

(Preparation of Ink Composition 1)
After mixing and stirring the following components, the mixture was filtered through a polytetrafluoroethylene (PTFE) membrane filter (pore size: 0.8 μm, manufactured by Advantech) to prepare Ink Composition 1.
-Colored resin particle dispersion (A1) (dispersed solid 20% by mass), 50 parts by mass-Water-soluble organic solvent: triethylene glycol (TEG) (manufactured by Tokyo Chemical Industry Co., Ltd.), 35 parts by mass-Olphin E1010 (Nissin Chemical) 1 part by mass ・ Ultra pure water, 14 parts by mass

(Inkjet printing and heat treatment)
The above ink composition 1 was filled in an ink cartridge, and then, using an ink jet printer (manufactured by Seiko Epson Corporation, PX-049A), a cotton master (manufactured by Akahori Sangyo Co., Ltd., D5005) was previously used for Kachiomaster PD-7 (Yokkaichi). Pre-treated cotton broad (so-called “cotton” in Tables 1-4 below) in which a 5% by weight aqueous solution of Synthetic Co., Ltd. was impregnated with 60% by weight based on the weight of the fabric and dried at 25 ° C. for 12 hours. .), A solid image was printed. In addition, printing was repeated by overlapping as appropriate so that the amount of ink ejected was about 20 g / m ² . Then, after drying at 25 ° C. for 12 hours, a heat fixing process was performed at a temperature of 200 ° C., a pressure of 0.20 N / cm ² and a time of 60 seconds using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., AF-54TEN). To obtain a colored cloth.

<Examples 2 to 5>
Except that the water-soluble organic solvent was changed to tetraethylene glycol (manufactured by Tokyo Kasei), polyethylene glycol 400 (PEG400, manufactured by Tokyo Kasei), hydroxyethylpyrrolidone (manufactured by Tokyo Kasei), and heptalactam (manufactured by Tokyo Chemical). In the same manner as in Example 1, ink compositions 2 to 5 were obtained.
In addition, ink-jet printing and heat treatment were performed in the same manner as in Example 1 except that the ink composition 1 was changed to the ink compositions 2 to 5, respectively, to obtain a colored cloth.
In Example 2, in addition to the pre-treated cotton broad, the printing was performed using a cotton / polyester blend (KDP6112-58, manufactured by Uji Textile), a polyester (KKT3399-58, manufactured by Uji Textile), and pretreatment. It was also carried out on cotton broad (D5005, manufactured by Akahori Sangyo Co., Ltd.) (described as "cotton (untreated)" in Tables 1 and 4 below), which were referred to as Examples 2a, 2b, and 2c, respectively. .

<Examples 6 to 9>
Triethylene glycol was changed to tetraethylene glycol, and the addition amount was changed to 25 parts by mass, 45 parts by mass, 20 parts by mass, and 48 parts by mass, respectively, and the ultrapure water was appropriately adjusted so that the total amount of the ink composition became 100 parts by mass. Ink compositions 6, 7, 8, and 9 were obtained in the same manner as in Example 1 except that the amount of the ink composition was adjusted.
In addition, ink-jet printing and heat treatment were performed in the same manner as in Example 1 except that the ink composition 1 was changed to the ink compositions 6, 7, 8, and 9, respectively, to obtain a colored cloth.

<Examples 10 to 15>
An ink composition was prepared in the same manner as in Example 1 except that the colored resin particle dispersion (A1) was changed to the colored resin particle dispersions (A2) to (A7), and triethylene glycol was changed to tetraethylene glycol. 10-15 were obtained.
In addition, ink-jet printing and heat treatment were performed in the same manner as in Example 1 except that the ink composition 1 was changed to each of the ink compositions 10 to 15 to obtain a colored cloth.

(Preparation of Colored Resin Particle Dispersion (A2))
In a reaction vessel equipped with a thermometer and a stirrer, 65 parts by mass of poly (3-methylpentyl adipate) diol (number average molecular weight 2000), 1.4 parts by mass of DMPA, 59 parts by mass of hexamethylene diisocyanate (HDI), trimethylolpropane 2 parts by mass were added, and ethyl acetate was added thereto to adjust the solid content to 30% by mass. After the reaction system was replaced with nitrogen gas, the mixture was stirred at 40 ° C. for 3 hours, and then 1.4 parts by mass of triethylamine (1 part by mass). .05 equivalents / carboxyl group). Next, C.I. I. 100 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) was added with stirring. Next, a solution obtained by dissolving 9 parts by mass of sodium dodecyl sulfate in 650 parts by mass of water was added to the above ethyl acetate solution, and after emulsification and chain extension reaction, ethyl acetate was distilled off at 30 to 40 ° C. under reduced pressure. The concentration was adjusted with water to obtain a colored resin particle dispersion (A2) having a solid content of 20% by mass and a volume average particle diameter of 150 nm.

(Preparation of Colored Resin Particle Dispersion (A3))
In a reaction vessel equipped with a thermometer and a stirrer, 56.2 parts by mass of poly (3-methylpentyl adipate) diol (number average molecular weight 2000), 5 parts by mass of DMPA, 63 parts by mass of hexamethylene diisocyanate (HDI), trimethylolpropane 2 parts by mass were added, and ethyl acetate was added thereto to adjust the solid content to 30% by mass. After the reaction system was replaced with nitrogen gas, the mixture was stirred at 40 ° C. for 3 hours, and then 5.8 parts by mass of triethylamine (1 part) was added. .05 equivalents / carboxyl group). Next, C.I. I. 100 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) was added with stirring. Next, a solution obtained by dissolving 9 parts by mass of sodium dodecyl sulfate in 650 parts by mass of water was added to the above ethyl acetate solution, and after emulsification and chain extension reaction, ethyl acetate was distilled off at 30 to 40 ° C. under reduced pressure. The concentration was adjusted with water to obtain a colored resin particle dispersion (A3) having a solid content of 20% by mass and a volume average particle diameter of 110 nm.

(Preparation of Colored Resin Particle Dispersion (A4))
In a reaction vessel equipped with a thermometer and a stirrer, 35.6 parts by mass of poly (3-methylpentyl adipate) diol (number average molecular weight 2000), 12.6 parts by mass of DMPA, 70.5 parts by mass of hexamethylene diisocyanate (HDI) Then, 2 parts by mass of trimethylolpropane was added, ethyl acetate was added thereto to adjust the solid content to 30% by mass, the reaction system was replaced with nitrogen gas, and the mixture was stirred at 40 ° C. for 3 hours. Parts by weight (1.05 equivalents / carboxyl group) were added. Next, C.I. I. 100 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) was added with stirring. Next, a solution obtained by dissolving 9 parts by mass of sodium dodecyl sulfate in 650 parts by mass of water was added to the above ethyl acetate solution, and after emulsification and chain extension reaction, ethyl acetate was distilled off at 30 to 40 ° C. under reduced pressure. The concentration was adjusted with water to obtain a colored resin particle dispersion (C) having a solid content of 20% by mass and a volume average particle size of 110 nm.

(Preparation of Colored Resin Particle Dispersion (A5))
In a reaction vessel equipped with a thermometer and a stirrer, 34.9 parts by mass of poly (3-methylpentyl adipate) diol (number average molecular weight 2000), 13.9 parts by mass of DMPA, 72 parts by mass of hexamethylene diisocyanate (HDI), Methylolpropane (2 parts by mass) was added, and ethyl acetate was added thereto to adjust the solid content to 30% by mass. After the reaction system was replaced with nitrogen gas, the mixture was stirred at 40 ° C. for 3 hours, and triethylamine (25.9 parts by mass) was added. (1.05 equivalent / carboxyl group) was added. Next, C.I. I. 100 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) was added with stirring. Next, a solution obtained by dissolving 9 parts by mass of sodium dodecyl sulfate in 650 parts by mass of water was added to the above ethyl acetate solution, and after emulsification and chain extension reaction, ethyl acetate was distilled off at 30 to 40 ° C. under reduced pressure. The concentration was adjusted with water to obtain a colored resin particle dispersion (A5) having a solid content of 20% by mass and a volume average particle diameter of 110 nm.

(Preparation of Colored Resin Particle Dispersion (A6))
In a reaction vessel equipped with a thermometer and a stirrer, 74.2 parts by mass of benzyl methacrylate (manufactured by Tokyo Kasei), 1.6 parts by mass of methyl methacrylate (manufactured by Tokyo Kasei), 1 mass of V601 (manufactured by Wako Pure Chemical) After charging the reaction system with nitrogen gas and stirring at reflux temperature for 6 hours, 1.8 parts by mass of triethylamine (1.05 equivalent / carboxyl group) was added. Next, C.I. I. 100 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) was added with stirring. Next, a solution obtained by dissolving 9 parts by mass of sodium dodecyl sulfate in 650 parts by mass of water was added to the above ethyl acetate solution, and after emulsification and chain extension reaction, ethyl acetate was distilled off at 30 to 40 ° C. under reduced pressure. The concentration was adjusted with water to obtain a colored resin particle dispersion (A6) having a solid content of 20% by mass and a volume average particle diameter of 150 nm.

(Preparation of Colored Resin Particle Dispersion (A7))
To a reaction vessel equipped with a thermometer and a stirrer, 8 parts by mass of hexylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 23 parts by mass of DMPA, 92 parts by mass of hexamethylene diisocyanate (HDI), and 2 parts by mass of trimethylolpropane were added. Was added to adjust the solid content concentration to 30% by mass, and the reaction system was replaced with nitrogen gas. After stirring at 40 ° C. for 3 hours, 2.9 parts by mass of triethylamine (1.05 equivalent / carboxyl group) was added. added. Next, C.I. I. 100 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) was added with stirring. Next, a solution obtained by dissolving 9 parts by mass of sodium dodecyl sulfate in 650 parts by mass of water was added to the above ethyl acetate solution, and after emulsification and chain extension reaction, ethyl acetate was distilled off at 30 to 40 ° C. under reduced pressure. The concentration was adjusted with water to obtain a colored resin particle dispersion (A7) having a solid content of 20% by mass and a volume average particle diameter of 170 nm.

<Examples 16 and 17>
C. I. Solvent Black 3 as C.I. I. Solvent Black 7 (manufactured by Tokyo Chemical Industry Co., Ltd.), C.I. I. Colored compositions (A8) and (A9) were prepared in the same manner as in Example 1 except that Disperse Blue 359 (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
An ink composition was prepared in the same manner as in Example 1 except that the colored resin particle dispersion (A1) was changed to the colored resin particle dispersions (A8) and (A9), and the triethylene glycol was changed to tetraethylene glycol. 16, 17 were obtained.
In addition, ink-jet printing and heat treatment were performed in the same manner as in Example 1 except that the ink composition 1 was changed to the ink compositions 16 and 17, respectively, to obtain a colored cloth.

<Examples 18 to 21>
Ink jet printing and heat treatment were performed in the same manner as in Example 1 except that the ink composition 1 was changed to the following ink compositions 18 to 21, respectively, to obtain a colored cloth.
In Example 18, in addition to the pre-treated cotton broad, printing was carried out on a cotton-polyester blend (KDP 6112-58, manufactured by Uji Textile), polyester (KKT3399-58, manufactured by Uji Textile), and This was also performed on untreated cotton broad (D5005, manufactured by Akahori Sangyo Co., Ltd.) to obtain Examples 18a, 18b, and 18c, respectively.

(Preparation of Ink Composition 18)
After mixing and stirring the following components, the mixture was filtered through a polytetrafluoroethylene (PTFE) membrane filter (pore size: 0.8 μm, manufactured by Advantech) to prepare an ink composition 18.
-Colored resin particle dispersion (A1) (dispersed solids 20% by mass), 35 parts by mass-CAB-O-JET200 (self-dispersible pigment, manufactured by Cabot Corporation, 19.92% by mass of dispersed solids), 15 parts by mass Water-soluble organic solvent: tetraethylene glycol (manufactured by Tokyo Kasei), 35 parts by mass Olfin E1010 (manufactured by Nissin Chemical), 1 part by mass Ultrapure water, 14 parts by mass

(Preparation of Ink Composition 19)
After mixing and stirring the following components, the mixture was filtered through a polytetrafluoroethylene (PTFE) membrane filter (pore size: 0.8 μm, manufactured by Advantech) to prepare an ink composition 19.
-Colored resin particle dispersion (A1) (dispersed solids 20% by mass), 30 parts by mass-CAB-O-JET200 (19.92% by mass of dispersed solids), 20 parts by mass-Water-soluble organic solvent: tetraethylene glycol (Tokyo Kasei) 35 parts by mass Olfin E1010 (Nissin Chemical Co., Ltd.), 1 part by mass Ultrapure water, 14 parts by mass

(Preparation of Ink Composition 20)
After mixing and stirring the following components, the mixture was filtered through a polytetrafluoroethylene (PTFE) membrane filter (pore size: 0.8 μm, manufactured by Advantech) to prepare an ink composition 20.
-Colored resin particle dispersion (A1) (dispersed solids 20% by mass), 40 parts by mass-CAB-O-JET200 (dispersed solids 19.92% by mass), 10 parts by mass-Water-soluble organic solvent: tetraethylene glycol (Tokyo Kasei) 35 parts by mass Olfin E1010 (Nissin Chemical Co., Ltd.), 1 part by mass Ultrapure water, 14 parts by mass

(Preparation of Ink Composition 21)
After mixing and stirring the following components, the mixture was filtered through a polytetrafluoroethylene (PTFE) membrane filter (pore size: 0.8 μm, manufactured by Advantech) to prepare an ink composition 21.
-Colored resin particle dispersion (A1) (dispersed solid matter 20% by mass), 45 parts by mass-CAB-O-JET200 (dispersed solid matter 19.92% by mass), 5 parts by mass-Water-soluble organic solvent: tetraethylene glycol (Tokyo Kasei) 35 parts by mass Olfin E1010 (Nissin Chemical Co., Ltd.), 1 part by mass Ultrapure water, 14 parts by mass

<Comparative Examples 1 to 3>
Ink compositions 1x to 3x in the same manner as in Example 1 except that triethylene glycol was changed to diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.), and glycerin (manufactured by Tokyo Chemical Industry Co., Ltd.). Got.
In addition, ink-jet printing and heat treatment were performed in the same manner as in Example 1 except that the ink composition 1 was changed to each of the ink compositions 1x to 3x to obtain a colored cloth.

<Comparative Example 4>
An ink composition 4x was obtained in the same manner as in Example 1, except that the colored resin particle dispersion (A1) was changed to the colored resin particle dispersion (Ax1).
Further, ink-jet printing and heat treatment were performed in the same manner as in Example 1 except that the ink composition 1 was changed to the ink composition 4x and the triethylene glycol was changed to tetraethylene glycol, to obtain a colored cloth.

(Preparation of Colored Resin Particle Dispersion (Ax1))
A reaction vessel equipped with a thermometer and a stirrer was charged with 34 parts by mass of poly (3-methylpentyl adipate) diol (number average molecular weight 2000), 15.1 parts by mass of DMPA, 26.3 parts by mass of IPDI, and 214 parts by mass of ethyl acetate. After the reaction system was replaced with nitrogen gas, the mixture was stirred at 40 ° C. for 3 hours, and 28.7 parts by mass of triethylamine (1.05 equivalent / carboxyl group) was added. Next, C.I. I. 100 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) was added with stirring. Next, a solution obtained by dissolving 9 parts by mass of sodium dodecyl sulfate in 650 parts by mass of water was added to the above ethyl acetate solution, and after emulsification and chain extension reaction, ethyl acetate was distilled off at 30 to 40 ° C. under reduced pressure. The concentration was adjusted with water to obtain a colored resin particle dispersion (Ax1) having a solid content of 20% by mass and a volume average particle diameter of 100 nm.

<Evaluation method>
(Color density)
Using the X-rite (X-rite colorimeter, iPro1) for the colored cloths obtained in each of the examples and comparative examples, the black color density OD (Optical Density) value was measured, and the following criteria were used. The evaluation was carried out using In addition, in the following evaluation, if it is C or more, there is no practical problem.
S: OD value 1.80 or more A: OD value 1.65 or more and less than 1.80 B: OD value 1.60 or more and less than 1.65 C: OD value 1.55 or more and less than 1.60 D: OD Value less than 1.55

(Continuous discharge)
The ink composition used in each of the examples and comparative examples was obtained by printing 100% solid of A4 size on plain paper using the above-described inkjet printer PX-049A, and repeatedly printing continuously without cleaning. Each printed matter was evaluated visually using the following criteria. In addition, in the following evaluation, if it is C or more, there is no practical problem.
A: Continuous printing of three or more A4 size solid images without streaking and blurring is possible.
B: Continuous printing of two A4 size solid images without streaking or blurring is possible.
C: Continuous printing of A4 size solid image is possible on one sheet without streaking or blurring.
D: No A4 size solid image can be printed without streaks or blurring.

The evaluation results are shown below.
In the colored resin particle dispersion, the acid value (mgKOH / g) of the polymer in the colored resin particles, the volume average particle diameter of the colored resin particles, the content (% by mass) of the polymer in the colored resin particles, and the ink Tables 1 to 4 also show the added amount of the colored resin particles in the preparation (content (% by mass) of the colored resin particles with respect to the total mass of the ink composition).
Here, the acid value of the polymer is obtained by applying a polymer prepared without adding a dye to a glass plate in the preparation of colored resin particles, and drying the coating at a temperature of 60 ° C. under a reduced pressure of 20 mmHg for 24 hours to obtain a coating film. Is dissolved in N-methylpyrrolidone and measured according to the indicator titration method of JIS K 1557. The volume average particle diameter of the colored resin particles is obtained by measuring the dispersion of the colored resin particles with a particle size distribution analyzer (Nanotrack UPA). EX150, manufactured by Nikkiso Co., Ltd. (trade name).
Further, regarding the water-soluble organic solvent used for preparing the ink, the solubility and boiling point of the polymer, and the amount of the water-soluble organic solvent added in the ink preparation (content (% by mass) of the water-soluble organic solvent with respect to the total mass of the ink composition) Are also shown in Tables 1 to 4.
Here, the solubility of the polymer was calculated as follows. In the production of the colored resin particles, the aqueous dispersion of the polymer particles produced without adding the dye was allowed to stand on a petri dish at 25 ° C. and dried until there was no loss in mass. 100 g of a water-soluble organic solvent is weighed in a glass vial, the solid of the polymer obtained above is added thereto, and ultrasonic waves are applied by an ultrasonic cleaner (1-6900-01, manufactured by AS ONE Corporation) for 30 minutes. The presence or absence of dissolution was visually evaluated. The weighed value of the polymer solid was appropriately changed, and the solubility (% by mass) was calculated from the weighed value of the maximum amount of the solid that completely dissolved and the mass of the water-soluble organic solvent.

Abbreviations in Tables 1 to 4 below will be described.
SB3: C.I. I. Solvent Black 3
SB7: C.I. I. Solvent Black 7
DB359: C.I. I. Disperse Blue 359
TEG: triethylene glycol (ethers)
TetraEG: tetraethylene glycol (ethers)
PEG400: polyethylene glycol 400 (ethers)
HEP: hydroxyethylpyrrolidone (amides)
HPL: Heptalactam (amides)
DEG: diethylene glycol 2P: 2-pyrrolidone Gly: glycerin TC: cotton, polyester blend PES: polyester

<Example 22>
In the ink composition 2 of Example 2, 10 parts by mass of Elastron BN-77 (block isocyanate, solid content concentration: 30% by mass, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added, and the amount of ultrapure water was reduced to 4 parts by mass. The same operation as in Example 2 was performed to obtain an ink composition 22. The ink composition 22 was subjected to inkjet printing and heat treatment on cotton in the same manner as in Example 2, and then JIS L 0844 (washing resistance), JIS L 0848 (sweat resistance), and JIS L 0849 (rub resistance). As a result of the tests according to (1) and (2), a significant improvement was observed in comparison with Example 2.

  As described above, in the example using the ink of the present invention, good results were obtained in both the color density of the obtained colored cloth and the continuous dischargeability of the ink.

Claims (14)

Water, colored resin particles, and an ink containing a water-soluble organic solvent,
The colored resin particles include at least one polymer selected from the group consisting of (meth) acrylic polymers, polyurethanes and polyureas, and at least one dye selected from the group consisting of oil-soluble dyes and disperse dyes. ,
The acid value of the polymer is 5 to 90 mgKOH / g,
The solubility of the polymer in the water-soluble organic solvent is 0.05% by mass or more;
The water-soluble organic solvent is an ether or an amide,
Ink, wherein the water-soluble organic solvent has a boiling point of 287 ° C. or higher.   The ink according to claim 1, comprising a self-dispersing pigment.   3. The ink according to claim 1, wherein the content of the water-soluble organic solvent is 25 to 45% by mass based on the total mass of the ink. The ink according to any one of claims 1 to 3, wherein the dye is a compound represented by the following general formula (MA).

In Formula (MA), R ^{1 to} R ²⁰ each independently represent a hydrogen atom or a substituent.   The dye is C.I. I. The ink according to any one of claims 1 to 4, wherein the ink is Solvent Black 3.   The ink according to any one of claims 1 to 5, wherein the polymer has an acid value of 10 to 80 mgKOH / g.   The ink according to any one of claims 1 to 6, wherein the polymer is a polyurethane.   The ink according to any one of claims 1 to 7, further comprising a crosslinking agent.   The ink according to any one of claims 1 to 8, which is used for inkjet.   The ink according to any one of claims 1 to 9, which is for printing.   An ink-jet printing method comprising a step of printing the ink according to any one of claims 1 to 10 on a fabric by an ink-jet method.   The inkjet printing method according to claim 11, further comprising a heat treatment step.   An ink cartridge containing the ink according to claim 1.   An ink jet printer comprising the ink according to claim 1.