WO2020004228A1 - Ink, ink cartridge, ink set, inkjet printer, and inkjet textile printing method - Google Patents

Abstract

The present invention provides: an ink which comprises water, an aqueous organic solvent, and colored resin particles, wherein the resin particles comprise a resin (B) and a dye (A) represented by a specific structure, and the mass ratio (dye (A))/(resin (B)) between the dye (A) and the resin (B) is at least 1.2; an ink cartridge being loaded with said ink; an ink set; an inkjet printer; and an inkjet textile printing method comprising a step for printing on a cloth with said ink by an inkjet method.

Description

Ink, ink cartridge, ink set, inkjet printer and inkjet printing method

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

Conventionally, a colorant used for coloring a fabric is either a dye or a pigment, and as a method of industrially coloring a fabric using these colorants, a screen printing method, a roller printing method, a transfer method, Ink jet systems and the like have been used. In particular, the ink jet method does not require the production of a plate compared to other methods, can quickly form an image with excellent gradation, and further uses only the required amount of ink as a formed image, so that waste liquid is reduced. It can be said that this is an excellent image forming method having environmental advantages such as a small amount.

Patent Literature 1 describes a printing ink including a coloring agent including a coloring material including a polymer compound, water, and a water-soluble organic solvent.
Patent Literature 2 describes an aqueous ink for inkjet containing a dispersion and a disperse dye.
Patent Document 3 discloses an inkjet printing liquid containing heat-reactive composite resin particles in an aqueous medium.
Patent Document 4 describes an inkjet ink including an aqueous medium and a capsule including a core containing one or more thermosetting compounds, a polymer shell surrounding the core.

Japanese Patent Application Laid-Open No. 2008-69203 Japanese Patent Application Laid-Open No. 10-168151 WO 2017/021278 European Patent No. 2933374

However, even these methods are insufficient from the viewpoint of simultaneously satisfying the color developing property of the image, the inkjet discharge property, the stability over time, and the color fastness (washing resistance, rub resistance, and sweat resistance), Needs improvement

It is an object of the present invention to color various kinds of fabrics, and to obtain the color development, inkjet dischargeability, stability with time, and color fastness (washing resistance, rub resistance, and sweat resistance) of an obtained image. An object of the present invention is to provide an ink excellent in the above, an ink cartridge filled with the ink, an ink set, an ink jet printer, and an ink jet printing method using the ink.

課題 Specifically, the object of the present invention has been achieved by the following means.

[1]
It contains water, an aqueous organic solvent, and colored resin particles, and the colored resin particles contain a dye (A) and a resin (B) represented by the following formula (1), and the dye (A) and the resin (B) Wherein the mass ratio (dye (A)) / (resin (B)) is 1.2 or more.

In equation (1),
R ₁₀₁ to R ₁₂₀ each independently represent a hydrogen atom or a substituent.

[2]
The ink according to [1], wherein the mass ratio of the dye (A) to the resin (B) (dye (A)) / (resin (B)) is 2 to 9.

[3]
The ink according to [1] or [2], wherein the resin has at least one selected from a carboxyl group, a salt of a carboxyl group, and a polyalkyleneoxy structure.

[4]
The ink according to any one of [1] to [3], wherein the resin is at least one selected from a urethane resin and a resin having a (meth) acrylate repeating unit.

[5]
The aqueous organic solvent contains 17% by mass or more based on the ink of a solvent having a boiling point of 150 ° C. or more at 1 atm consisting of only carbon atoms, hydrogen atoms, and oxygen atoms, or contains only carbon atoms, hydrogen atoms, and oxygen atoms. The ink according to any one of [1] to [4], comprising a solvent having a boiling point of 200 ° C. or more at 1 atm in an amount of 15% by mass or more based on the ink.

[6]
The ink according to any one of [1] to [5], wherein the aqueous organic solvent contains tetraethylene glycol.

[7]
The ink according to any one of [1] to [6], further comprising a crosslinking agent.
[8]
The ink according to any one of [1] to [7], further comprising a wax.
[9]
The ink according to any one of [1] to [8], further comprising a pigment.

[10]
The ink according to any one of [1] to [9], wherein the ink is for inkjet.
[11]
The ink according to any one of [1] to [9], wherein the ink is for printing.

[12]
An ink-jet printing method comprising the step of printing the ink according to any one of [1] to [11] on a fabric by an ink-jet method.
[13]
The inkjet printing method according to [12], further comprising a heat treatment step.
[14]
The inkjet printing method according to [12] or [13], further comprising a pretreatment step of applying an aqueous pretreatment liquid containing a coagulant to the fabric to obtain a pretreated fabric.
[15]
The inkjet printing method according to [14], wherein the coagulant is an ammonium cationic polymer.
[16]
The inkjet printing method according to any one of [12] to [15], wherein the fabric contains at least one of cotton and polyester.

[17]
An ink set containing at least a black ink, a yellow ink, a magenta ink, and a cyan ink, wherein the black ink is the ink according to any one of [1] to [11].
[18]
An ink cartridge filled with the ink according to any one of [1] to [11].
[19]
An ink jet printer filled with the ink according to any one of [1] to [11].
[20]
What is claimed is: 1. A method for producing an aqueous dispersion of colored resin particles comprising colored resin particles containing a dye and a resin dispersed in water, comprising the following steps (1) and (2).
Step (1): a step of emulsifying a mixture containing the dye (a), resin (b), water (c), and organic solvent (d) represented by the following formula (1) to obtain an emulsion. (2): a step of removing the organic solvent (d) from the emulsion obtained in the step (1), provided that the mass of the dye (a) and the resin (b) in the mixture of the step (1) The ratio (a) / (b) is 1.2 or more, and the mass ratio (a) / (d) of the dye (a) and the organic solvent (d) in the mixture in the step (1) is 1 /. 9 to 1/1.

In equation (1),
R ₁₀₁ to R ₁₂₀ each independently represent a hydrogen atom or a substituent.

ADVANTAGE OF THE INVENTION According to this invention, various types of cloths can be colored, and extremely high color developing property, inkjet dischargeability, and stability over time can be achieved. Furthermore, dyeing fastness (washing resistance, abrasion resistance, Ink, an ink cartridge filled with the ink, an ink set, an ink jet printer, and an ink jet printing method using the ink.
In the present invention, by using a specific dye, by containing it in the colored resin particles at a high concentration, while suppressing the solid content concentration in the ink, it is possible to increase the dye concentration in the ink, thereby extremely It is presumed that both high color developability, inkjet dischargeability, and stability over time can be achieved. Furthermore, since the content of the water-dispersible resin contained in the colored resin particles is small, good properties are exhibited even in a fastness test for contact with water such as washing, sweat, and wet friction.

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, 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), an aryloxy group (preferably having a carbon number of 30). 6 to 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.

に お い て In this specification, “(meth) acrylate” is used to mean “either or both of acrylate and methacrylate”. The same applies to “(meth) acrylic group”, “(meth) acrylic acid”, “(meth) acrylamide”, “(meth) acryloyl group”, “(meth) acrylic” and the like.

[ink]
The ink of the present invention contains (a) water, (b) an aqueous organic solvent, and (c) colored resin particles, wherein the colored resin particles are a dye (A) represented by the following formula (1), and a resin ( B), wherein the mass ratio (dye (A)) / (resin (B)) of the dye and the resin represented by the following formula (1) is 1.2 or more.

In equation (1),
R ₁₀₁ to R ₁₂₀ each independently represent a hydrogen atom or a substituent.

<(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 of the present invention is preferably from 40 to 80% by mass, more preferably from 45 to 75% by mass, and particularly preferably from 50 to 75% by mass. When the content of water is within the above range, the stability of the ink is excellent (the sedimentation is unlikely to occur), and the ejection stability of the inkjet ink is also excellent.

<(B) aqueous organic solvent>
The ink of the present invention contains an aqueous organic solvent.
The aqueous 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 is mixed with water at an arbitrary ratio. Are particularly preferred. Examples of the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, 1,2,6 -Hexanetriol, thioglycol, hexylene glycol, glycerin, diglycerin, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,5-pentanediolol, 1,6-hexanediol, ethylene glycol monoethyl ether, Examples include ethylene glycol monobutyl ether and acetonitrile. Preferred are trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, glycerin, 2-pyrrolidone, 1,5-pentanediol, 1,6-hexanediol, and ethylene glycol monobutyl ether. Preferred are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, 2-pyrrolidone, ethylene glycol monobutyl ether and tetraethylene glycol, and particularly preferred are ethylene glycol, glycerin, 2-pyrrolidone and tetraethylene glycol.
The aqueous organic solvent preferably contains tetraethylene glycol.

含有 The content of the aqueous organic solvent in the ink is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass. When the content of the aqueous organic solvent is within the above range, the stability of the ink is excellent (sedimentation and the like are unlikely to occur), and the ejection stability as an inkjet ink is also excellent.

Further, from the viewpoint of suppressing discoloration, the water-soluble organic solvent preferably contains a solvent consisting of only carbon atoms, hydrogen atoms, and oxygen atoms. More preferably, the content is 30% by mass or more based on the organic solvent.

Furthermore, the water-soluble organic solvent contains only a carbon atom, a hydrogen atom, and an oxygen atom, and contains 17% by mass or more of a solvent having a boiling point of 150 ° C. or more at 1 atm with respect to the ink. It is preferable that a solvent containing only oxygen atoms and having a boiling point of 200 ° C. or more at 1 atm is contained in the ink in an amount of 15% by mass or more. By using the solvent having the above boiling point in a prescribed amount or more, the association of the dye of the formula (1) on the fabric can be suppressed, and the dyeing density can be improved.
In addition, 1 atmospheric pressure is 101325 Pa.

Examples of the solvent containing only carbon atoms, hydrogen atoms, and oxygen atoms include propylene glycol (boiling point: 188.2 ° C.), ethylene glycol (boiling point: 197.3 ° C.), diethylene glycol (boiling point: 244.3 ° C.), and diethylene glycol (boiling point: 244.3 ° C.). ° C), triethylene glycol (boiling point 276 ° C), tetraethylene glycol (boiling point 314 ° C), and glycerin (boiling point 290 ° C) are preferred.

<(C) Colored resin particles>
The ink of the present invention contains colored resin particles.
The average particle size of the colored resin particles is preferably 200 nm or less, more preferably 20 to 200 nm, and further preferably 40 to 150 nm. When the average particle diameter of the colored resin particles is 200 nm or less, it is easy to directly print on a fabric by an inkjet 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.

The colored resin particles in the ink of the present invention contain the dye (A) represented by the following formula (1) and the resin (B), and have a mass ratio of the dye represented by the following formula (1) to the resin (dye ( A)) / (Resin (B)) is 1.2 or more.

In equation (1),
R ¹⁰¹ to R ¹²⁰ each independently represent a hydrogen atom or a substituent.

(Dye (A) represented by formula (1))
In equation (1),
R ¹⁰¹ to R ¹²⁰ 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).

It is preferable that R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group. The alkyl group is more preferably an alkyl group having 1 to 30 carbon atoms, further preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms, and most preferably represents a methyl group.
R ¹⁰¹ and R ¹⁰² preferably represent a hydrogen atom.

The substituent for R ₁₀₃ to R ₁₁₈ is more preferably a halogen atom, an alkyl group, an alkoxy group, a nitro group, an aryl group, an acylamino group, or an alkoxycarbonyl group.
R ₁₀₃ to R ₁₁₈ preferably represent a hydrogen atom.

R ¹¹⁹ and R ¹²⁰ 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.

When R ¹⁰¹ to R ¹²⁰ each independently represent a substituent, each substituent may have a further substituent. The further substituent is not particularly limited, and examples thereof include a substituent selected from the above-mentioned substituent group A1.

染料 As the dye (A) represented by the above formula (1), C.I. I. Solvent Black 3 is preferred. C. I. Solvent Black 3 can be a commercially available product, for example, Oil Black HBB, Oil Black 860 (both manufactured by Orient Chemical Industry Co., Ltd.).

(Resin (B))
As the resin (B), any resin may be used as long as it can disperse the dye (A) in water. Preferred resins include urethane resins, resins having (meth) acrylate repeating units, and polyvinyl alcohol. And an acetal thereof, a formalin condensate of an aromatic sulfonate, and the like. From the viewpoint of color fastness, the resin (B) is at least selected from a urethane resin and a resin having a (meth) acrylic repeating unit. It is preferable to use one type.

The resin (B) is preferably a resin having at least one selected from a carboxyl group, a salt of a carboxyl group, and a polyalkyleneoxy structure. By having these functional groups, it has good ink stability, and also has good washing resistance and sweat resistance.

(Urethane resin)
The urethane resin may be synthesized by a known method, or a commercially available product may be used.
As the urethane resin, a resin obtained by reacting a polyisocyanate and a polyol is preferable. The polyisocyanate is not particularly limited as long as the polyisocyanate contains two or more isocyanate groups in one molecule. Examples of polyisocyanates 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, and specific examples thereof include aliphatic and alicyclic compounds such as HDI, IPDI, dodecane diisocyanate, cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate. Diisocyanates or mixtures of these isocyanates are more preferred.

The polyol is not particularly limited as long as it contains two or more hydroxyl groups in one molecule, and for example, a polymer polyol or a low molecular weight polyol can be used. Examples of the polymer polyol include a polyether polyol, a polyester polyol, and a polycarbonate polyol.
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 ( Diols having an alicyclic structure having 6 to 12 carbon atoms, such as (hydroxyethyl) cyclohexane, 2,7-norbornanediol, tetrahydrofuranmethanol, and 2,5-bis (hydroxymethyl) -1,4-dioxane; 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, -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 1,2-methyl-1,8-octanediol; alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; glycerin, trimethylolethane, trimethylolpropane, Polyfunctional glycols such as butyrolpropane, 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 following method for producing a 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 colored resin in water and imparting dispersion stability of a colored resin particle dispersion. Examples of the carboxyl group-containing polyol include, but are not limited to, 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 (aliphatic tertiary such as trimethylamine, triethylamine triethanolamine, N-methyldiethanolamine and 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, neutralize the carboxyl group and / or sulfonic acid group with a neutralizing agent to form a carboxylate group and / or sulfonate group. Can be. The amount of the neutralizing agent used is preferably such that 10 to 100 mol% of the carboxyl groups and / or sulfonic acid groups contained in the resin is neutralized, preferably 50 to 98 mol%, more preferably 70 to 95 mol%. It is.

(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, amines (primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propylamine and octylamine), secondary monoamines (dimethylamine, diethylamine and dibutylamine), tertiary monoamines ( 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 the like. Use of two or more types 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.

The urethane resin may have a crosslinked structure.
The crosslinked structure refers to a structure obtained by using, as at least one monomer, a compound having a total of three or more hydroxyl groups and isocyanate groups in the molecule.
Examples of the compound having three or more hydroxyl groups and isocyanate groups in the molecule include trimethylolpropane, trimethylolethane, and pentaerythritol.

The urethane resin may further have a urea bond. A resin having a urethane bond and a urea bond is also referred to as “urethane / urea resin”.
One type of preferred embodiment of the dye polymer in the present invention is a urethane / urea resin in which a first partial structure containing a urethane bond and a second partial structure containing a urethane bond are bound by a urea bond.

The colored resin particles are preferably used as a dispersion.
A method for producing a colored resin particle dispersion using, for example, a urethane resin as the resin (B) is not particularly limited, and examples thereof include the following methods. A polymer having two or more isocyanate groups in one molecule 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 isocyanate, a polyol having two or more hydroxyl groups in one molecule, an acidic group-containing polyol or a salt thereof is urethanized by a one-shot method or a multi-stage method to synthesize a urethane resin, and if necessary, the urethane resin Is neutralized with a neutralizing agent, a dye is added, water is dropped to a place where the reaction solution is vigorously stirred, and a solvent is removed as necessary to obtain a colored resin particle dispersion. Can be

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.

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

(Resin having (meth) acrylate repeating unit)
As the resin having a (meth) acrylate repeating unit, any resin may be used as long as it has a (meth) acrylate repeating unit. However, a resin composed of only a (meth) acrylate repeating unit and copolymerizable with (meth) acrylate Examples of the resin include a resin made of a copolymer with a monomer.
As the resin having a (meth) acrylate repeating unit, a resin having a hydrophilic repeating unit and a hydrophobic repeating unit is preferable.

Examples of the hydrophobic repeating unit include a linear alkyl (meth) acrylate (preferably a linear alkyl (meth) acrylate having 3 to 18 carbon atoms) and a branched alkyl (meth) acrylate (preferably a branched alkyl (meth) acrylate having 3 to 18 carbon atoms) (Meth) acrylate, more preferably isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate), aliphatic (meth) acrylate having a ring structure (preferably cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl ( (Meth) acrylate, adamantyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, etc. (meth) acrylate having an aromatic group (preferably phenyl (meth) acrylate, benzyl (meth) acrylate Over DOO, phenethyl (meth) acrylate, phenoxyethyl (meth) acrylate, naphthyl (meth) acrylate), and (meth) acrylate and copolymerizable with styrene derivatives (preferably styrene).

As the hydrophilic repeating unit, a repeating unit having a hydrophilic group selected from a hydroxyl group, an acid group (preferably a carboxyl group, a sulfonic acid group, a phosphoric acid group) or a salt thereof, and a polyoxyalkylene group is preferred.
Specifically, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl acid phosphate, polyethylene glycol monomethyl ether (meth) A) acrylate, styrene carboxylic acid, styrene sulfonic acid and the like.
Among them, a copolymer having at least a hydrophobic (meth) acrylate and a methacrylate having an acid group, and a copolymer having at least styrene and a (meth) acrylate having an acid group are preferable.

A method for producing a colored resin particle dispersion using a resin having a (meth) acrylate repeating unit as the resin (B) is not particularly limited, and examples thereof include the following methods.
A monomer containing a (meth) acrylate monomer is polymerized in an organic solvent using a known method (for example, a radical polymerization method) to obtain a resin solution, and then a dye (A), water and, if necessary, a neutralizing agent A method in which a surfactant is added and emulsification is performed, and then the solvent is removed. Alternatively, the dye (A), a monomer, and an emulsifier (for example, a surfactant) are emulsified in water, and the monomer is dissolved in the presence of a polymerization initiator. A method of obtaining a colored resin particle dispersion by polymerization.

The content of the hydrophobic repeating unit in the resin having the (meth) acrylate repeating unit is preferably from 30 mol% to 95 mol%, more preferably 50 mol%, based on all repeating units of the resin having the (meth) acrylate repeating unit. % To 90 mol% is more preferred.
The content of the hydrophilic repeating unit in the resin having the (meth) acrylate repeating unit is preferably from 5 mol% to 70 mol%, more preferably 10 mol%, based on all repeating units of the resin having the (meth) acrylate repeating unit. % To 50 mol% is more preferred.

The weight average molecular weight (Mw) of the resin (B) is preferably from 1500 to 1,000,000, more preferably from 2,000 to 500,000, and still more preferably from 5,000 to 200,000. The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin (B) can be measured by gel permeation chromatography (GPC).
In the present specification, GPC was measured using HLC-8220GPC (manufactured by Tosoh Corporation) and columns were measured using TSKgel SuperHZM-H, TSKgel SuperHZ4000, 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.

The acid value of the resin is preferably from 5 to 200 mgKOH / g, more preferably from 10 to 150, still more preferably from 20 to 130 mgKOH / g, and particularly preferably from 30 to 120 mgKOH / 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, if the acid value is 200 mgKOH / g or less, the hydrophilicity of the ink film of the dispersion of the colored resin particles after heat fixing does not increase, and the color fastness such as washing resistance and sweat resistance does not decrease. preferable.
Here, the acid value of the resin is defined by the acid value of the resin before neutralization. For example, when the resin contains a carboxylate or a sulfonate neutralized by a base, the acid value is calculated on the assumption that the resin contains a carboxylic acid or a sulfonic acid that is not neutralized.
The acid value can be measured according to the indicator titration method of JIS K 1557.

で は In the present invention, the mass ratio (dye (A)) / (resin (B)) of the dye (A) and the resin (B) represented by the above formula (1) in the colored resin particles is 1.2 or more. Preferably, the ratio of (dye (A)) / (resin (B)) is 1.5 or more, more preferably 2 or more, and still more preferably 2.5 or more. When the ratio of (dye (A)) / (resin (B)) is 1.2 or more, the concentration of the dye can be increased without increasing the solid concentration in the ink, and a high dyeing concentration can be achieved. Agglomeration between the colored resin particles can be suppressed, and both inkjet dischargeability and temporal stability can be achieved. The upper limit of (dye (A)) / (resin (B)) is preferably 19 or less, more preferably 9 or less, still more preferably 7 or less, and particularly preferably 5.5 or less. By setting (dye (A)) / (resin (B)) to an appropriate upper limit, the dispersion stability of the colored resin particles is improved, and the ink jetting property and the stability over time are further improved.

The content of the colored resin particles in the ink of the present invention is preferably from 1 to 20% by mass, more preferably from 2 to 15% by mass, and more preferably from 3 to 12% by mass, based on the total amount of the ink, from the viewpoints of ensuring ejection stability and color development. Is more preferred.
The content of the dye (A) in the ink of the present invention is preferably 0.5 to 15% by mass, more preferably 1 to 12% by mass, and further preferably 2 to 10% by mass, based on the total amount of the ink.

In the ink jet printing method of the present invention, a crosslinking agent described below can be used in order to further increase the adhesion between the fabric and the resin and improve the image fastness. Therefore, the resin 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.
It is also preferable not to use a crosslinking agent in the inkjet ink for textile printing. It is also preferred that the colored fine particles of the inkjet ink for textile printing do not contain a crosslinking agent. Furthermore, it is also preferred that the resin does not have a group that can react with the crosslinkable group of the crosslinking agent.

In the colored resin particles of the ink of the present invention, the specific dye is preferably present in a form covered with the resin. 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 colored resin particles preferably have a form in which the dye is included in the polymer, that is, have a core-shell structure. The core is made of the specific dye, and the shell is made of the resin.
The core-shell structure can be confirmed by a transmission electron microscope (TEM).

<(D) Crosslinking agent>
The ink of the present invention may further contain a crosslinking agent.
As described above, in the inkjet printing method of the present invention, it is preferable to use a crosslinking agent in order to further increase the adhesion between the fabric and the resin and improve the image fastness. It is preferable that the resin and the component constituting the fabric are bonded by the cross-linking 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 sulfonic acid 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.
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 90 ° C to 180 ° C, more preferably in the range of 90 ° C to 120 ° C, and particularly preferably in the range of 110 ° C to 120 ° C.
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.

The crosslinking agent is preferably present in the ink of the present invention in the form of particles. The crosslinker in the form of particles is referred to as “crosslinker particles”.

It is preferable that the cross-linking agent particles have a volume average particle diameter (MV) of 200 nm or less from the viewpoint of improving dischargeability in ink jet.
The volume average particle diameter can be measured by the same method as the above-described colored resin particles.

Examples of the crosslinking agent particles include, but are not limited to, elastron BN-77 (block isocyanate, volume average particle diameter 19 nm, dissociation temperature of 120 ° C. or higher, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), elastron BN- 27 (block isocyanate, volume average particle diameter 108 nm, dissociation temperature of 180 ° C. or higher, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), duranate WM44-70G (block isocyanate, volume average particle diameter 42 nm, dissociation temperature of about 90 ° C., manufactured by Asahi Kasei Corporation), TRIXENE AQUA BI200 (block isocyanate, volume average particle diameter 94 nm, dissociation temperature 110-120 ° C., manufactured by BAXENDEN) and the like.

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 resin and the fabric. More preferably, it is 8 to 8% by mass, and still more preferably 1 to 5% by mass.

<(E) Pigment>
The ink of the present invention preferably further contains a pigment. The pigment is preferably dispersed in the ink of the present invention.
As described above, in the ink jet printing method of the present invention, the resin forms a film on the fabric, but depending on the color, the pigment is further dispersed in the film to adjust the hue or to increase the color density. It is preferable because it can be increased. Only one pigment may be used, or two or more pigments may be used.

顔料 The pigment that can be used in the present invention is not particularly limited, and examples thereof include carbon black and aniline black. As the pigment, any of a water dispersion of a pigment obtained by dispersing a pigment in water using a dispersant or a self-dispersion pigment can be preferably used, and a self-dispersion pigment is preferable. Examples of self-dispersible pigments that can be used include self-dispersible carbon blacks CAB-O-JET # 200, 300, and 400 (all manufactured by Cabot Corporation), BONJET CW-1 (500 μmol / g as a carboxy group), and CW-CW-1. Commercial products such as -2 (470 μmol / g as a carboxy group) (above, manufactured by Orient Chemical Co., Ltd.) and Aqua-Black # 162 (about 800 μmol / g as a carboxyl group) of Tokai Carbon Co., Ltd.

When the inkjet ink for textile printing of the present invention contains a pigment, the content of the pigment in the inkjet ink for textile printing is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0.5 to 10% by mass. 5 mass% is more preferred.

<Wax>
The ink of the present invention preferably contains a wax. The frictional resistance of the obtained ink film surface can be reduced, and the frictional property can be improved.

The wax is preferably present in the ink of the present invention in the form of particles. The wax in the form of particles is called "wax particles".
As the wax particles, it is preferable to use a dispersion in which the wax is dispersed in water. As the wax, polyethylene (also expressed as olefin), paraffin, carnauba (also expressed as ester) is preferable, and more preferably. Carnauba is used from the viewpoint of improving the frictional property and the color density. These may be used alone or in combination of two or more, or two or more may be used as particles of a mixture thereof.
The dispersion form of the wax particles is preferably anionic or nonionic, and particularly preferably nonionic. In the present invention, it is considered that the nonionic property makes it easy for the wax component to be unevenly distributed on the surface of the ink film. In addition, when a colorless component other than the colorant is included in the ink, the interaction between the colorant and the pretreatment agent on the fabric is usually inhibited, and the color density may be deteriorated. It is presumed that the use can suppress the deterioration of the color density.

The melting point of the wax is preferably in the range of 60 ° C. to 120 ° C., and more preferably in the range of 60 ° C. to 100 ° C., from the viewpoint of improving stability and frictional properties. By increasing the melting point, the stability of the printing ink can be improved. On the other hand, not increasing the melting point more than necessary is effective for improving the friction property.
The melting point of the wax can be measured with a general melting point measuring device.

(4) The volume average particle diameter (MV) of the wax particles is preferably 0.3 μm or less, more preferably 0.2 μm or less, and particularly preferably 0.1 μm or less, from the viewpoint of dischargeability in ink jet.

The content of the wax in the ink is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 1 to 5% by mass.

As the wax particles, commercially available products may be used, and without particular limitation, examples thereof include Polylon L-787 (manufactured by Chukyo Yushi Co., Ltd., polyethylene, nonion, melting point of 102 ° C., volume average particle diameter of 0.1 mm). 1 μm), Hydrin-703 (Chukyo Yushi Co., Ltd., paraffin, anion, melting point 75 ° C., volume average particle size 0.1 μm), R108 (Chukyo Yushi Co., Ltd., paraffin, nonion, melting point 66 ° C., average particle size 0.2 μm) ), Cellosol 524 (manufactured by Chukyo Yushi Co., Ltd., carnauba, nonion, melting point: 83 ° C., volume average particle size: 0.07 μm), and more preferably, R108 (manufactured by Chukyo Yushi Co., paraffin, nonion, melting point: 66 ° C.) , Volume average particle diameter 0.2 μm), Cellosol 524 (manufactured by Chukyo Yushi Co., Ltd., carnauba, nonion, melting point 83 ° C., volume average particle diameter 0.07 μm) ). Particularly preferred, Cellosol 524 (Chukyo Yushi Co., carnauba, nonionic, mp 83 ° C., a volume-average particle diameter 0.07 .mu.m) and the like.

<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.

The ink of the present invention is preferably an ink-jet ink (ink-jet ink).
Further, the ink of the present invention is preferably a printing ink, and particularly preferably an inkjet ink for printing.

<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.

イ ン ク The ink 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.

When the ink of the present invention is used for inkjet (ink-jet ink), the surface tension of the ink at 25 ° C. is preferably adjusted to 20 mN / m to 70 mN / m, and adjusted to 25 mN / m to 60 mN / m. Is more 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.

[ink cartridge]
The ink cartridge of the present invention is an ink cartridge filled with the above-described ink of the present invention (preferably an ink jet printing ink).

[Inkjet printer]
The ink jet printer of the present invention is an ink jet printer filled with the ink of the present invention (preferably an ink jet printing ink).

[Ink set]
By using an ink set containing the ink of the present invention (preferably an inkjet ink for textile printing), a clearer image can be obtained when performing multicolor printing. The ink set preferably contains at least one selected from a black ink, a cyan ink, a magenta ink, and a yellow ink, and contains all the black ink, cyan ink, magenta ink, and yellow ink. Is preferred. Among these, the black ink is the ink of the present invention, so that the image clarity is particularly excellent.

染料 As the cyan ink, magenta ink, yellow ink and other color inks used in the ink set of the present invention, dye or pigment inks are preferable.

The dye is not particularly limited, but the following dyes are particularly preferable. 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: 1,35,55,56,58,64,64: 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.

As a pigment,
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.

[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 (preferably an 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 process is unnecessary, the process 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 in the second aspect 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 an aqueous dispersion of a dye, a resin or a pigment, but is not particularly limited, and may be an organic acid, a polyvalent metal salt, and a cationic compound. It is preferable that at least one kind is selected.
In particular, when the aggregating agent is a cationic compound or a polyvalent metal salt and the colored resin particles have an anionic group (preferably an acid group), a high-concentration colored cloth can be formed by printing with the above-described inkjet printing method. Obtainable. This is because the pre-treated cationic compound or polyvalent metal salt aggregates at the moment of contact with the ink containing the colored resin particles having an anionic group and stays on the fabric surface, resulting in a surface It is considered that the amount of the dye present in the dye increases and the concentration can be 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, 3- 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. 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 resin is likely to 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 220 ° C, more preferably from 130 to 200 ° C. 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>
The fabric colored with the inkjet ink for textile printing of the present invention is 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.
Among these, the effects of the present invention are remarkably exhibited when applied to a fabric containing at least one selected from cotton and polyester (specifically, cotton, polyester, and a blend of cotton / polyester).
Clothing includes T-shirts, trainers, jerseys, pants, sweatsuits, dresses, blouses, and the like. It is also suitable for bedding and handkerchiefs.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not construed as being limited by the following Examples.

(Synthesis of urethane resin U-1)
In a closed reaction vessel equipped with a thermometer and a stirrer, 50 parts by mass of poly (caprolactone) diol (number average molecular weight 520), 15.2 parts by mass of 2,2-dimethylolbutanoic acid (DMBA), hexamethylene diisocyanate (HDI) 80 parts by mass, 2 parts by mass of trimethylolpropane, and 98.4 parts by mass of ethyl acetate were charged, and 0.08 part by weight of Neostan U-600 (trade name, manufactured by Nitto Kasei Kogyo KK) was added as a catalyst. Was. After replacing the reaction system with nitrogen gas, the reaction was carried out at 70 ° C. for 12 hours with stirring. Then, a urethane resin (U-1) having a residual isocyanate group at a terminal was synthesized. The presence of the residual isocyanate group was confirmed by potentiometric titration. Ethyl acetate was added thereto to adjust the solid content to 30% by mass. The obtained urethane resin (U-1) had a weight average molecular weight in terms of polystyrene of 6,400 and an acid value of 39 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RU-1)
C. I. 17.6 parts by mass of a solution obtained by dissolving Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) at a concentration of 30% by mass in ethyl acetate, 30% by mass of the obtained urethane resin (U-1) 3.2 parts by mass of an ethyl acetate solution, 0.9 equivalent of triethylamine with respect to the carboxyl group, and 10.4 parts by mass of ethyl acetate were mixed. This was mixed with 47.4 parts by mass of a 1% aqueous solution of sodium dodecyl sulfate, and emulsified at 16,000 rpm for 12 minutes using a homogenizer (ED-1 manufactured by Nippon Seiki Co., Ltd.). After the obtained emulsion was filtered using a 1-micron filter, the mixture was heated to 45 ° C. under aeration and stirring conditions, a part of the organic solvent and water were distilled off, and the mixture was filtered with a 0.8-micron filter to obtain a solid content concentration. A colored resin particle dispersion (RU-1) of 20% by mass was obtained.
The acid value of the resin in the colored resin particle dispersion (RU-1) was 39 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RU-2)
C. I. Synthesis of a colored resin particle dispersion RU-1 except that Solvent Black 3 was replaced by 11.4 parts by mass of a 30% by mass ethyl acetate solution and urethane resin (U-1) was replaced by 9.4 parts by mass of a 30% by mass ethyl acetate solution. Using the same technique as described above, a colored resin particle dispersion RU-2 was synthesized.
The acid value of the resin in the colored resin particle dispersion (RU-2) was 39 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RU-3)
C. I. Synthesis of Colored Resin Particle Dispersion RU-1 except that Solvent Black 3 was replaced with a 30% by mass ethyl acetate solution of 13.9 parts by mass and a urethane resin (U-1) was replaced with 6.9 parts by mass of a 30% by mass ethyl acetate solution. Using the same technique as described above, a colored resin particle dispersion RU-3 was synthesized.
The acid value of the resin in the colored resin particle dispersion (RU-3) was 39 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RU-4)
C. I. Synthesis of colored resin particle dispersion RU-1 except that Solvent Black 3 was replaced by 30% by mass of ethyl acetate solution of 14.9 parts by mass and urethane resin (U-1) by 30% by mass of ethyl acetate solution of 5.9 parts by mass. Using the same technique as described above, a colored resin particle dispersion RU-4 was synthesized.
The acid value of the resin in the colored resin particle dispersion (RU-4) was 39 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RU-5)
C. I. Synthesis of Colored Resin Particle Dispersion RU-1 except that Solvent Black 3 was replaced by 18.2 parts by mass of a 30% by mass ethyl acetate solution and urethane resin (U-1) by 2.6 parts by mass of a 30% by mass ethyl acetate solution. Using the same technique as described above, a colored resin particle dispersion RU-5 was synthesized.
The acid value of the resin in the colored resin particle dispersion (RU-5) was 39 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RU-6)
C. I. Synthesis of colored resin particle dispersion RU-1 except that Solvent Black 3 was replaced by 18.9 parts by mass of a 30% by mass ethyl acetate solution and urethane resin (U-1) was replaced by 2.1 parts by mass of a 30% by mass ethyl acetate solution. Using the same technique as described above, a colored resin particle dispersion RU-6 was synthesized.
The acid value of the resin in the colored resin particle dispersion (RU-6) was 39 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RU-7)
C. I. Synthesis of colored resin particle dispersion RU-1 except that Solvent Black 3 was changed to 19.3 parts by mass of a 30% by mass ethyl acetate solution and urethane resin (U-1) was changed to 1.5 parts by mass of a 30% by mass ethyl acetate solution. Using the same technique as described above, a colored resin particle dispersion RU-7 was synthesized.
The acid value of the resin in the colored resin particle dispersion (RU-7) was 39 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion X-1 for Comparison)
C. I. Synthesis of colored resin particle dispersion RU-1 except that Solvent Black 3 was replaced by 10.4 parts by mass of a 30% by mass ethyl acetate solution and urethane resin (U-1) by 10.4 parts by mass of a 30% ethyl acetate solution. Using the same technique, a colored resin particle dispersion X-1 was synthesized.
The acid value of the resin in the colored resin particle dispersion (X-1) was 39 mgKOH / g.

染料 The dye / resin (mass ratio) and average particle diameter (MV) of the obtained colored resin particle dispersion were as shown in Table 1 below. The resin or prepolymer used is also described.

(Synthesis of Resin A-1 Having (meth) acrylate Repeating Unit)
Under a nitrogen stream, 78 g of ethyl acetate was heated to 75 ° C. A solution prepared by dissolving 86.3 g of benzyl methacrylate (M-1), 18.1 g of methacrylic acid (M-4), and 3.5 g of V-65 manufactured by Wako Pure Chemical Industries as a polymerization initiator in 78 g of ethyl acetate was used as a solution. It was dropped over time. After reacting at 75 ° C. for 1 hour, 1.7 g of V-65 was added, and after further reacting for 2 hours, the concentration was adjusted by adding ethyl acetate, and benzyl methacrylate / methacrylic acid (molar ratio 70/30). A 30% by mass solution of the copolymer (A-1) in ethyl acetate (a 30% by mass solution of the resin (A-1) in ethyl acetate) was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 12,000, and the degree of dispersion was 1.8. The acid value of the obtained polymer was 113 mgKOH / g. ^The total amount of residual monomers determined by ¹ H-NMR was 0.8% by mass based on the polymer.

The monomers shown in Table 2 below were used in the following molar ratio, and the following monomers were polymerized in the same manner to obtain Resins A-1 to A-6. Resins A-1 to A-6 each have a (meth) acrylate repeating unit.
The weight average molecular weight (Mw), dispersity, and acid value (mgKOH / g) of the obtained resin are also shown.

The monomers (M-1) to (M-8) are as follows.
M-1: benzyl methacrylate M-2: butyl acrylate M-3: styrene M-4: methacrylic acid M-5: acrylic acid M-6: 2-methacryloyloxyethyl succinic acid (light ester HO- manufactured by Kyoeisha Chemical Co., Ltd.) MS (N))
M-7: 2-methacryloxyethyl acid phosphate (Light ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.)
M-8: polyethylene glycol monomethyl ether methacrylate (having an average of 9 ethyleneoxy repeating units) (Light ester 130MA manufactured by Kyoeisha Chemical Co., Ltd.)

(Synthesis of Colored Resin Particle Dispersion RA-1)
A colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of the resin A-1 was used instead of the 30% by mass ethyl acetate solution of the urethane resin (U-1) and sodium hydroxide was used instead of triethylamine) Using the same method as in the synthesis of RU-1), a colored resin particle dispersion (RA-1) having a solid content concentration of 20% by mass was obtained.
The acid value of the resin of the colored resin particle dispersion (RA-1) was 113 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RA-2)
A colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of the resin A-2 was used instead of the 30% by mass ethyl acetate solution of the urethane resin (U-1) and sodium hydroxide was used instead of triethylamine) Using the same method as in the synthesis of RU-1), a colored resin particle dispersion (RA-2) having a solid content concentration of 20% by mass was obtained.
The acid value of the resin of the colored resin particle dispersion (RA-2) was 82 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RA-3)
A colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of the resin A-3 was used instead of the 30% by mass ethyl acetate solution of the urethane resin (U-1) and sodium hydroxide was used instead of triethylamine) Using the same method as in the synthesis of RU-4), a colored resin particle dispersion (RA-3) having a solid content concentration of 20% by mass was obtained.
The acid value of the resin of the colored resin particle dispersion (RA-3) was 94 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RA-4)
A colored resin particle dispersion (except for using a 30% by mass ethyl acetate solution of the resin A-4 instead of the 30% by mass ethyl acetate solution of the urethane resin (U-1) and using sodium hydroxide instead of triethylamine) ( Using the same method as in the synthesis of RU-1), a colored resin particle dispersion (RA-4) having a solid content concentration of 20% by mass was obtained.
The acid value of the resin of the colored resin particle dispersion (RA-4) was 60 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RA-5)
A colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of the resin A-5 was used instead of the 30% by mass ethyl acetate solution of the urethane resin (U-1) and sodium hydroxide was used instead of triethylamine) Using the same method as in the synthesis of RU-3), a colored resin particle dispersion (RA-5) having a solid content concentration of 20% by mass was obtained.
The acid value of the resin of the colored resin particle dispersion (RA-5) was 48 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RA-6)
A colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of resin A-6 was used instead of the 30% by mass ethyl acetate solution of urethane resin (U-1) and sodium hydroxide was used instead of triethylamine) Using the same method as in the synthesis of RU-4), a colored resin particle dispersion (RA-6) having a solid content concentration of 20% by mass was obtained.
The acid value of the resin of the colored resin particle dispersion (RA-6) was 28 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RA-7)
A colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of the resin A-1 was used instead of the 30% by mass ethyl acetate solution of the urethane resin (U-1) and sodium hydroxide was used instead of triethylamine) Using the same technique as in the synthesis of RU-2), a colored resin particle dispersion (RA-7) having a solid content concentration of 20% by mass was obtained.
The acid value of the resin of the colored resin particle dispersion (RA-7) was 113 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion X-2 for Comparison)
A colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of the resin A-1 was used instead of the 30% by mass ethyl acetate solution of the urethane resin (U-1) and sodium hydroxide was used instead of triethylamine) Using the same method as in the synthesis of X-1), a colored resin particle dispersion (X-2) having a solid content concentration of 20% by mass was obtained.
The acid value of the resin of the colored resin particle dispersion (X-2) was 113 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RS-1)
C. I. Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) 16.9 parts by mass, Resin S-1 (formalin condensate of sodium naphthalene sulfonate (manufactured by Kao Corporation, Demol N)) 3.1 parts by mass, 80 parts by mass of water were mixed and dispersed using a sand grinder. The resulting dispersion was filtered through a 1-micron filter and then through a 0.8-micron filter to obtain a colored resin particle dispersion RS-1 having a solid content of 20%.

(Synthesis of colored resin particle dispersion RS-2)
C. I. 14.3 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industry) and 5.7 parts by mass of resin S-1 (formalin condensate of sodium naphthalenesulfonate (manufactured by Kao Corporation, Demol N)). A colored resin particle dispersion (RS-2) having a solid content concentration of 20% by mass was obtained using the same method as in the synthesis of the colored resin particle dispersion (RS-1) except for using the same.

(Synthesis of colored resin particle dispersion X-3 for comparison)
C. I. Colored resin except for 10 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) and 10 parts by mass of resin S-1 (formalin condensate of sodium naphthalene sulfonate (manufactured by Kao Corporation, Demol N)) Using the same method as in the synthesis of the particle dispersion (RS-1), a colored resin particle dispersion (X-3) having a solid content concentration of 20% by mass was obtained.

染料 The dye / resin (mass ratio) and the average particle diameter (MV) of the obtained colored resin particle dispersion were as shown in Table 3 below. Table 3 below also shows the resins used.

(Preparation of inkjet ink for textile printing)
The colored resin particle dispersion obtained above was mixed with 1.2 parts by weight (solid content) of a self-dispersible carbon black pigment CAB-O-JET 200 (manufactured by Cabot Corporation) as shown in Table 4 below. 4.5 parts by mass (solid content) of Elastron BN-77 (block isocyanate, volume average particle diameter 19 nm, dissociation temperature of 120 ° C. or more, manufactured by Daiichi Kogyo Seiyaku), 1 mass of Surfynol 104 (manufactured by Nissin Chemical Industry) Parts (solids), 3.5 parts by mass (solids) of carnauba wax, a solvent shown in Table 4 below, and ultrapure water were mixed to prepare 100 parts by mass as a whole. This was filtered through a cellulose acetate membrane filter (pore size: 0.8 μm), and the inkjet inks for printing (BI-1) to (B1-26) and (HI-1) to (HI-5) shown in Table 3 below. Was prepared respectively.

Abbreviations in the table are described below.
TET: tetraethylene glycol GLY: glycerin DEG: diethylene glycol PG: propylene glycol

Examples 1 to 7, 10 to 32, Comparative Examples 1 to 14 (inkjet printing)
Katiomaster PD-7 (amine / epichlorohydrin condensation type ammonium cationic polymer flocculant; manufactured by Yokkaichi Gosei Co., Ltd., solid content 50% by mass) (50 parts by mass), BYK348 (manufactured by BYK Japan Japan Co., Ltd.) (5) Parts by mass), glycerin (100 parts by mass) and water (845 parts by mass) were mixed and stirred to prepare an aqueous pretreatment liquid.
The prepared aqueous pretreatment liquid was padded with a cotton cloth (with cotton broadsil, manufactured by Shisen, Co., Ltd., product code A02-01002) (referred to as "cotton" in the table below) and a polyester cloth (Shinosen, Inc.). (Product code A02-01019) (referred to as “polyester” in the table below) and a blend of 65% polyester and 35% cotton (blend polyester 65 / cotton 35 broad; product code A02-01030 manufactured by Shimosen Co., Ltd.) Each was squeezed at a squeezing ratio of 70% and dried for 24 hours to obtain a pretreated fabric. The squeezing ratio (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid with respect to the cloth after squeezing the cloth containing the aqueous treatment liquid.

The ink jet ink for textile printing obtained above is filled in an ink cartridge, and an image is recorded on the pretreated cloth shown in the table below using an ink jet printer (PX-045A, manufactured by Seiko Epson Corporation). A colored cloth was obtained.

(Heat treatment)
After drying the obtained colored cloth at 20 ° C. for 12 hours, the ink was heated at 200 ° C. for 60 seconds using a heat press machine (desk-top automatic flat press machine AF-54TEN, manufactured by Asahi Textile Machinery Co., Ltd.). Was established.

(Evaluation method)
The dyeing characteristics of the image of the obtained colored cloth were evaluated using a colorimeter (Gretag Macbeth Spectrolino, manufactured by X-Rite).

<Color development>
The color development was evaluated based on the following criteria based on OD (Optical Density) value.
SS: OD value 1.6 or more S: OD value 1.4 or more and less than 1.6 A: OD value 1.2 or more and less than 1.4 B: OD value 1.0 or more and less than 1.2 C: OD value 1. Less than 0

着色 The obtained colored cloth was evaluated for washing resistance, sweat resistance, friction resistance, ejection stability, and stability over time as described below.

<Washing resistance>
Washing resistance was evaluated based on JIS L-0844 A-2 (revised in 2011). The evaluation result of the washing resistance indicates that the larger the value, the better the fastness.
<Sweat resistance>
The sweat resistance was evaluated based on JIS L-0848 (revised in 2004). The results of the sweat resistance evaluation indicate that the larger the value, the better the fastness.
<Friction resistance>
The friction resistance was evaluated based on JIS L-0849 type II (revised in 2013). The evaluation results of the friction resistance show that the larger the numerical value, the better the fastness.

<Discharge stability>
The number of sheets that can be printed on the entire surface of the A4 fabric without blurring the image and clogging the nozzles of the inkjet head was evaluated according to the following criteria.
A: 4 or more sheets can be printed B: 3 to less than 4 sheets can be printed C: 2 to 3 sheets can be printed D: 1 to less than 2 sheets can be printed E: 1 sheet cannot be printed <Stability over time>
After the ink was heated at 50 ° C. for one month in a closed container, the ejection stability was similarly evaluated.

評 価 The evaluation results of Examples 1 to 7, 10 to 32, and Comparative Examples 1 to 14 are shown in Table 5 below.

 

(Preparation of inkjet ink for textile printing)
The components shown in Table 6 below, 1 part by mass (solid content) of Surfynol 104 (manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, and ultrapure water were mixed so that the total amount of the ink became 100 parts by mass, and the cellulose acetate filter was used. (Pore size: 0.8 μm), and inkjet inks for printing (BI-27) to (B1-34) shown in the following table were prepared.

Abbreviations in the table are described below.
GLY: glycerin PG: propylene glycol P1: self-dispersion type carbon black pigment CAB-O-JET 200 (manufactured by Cabot Corporation)
W1: Carnauba wax CL1: Elastron BN-77 (block isocyanate, volume average particle diameter 19 nm, dissociation temperature of 120 ° C. or more, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Examples 33 to 40
A colored cloth was obtained and evaluated in the same manner as in Example 1 except that the obtained ink jet printing inks (BI-27) to (BI-34) were used.
Table 7 below shows the evaluation results of Examples 33 to 40.

Examples IS-1 to IS-3, Comparative Example IS-1C
[Preparation of inkjet ink (Qm)]
(Preparation of pigment dispersion)
3 g of a styrene-acrylic acid copolymer (Joncryl 678, manufactured by BASF, trade name), 1.3 g of dimethylaminoethanol, and 80.7 g of ion-exchanged water were stirred and mixed at 70 ° C. Then, C.I. I. Pigment Red 112 (15 g) and zirconia beads having a particle diameter of 0.5 mm were filled at a volume ratio of 50% and dispersed using a sand grinder mill to obtain a pigment dispersion having a pigment content of 15% by mass.

(Preparation of aqueous binder)
50 g of 2-butanone was placed in a three-necked flask, and the internal temperature was heated to 75 ° C., and a mixture of 80 g of n-butyl methacrylate, 20 g of acrylic acid, 50 g of 2-butanone, and 0.5 g of azoisobutyronitrile was added thereto for 3 hours. The solution was dropped. After the dropwise addition, the mixture was heated under reflux for 5 hours, cooled to room temperature, and heated under reduced pressure to obtain a polymer residue. 350 mL of ion-exchanged water and 1.05 times mol of sodium hydroxide of acrylic acid added as a monomer were added and dissolved therein. The mixture was diluted with ion-exchanged water so that the total amount was 500 g, to obtain a 20% by mass aqueous solution of an aqueous binder.

(Preparation of pigment ink)
46.6 g of the pigment dispersion, 15 g of a 20% by weight aqueous solution of the aqueous binder, 2.9 g of PDX-7664A (trade name, manufactured by BASF), 10 g of triethylene glycol monobutyl ether, 5 g of 1,2-hexanediol, and 5 g of diethylene glycol 11 0.2 g and Olfine 465 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.) 0.6 g, and ion-exchanged water was added thereto to adjust the total amount to 100 g. The mixture was filtered through a 0.8 μm filter, and inkjet ink (Qm ) Got. The inkjet ink (Qm) is a magenta ink.

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

[Preparation of inkjet ink (Qy)]
C. I. Pigment Red 112, and C.I. I. An ink-jet ink (Qy) was prepared in the same manner as in the preparation of the ink-jet ink (Qm) except that Pigment Yellow 180 was used. The inkjet ink (Qy) is a yellow ink.

[Preparation of inkjet ink (Qb)]
C. I. An ink-jet ink (Qb) was prepared in the same manner as in the preparation of the ink-jet ink (Qm) except that carbon black was used instead of Pigment Red 112. The inkjet ink (Qb) is a black ink.

[Preparation of ink set for inkjet printing]
Ink jet printing ink sets S1 to S3 and X1 were prepared using combinations of the ink jet inks shown in the table below.

(Ink set evaluation method)
(Preparation of aqueous pretreatment liquid containing flocculant)
Katiomaster PD-7 (containing a flocculant; Yokkaichi Gosei Co., Ltd., solid content 50% by mass) (50 parts by mass), BYK348 (by Big Chemie Japan KK) (5 parts by mass), glycerin (100 parts by mass), Water (845 parts by mass) was mixed and stirred to prepare an aqueous pretreatment liquid.
(Pretreatment step)
The aqueous pretreatment liquid prepared above was applied to a polyester fabric (polyester tropical (manufactured by Teijin Limited), a product of Aizen Co., product code A02-01019) and a cotton fabric (with cotton broadsil, color Squeezed at a 70% squeezing rate for each of a blend of 65% polyester and 35% cotton (blend polyester 65 / cotton 35broad, product code of Aizen Co., Ltd., product code A02-01030). Dry for 24 hours. The squeezing ratio (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid with respect to the cloth after squeezing the cloth containing the aqueous treatment liquid.

(Inkjet printing, heat treatment and evaluation)
The ink sets for ink jet textile printing S1 to S3 and X1 are loaded into an ink cartridge, and the polyester fabric (polyester tropical (polyester) after the pre-treatment step) is loaded using an ink jet printer (Carario PX-045A, manufactured by Seiko Epson Corporation). Manufactured by Teijin Limited, product name of Aizen Co., product code A02-01019), cotton fabric after pretreatment step (with cotton broadsil, product code of A02-01002, product of Shiseize Co., Ltd.), and pretreatment After the process, an image was printed on a blend of 65% polyester and 35% cotton (blend polyester 65 / cotton 35 broad, product code A02-01030, manufactured by Shisensen Co., Ltd.), and dried at room temperature for 12 hours. After drying, heat treatment was carried out using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: tabletop automatic flat press AF-54TEN type) at a temperature of 200 ° C., a pressure of 0.20 N / cm ² and a time of 60 seconds, A colored cloth was obtained.

The resulting colored cloth was subjected to a visual sensory evaluation.
All three types of fabrics were evaluated on a four-point scale: A: clear, B: clear by two types, C: clear only one type, and D: no clear image. The results are shown in Table 8 below.

場合 When the ink set of the present invention was used, clear images were obtained in all three types of fabrics as compared with the ink set for comparison. It is presumed that the use of the black ink of the present invention exerted the effect of tightening the color ink image, and that a clear image was obtained.

ADVANTAGE OF THE INVENTION According to this invention, various types of cloths can be colored, and the coloring property of an obtained image, inkjet dischargeability, aging stability, dyeing fastness (washing resistance, abrasion resistance, and sweat resistance) Ink), an ink cartridge filled with the above ink, an ink set, an ink jet printer, and an ink jet printing method using the above ink can be provided.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application (No. 2018-121347) filed on June 26, 2018, the contents of which are incorporated herein by reference.

Claims (20)

1. It contains water, an aqueous organic solvent, and colored resin particles, and the colored resin particles contain a dye (A) and a resin (B) represented by the following formula (1), and the dye (A) and the resin (B Wherein the mass ratio (dye (A)) / (resin (B)) is 1.2 or more.
   

   

   
   In equation (1),
   R ₁₀₁ to R ₁₂₀ each independently represent a hydrogen atom or a substituent.
2. The ink according to claim 1, wherein the mass ratio of the dye (A) to the resin (B) (dye (A)) / (resin (B)) is 2 to 9.
3. The ink according to claim 1 or 2, wherein the resin has at least one selected from a carboxyl group, a salt of a carboxyl group, and a polyalkyleneoxy structure.
4. The ink according to any one of claims 1 to 3, wherein the resin is at least one selected from a urethane resin and a resin having a (meth) acrylate repeating unit.
5. The aqueous organic solvent contains 17% by mass or more based on the ink of a solvent having a boiling point of 150 ° C. or more at 1 atm consisting of only carbon atoms, hydrogen atoms, and oxygen atoms, or contains only carbon atoms, hydrogen atoms, and oxygen atoms. The ink according to any one of claims 1 to 4, wherein the ink contains a solvent having a boiling point at 200 ° C or higher at 1 atm of 15% by mass or more based on the ink.
6. (6) The ink according to any one of (1) to (5), wherein the aqueous organic solvent contains tetraethylene glycol.
7. (7) The ink according to any one of (1) to (6), further comprising a crosslinking agent.
8. (8) The ink according to any one of (1) to (7), further comprising a wax.
9. The ink according to any one of claims 1 to 8, further comprising a pigment.
10. The ink according to any one of claims 1 to 9, wherein the ink is for inkjet.
11. イ ン ク The ink according to any one of claims 1 to 9, wherein the ink is for textile printing.
12. (12) An ink jet printing method, which comprises a step of printing the ink according to any one of (1) to (11) on a fabric by an ink jet method.
13. The inkjet printing method according to claim 12, further comprising a heat treatment step.
14. 14. The inkjet printing method according to claim 12 or 13, further comprising a pretreatment step of applying an aqueous pretreatment liquid containing a coagulant to the fabric to obtain a pretreated fabric.
15. The ink jet printing method according to claim 14, wherein the coagulant is an ammonium cationic polymer.
16. イ ン ク ジ ェ ッ ト The inkjet printing method according to any one of claims 12 to 15, wherein the fabric contains at least one of cotton and polyester.
17. An ink set containing at least black ink, yellow ink, magenta ink, and cyan ink, wherein the black ink is the ink according to any one of claims 1 to 11.
18. An ink cartridge filled with the ink according to any one of claims 1 to 11.
19. An ink jet printer filled with the ink according to any one of claims 1 to 11.
20. What is claimed is: 1. A method for producing an aqueous dispersion of colored resin particles comprising colored resin particles containing a dye and a resin dispersed in water, comprising the following steps (1) and (2).
    Step (1): a step of emulsifying a mixture containing the dye (a), resin (b), water (c), and organic solvent (d) represented by the following formula (1) to obtain an emulsion. (2): a step of removing the organic solvent (d) from the emulsion obtained in the step (1), provided that the dye (a) and the resin (b) in the mixture in the step (1) are removed. The mass ratio (a) / (b) is 1.2 or more, and the mass ratio (a) / (d) of the dye (a) and the organic solvent (d) in the mixture in the step (1) is 1 / 9 to 1/1.
    

    

    
    In equation (1),
    R ₁₀₁ to R ₁₂₀ each independently represent a hydrogen atom or a substituent.