JPWO2020004228A1 - Inks, ink cartridges, ink sets, inkjet printers and inkjet printing methods - Google Patents

Abstract

The present invention contains water, an aqueous organic solvent, and colored resin particles, and the resin particles contain a dye (A) and a resin (B) represented by a specific structure, and the dye (A) and the resin ( Ink having a mass ratio (dye (A)) / (resin (B)) of B) of 1.2 or more, an ink cartridge filled with the above ink, an ink set, an inkjet printer, and the above ink are applied to a cloth by an inkjet method. Provided is an inkjet printing method having a printing step.

Description

The present invention relates to inks, ink cartridges, ink sets, inkjet printers and inkjet printing methods.

Conventionally, the colorant used for coloring the cloth is either a dye or a pigment, and as a method for industrially coloring the cloth using these colorants, a screen printing method, a roller printing method, a transfer method, etc. Inkjet methods and the like have been used. In particular, the inkjet method does not require the preparation of a plate as compared with other methods, can quickly form an image having excellent gradation, and further, since only the required amount of ink is used as the formed image, waste liquid is generated. It can be said that this is an excellent image forming method having environmental advantages such as less.

Patent Document 1 describes a printing ink containing a colorant, water, and a water-soluble organic solvent in which a coloring material is included by a polymer compound.
Patent Document 2 describes a water-based 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.
Further, Patent Document 4 describes an inkjet ink containing a core containing one or more thermosetting compounds, a capsule composed of a polymer shell surrounding the core, and an aqueous medium.

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

However, even these methods are insufficient from the viewpoint of simultaneously satisfying the color development property, inkjet ejection property, aging stability, and dyeing fastness (washing resistance, abrasion resistance, and sweat resistance) of the image. Needs improvement

The subject of the present invention is that various kinds of fabrics can be colored, and the color development property, ink jet ejection property, aging stability, and dyeing fastness (washing resistance, abrasion resistance, and sweat resistance) of the obtained image can be colored. ), An ink cartridge filled with the above ink, an ink set, an inkjet printer, and an inkjet printing method using the above ink.

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

[1]
The colored resin particles contain 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). ) Is an ink having a mass ratio (dye (A)) / (resin (B)) of 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 (dye (A)) / (resin (B)) of the dye (A) to the resin (B) is 2-9.

[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 of a solvent having a boiling point of 150 ° C. or higher at 1 atm consisting of only carbon atoms, hydrogen atoms and oxygen atoms, or from only carbon atoms, hydrogen atoms and oxygen atoms. The ink according to any one of [1] to [4], which contains 15% by mass or more of a solvent having a boiling point of 200 ° C. or higher at 1 atm with respect to 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 containing a cross-linking agent.
[8]
The ink according to any one of [1] to [7], further containing wax.
[9]
The ink according to any one of [1] to [8], further containing 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 inkjet printing method comprising a step of printing the ink according to any one of [1] to [11] on a fabric by an inkjet method.
[13]
The inkjet printing method according to [12], which further comprises a heat treatment step.
[14]
The inkjet printing method according to [12] or [13], which comprises a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to the fabric to obtain a pretreated fabric.
[15]
The inkjet printing method according to [14], wherein the flocculant 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 black ink, yellow ink, magenta ink, and 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 inkjet printer filled with the ink according to any one of [1] to [11].
[20]
A method for producing a colored resin particle aqueous dispersion in which colored resin particles containing a dye and a resin are dispersed in water, which comprises the following steps (1) and (2).
Step (1): A step of emulsifying a mixture containing the dye (a), the resin (b), the water (c), and the organic solvent (d) represented by the following formula (1) to obtain an emulsion. (2): Step of removing the organic solvent (d) from the emulsion obtained in the step (1) However, 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 of the step (1) is 1 /. It is 9 to 1/1.

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

According to the present invention, various kinds of fabrics can be colored, and both extremely high color development property, inkjet ejection property, and stability over time are achieved, and further, dyeing fastness (washing resistance, abrasion resistance, etc.) And an ink jet printing method using an ink, an ink cartridge filled with the ink, an ink set, an inkjet printer, and an ink having excellent sweat resistance).
In the present invention, by using a specific dye and containing it in the colored resin particles at a high concentration, it is possible to increase the dye concentration in the ink while suppressing the solid content concentration in the ink, which makes it extremely possible. It is presumed that high color development, inkjet ejection properties, and stability over time are compatible. Furthermore, since the content of the water-dispersible resin contained in the colored resin particles is small, good characteristics are exhibited even in a fastness test in contact with water such as washing, sweat, and wet friction.

Hereinafter, the present invention will be described in detail.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
As used herein, the term "substituent group A" refers to the substituents described in [0117] of International Publication No. 2017/131107.
Further, in the present specification, the substituent group A1 includes the following substituents.

(Substituent group A1)
Halogen atom, alkyl group (preferably 1 to 30 carbon atoms), cycloalkyl group (preferably 3 to 30 carbon atoms), aryl group (preferably 6 to 30 carbon atoms), heterocyclic group (preferably 3 to 30 carbon atoms). 30), acyl group (preferably 2 to 30 carbon atoms), hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, alkoxy group (preferably 1 to 30 carbon atoms), aryloxy group (preferably carbon number of carbons). 6 to 30), acyloxy group (preferably 2 to 30 carbon atoms), alkoxycarbonyl group (preferably 2 to 30 carbon atoms), aryloxycarbonyl group (preferably 7 to 30 carbon atoms), carbamoyl group, sulfamoyl group, Alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group (preferably 6 to 30 carbon atoms), amino group, acylamino group (preferably 1 to 30 carbon atoms), alkylsulfonylamino group (preferably carbon number 1 to 30) 1 to 30), an arylsulfonylamino group (preferably 6 to 30 carbon atoms), and a substituent formed by combining two or more of these.

As used herein, "(meth) acrylate" is used to mean "one or both of acrylate and methacrylate". The same applies to "(meth) acrylic group", "(meth) acrylic acid", "(meth) acrylamide", "(meth) acryloyl group", "(meth) acrylic group" and the like.

[ink]
The ink of the present invention contains (a) water, (b) an aqueous organic solvent, and (c) colored resin particles, and the colored resin particles are the dye (A) represented by the following formula (1), and the resin ( An ink containing B) and having a mass ratio of dye to resin (dye (A)) / (resin (B)) represented by the following formula (1) of 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 pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used, but ultrapure water can be used. More preferred.
The content of water in the ink of the present invention 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 (precipitation and the like are 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 in an arbitrary ratio. Is particularly preferable. Examples of the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, 1, 2, 6 -Hexane triol, thioglucol, hexylene glycol, glycerin, diglycerin, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol monoethyl ether, Examples thereof 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, ethylene glycol monobutyl ether, and more. Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, 2-pyrrolidone, ethylene glycol monobutyl ether and tetraethylene glycol are preferable, and ethylene glycol, glycerin, 2-pyrrolidone and tetraethylene glycol are particularly preferable.
The aqueous organic solvent preferably contains tetraethylene glycol.

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 further 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 (precipitation and the like are unlikely to occur), and the ejection stability of the inkjet ink is also excellent.

From the viewpoint of suppressing discoloration, the water-soluble organic solvent preferably contains a solvent consisting only of carbon atoms, hydrogen atoms and oxygen atoms, and the solvent consisting only of carbon atoms, hydrogen atoms and oxygen atoms is water-soluble. It is more preferable that the content is 30% by mass or more with respect to the organic solvent.

Further, the water-soluble organic solvent is composed of only carbon atoms, hydrogen atoms and oxygen atoms, and contains 17% by mass or more of a solvent having a boiling point of 150 ° C. or higher at 1 atm with respect to the ink, or carbon atoms, hydrogen atoms, and the like. It is preferable that the solvent contains only oxygen atoms and has a boiling point of 200 ° C. or higher at 1 atm in an amount of 15% by mass or more based on the ink. By using a solvent having the above boiling point in a specified amount or more, it is possible to suppress the association of the dye of the formula (1) on the fabric, and the dyeing concentration is improved.
It should be noted that 1 atm = 101325 Pa.

Examples of the solvent composed of 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 preferable.

<(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 even more preferably 40 to 150 nm. When the average particle size of the colored resin particles is 200 nm or less, it becomes easy to directly print on the fabric by the inkjet method.
For the average particle size of the colored resin particles, the value of the volume average particle size (MV) measured using a particle size distribution measuring device (Nanotrack UPA EX150, manufactured by Nikkiso Co., Ltd., trade name) was used.

In the ink of the present invention, the colored resin particles are dispersed and present.
At the time of dispersion, the colored resin particles are easily compatible with water (easy to get wet) due to the properties of the colored resin particles themselves or by using a dispersant in combination, and the colored resin particles are regenerated by electrostatic repulsion (repulsive force) or steric repulsion. It has the function of preventing aggregation and suppressing the formation of sedimentation.
A known method can be used as a method for dispersing the colored resin particles.

The colored resin particles in the ink of the present invention include the dye (A) represented by the following formula (1) and the resin (B), and the mass ratio of the dye to the resin represented by the following formula (1) (dye (dye (1)). 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 the 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 above-mentioned Substituent Group A (preferably a substituent selected from the above-mentioned 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 representing a methyl group.
R ¹⁰¹ and R ¹⁰² preferably represent a hydrogen atom.

As the _{substituent in R 103 to} R ₁₁₈ , a halogen atom, an alkyl group, an alkoxy group, a nitro group, an aryl group, an acylamino group and an alkoxycarbonyl group are more preferable.
R _{103 to} R ₁₁₈ preferably represent a hydrogen atom.

Each of R ¹¹⁹ and R ¹²⁰ independently and preferably represents an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms. It is particularly preferable to represent an alkyl group of 1 to 6, and most preferably a methyl group.

When R ^{101 to} R ¹²⁰ each independently represent a substituent, each substituent may have an additional substituent. The further substituent is not particularly limited, and examples thereof include a substituent selected from the above-mentioned Substituent Group A1.

Examples of the dye (A) represented by the above formula (1) include C.I. I. Solvent Black 3 is preferable. C. I. Commercially available products can be used as Solvent Black 3, and examples thereof include Oil Black HBB and Oil Black 860 (both manufactured by Orient Chemical Industries Co., Ltd.).

(Resin (B))
Any resin (B) may be used as long as the dye (A) can be dispersed in water, but preferred resins include urethane resin, resin having a (meth) acrylate repeating unit, and polyvinyl alcohol. , And its acetal form, formalin condensate of aromatic sulfonate, etc., and from the viewpoint of dyeing fastness, the resin (B) is selected from at least a urethane resin and a resin having a (meth) acrylic repeating unit. It is preferably one kind.

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.
The urethane resin is preferably a reaction of polyisocyanate and polyol. The polyisocyanate is not particularly limited as long as it is a polyisocyanate containing 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-naphthalenediocyanate, xylylene diisocyanate, 2,6-diisocyanate methylca. Aromatic, aliphatic, alicyclic organic diisocyanates such as proate, isophorone diisocyanate (IPDI), methylcyclohexane-2,4- (or 2,6-) diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), Alternatively, a multimer containing a polyfunctional isocyanate group such as these bullets and isocyanurates, or a single or a mixture of these isocyanates can be mentioned.
Particularly from the viewpoint of weather resistance, it is preferably an aliphatic and / or alicyclic organic diisocyanate compound, and specifically, an aliphatic or alicyclic compound such as HDI, IPDI, dodecane diisocyanate, cyclohexanediisocyanate, or dicyclohexylmethanediisocyanate. 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. As an example of the polymer polyol, a polyether polyol, a polyester polyol, a polycarbonate polyol and the like can be used.
The above-mentioned polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, random copolymers of ethylene oxide and butylene oxide, and block copolymers. Further, a polyether polyester polyol having an ether bond and an ester bond can also be used.
The polyester polyol is not particularly limited, but for example, polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol, polybutylene succinate polyol, polyethylene seva. Examples thereof include catepolyester, polybutylene sevacate polyol, poly-ε-caprolactone polyol, poly (3-methyl-1,5-pentylene adipate) polyol and the like.
Examples of the polycarbonate polyol include a linear aliphatic polycarbonate polyol, a branched chain aliphatic polycarbonate polyol, a polycarbonate polyol having an alicyclic structure in the main chain, and a polycarbonate polyol having an aromatic ring in the main chain.
The low molecular weight polyol is not particularly limited, but low molecular weight diols can be used, for example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 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 An aliphatic diol having 2 to 9 carbon atoms such as −hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol; 1,4-cyclohexanedimethanol , 1,3-Cyclohexanedimethanol, 1,4-Cyclohexanediol, 1,4-bis (hydroxyethyl) cyclohexane, 2,7-norbornandiol, tetrahydrofurandimethanol, 2,5-bis (hydroxymethyl) -1, Examples thereof include diols having an alicyclic structure having 6 to 12 carbon atoms such as 4-dioxane. Further, as the low molecular weight polyol, a low molecular weight polyhydric alcohol such as trimethylolpropane, pentaerythritol, or sorbitol may be used.

As the polyol, 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 , Polyethylene glycol, polypropylene glycol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol and other linear aliphatic glycols; 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-propane Adicyclic branched glycols such as diol, 2-methyl-1,8-octanediol; alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; glycerin, trimethylolethane, trimethylpropane, etc. Polyfunctional glycols such as tributyrolepropane, pentaerythritol, and sorbitol; can be used alone or in combination of two or more, and can also be used as a copolymer of two or more. can.

(Acid group-containing polyol or salt thereof)
The acidic group-containing polyol that can be used in the method for producing the colored resin particle dispersion below is a compound having two or more hydroxyl groups and one or more acidic groups in one molecule. It is used for the introduction of carboxylate groups or sulfonate groups for the purpose of self-emulsifying the colored resin in water and imparting dispersion stability of the colored resin particle dispersion. The carboxyl group-containing polyol is not particularly limited, and is, for example, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanic acid, 2,2-dimethyloloctane. Examples include acid. Examples of the sulfonic acid-containing polyol include sulfonic acid diol {3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid} and sulfamic acid diol {N, N-bis (2-hydroxylyl) sulfamic acid. } And its alkylene oxide adduct and the like. The salts of these carboxyl group and / or sulfone group-containing polyols are not particularly limited, and are, for example, ammonium salts and amine salts [primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propyl). Amines and octylamines) salts, secondary monoamines (dimethylamines, diethylamines and dibutylamines) salts, tertiary monoamines (trimethylamines, triethylamines, triethanolamines, N-methyldiethanolamines and N, N-dimethylethanolamines, etc. Monoamines; heterocyclic tertiary monoamines such as N-methylpiperidin and N-methylmorpholin; benzyldimethylamine, α-methylbenzyldimethylamine; and aromatic ring-containing tertiary monoamines such as N-dimethylaniline) salts], alkali metals Examples include (sodium, potassium and lithium cation) salts, and the combination of two or more of these.

If the polyol is a carboxyl group and / or sulfo group-containing polyol rather than a salt, use a neutralizer to neutralize the carboxyl and / or sulfonic acid groups to the carboxylate and / or sulfonate groups. Can be done. As the amount of the neutralizing agent to be used, it is preferable to use an amount in which 10 to 100 mol% of the carboxyl group and / or the sulfonic acid group contained in the resin is neutralized, and 50 to 98 mol%, more preferably 70 to 95 mol%. Is.

(Neutralizer)
The neutralizing agent is not particularly limited, and examples thereof include alkaline compounds capable of neutralizing the above-mentioned carboxyl group and / or sulfone group. For example, ammonia, amines [primary amines with 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-methylpiperidin and N-methylmorpholin; benzyldimethylamine, α -Methylbenzyldimethylamine; and aromatic ring-containing tertiary monoamines such as N-dimethylaniline)], alkali metals (sodium, potassium and lithium cations), alkali metal hydroxides, and combinations of two or more of these. ..

(Chain extender)
The chain extender is not particularly limited, and is, for example, 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. One of these may be used alone, or two or more thereof may be used in combination.

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

The urethane resin may further have a urea bond. A resin having a urethane bond and a urea bond is also called a "urethane / urea resin".
One of the preferred forms 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 bonded by a urea bond.

The colored resin particles are preferably used as a dispersion.
The method for producing the 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. Poly 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 (for example, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, etc.) A urethane resin is synthesized by subjecting isocyanate, a polyol having two or more hydroxyl groups in one molecule, an acidic group-containing polyol or a salt thereof, to a urethanization reaction by a one-shot method or a multi-step method, and if necessary, the above-mentioned urethane resin. Is neutralized with a neutralizing agent, a dye is added, water is added dropwise to the place where the reaction solution is strongly stirred, and then the solvent is removed if necessary to obtain a colored resin particle dispersion. Be done.

Further, as a method for producing the colored resin particle dispersion, 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 may be used in advance. It is also possible to synthesize a prepolymer under the condition of excess isocyanate, add a dye, disperse it in water, and then add a chain extender to obtain a colored resin particle dispersion.

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

(Resin having (meth) acrylate repeating unit)
The resin having the (meth) acrylate repeating unit may be any resin as long as it has the (meth) acrylate repeating unit, but it can be copolymerized with the resin consisting of only the (meth) acrylate repeating unit and the (meth) acrylate. Examples thereof include a resin made of a copolymer with a monomer.
As the resin having the (meth) acrylate repeating unit, a resin having a hydrophilic repeating unit and a hydrophobic repeating unit is preferable.

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

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 as the hydrophilic group is preferable.
Specifically, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloxyethyl acid phosphate, polyethylene glycol monomethyl ether (meth). ) Acrylate, styrene carboxylic acid, styrene sulfonic acid and the like can be mentioned.
Among these, a copolymer having at least a hydrophobic (meth) acrylate and a metal acrylate having an acid group, and a copolymer having at least a styrene and a (meth) acrylate having an acid group are preferable.

The method for producing the 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 a neutralizing agent if necessary. , A method of adding a surfactant to emulsify and then removing the solvent, or emulsifying a dye (A), a monomer, and an emulsifier (for example, a surfactant) in water to form a monomer in the presence of a polymerization initiator. A method for 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 30 mol% to 95 mol%, preferably 50 mol%, based on all the repeating units of the resin having the (meth) acrylate repeating unit. % To 90 mol% is more preferable.
The content of the hydrophilic repeating unit in the resin having the (meth) acrylate repeating unit is preferably 5 mol% to 70 mol%, preferably 10 mol, based on all the repeating units of the resin having the (meth) acrylate repeating unit. % To 50 mol% is more preferable.

The weight average molecular weight (Mw) of the resin (B) is preferably 1500 to 1,000,000, more preferably 2000 to 500000, and even more preferably 5000 to 20000. 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, unless otherwise specified, the GPC is HLC-8220 GPC (manufactured by Tosoh Corporation), and the columns are measured with TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation). 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 5 to 200 mgKOH / g, more preferably 10 to 150, still more preferably 20 to 130 mgKOH / g, and particularly preferably 30 to 120 mgKOH / g.
When the acid value is 5 mgKOH / g or more, when the colored resin particles are used as the dispersion, the dispersibility of the dispersion can be maintained and the stability of the ink is not deteriorated, which is preferable. On the other hand, when 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 dyeing 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 base-neutralized carboxylate or sulfonate, the acid value is calculated assuming that the resin contains an unneutralized carboxylic acid or sulfonic acid.
The acid value can be measured according to the indicator titration method of JIS K 1557.

In the present invention, the mass ratio (dye (A)) / (resin (B)) of the dye (A) represented by the above formula (1) to the resin (B) in the colored resin particles is 1.2 or more. The amount of (dye (A)) / (resin (B)) is preferably 1.5 or more, more preferably 2 or more, still more preferably 2.5 or more. By setting (dye (A)) / (resin (B)) to 1.2 or more, the dye concentration can be increased without increasing the solid content concentration in the ink, and a high dyeing concentration can be achieved. Aggregation between colored resin particles can be suppressed, and both inkjet ejection properties and aging 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 value, the dispersion stability of the colored resin particles is improved, and the inkjet ejection 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 1 to 20% by mass, more preferably 2 to 15% by mass, and 3 to 12% by mass, based on the total amount of the ink, for the purpose of ensuring ejection stability and color development. Is more preferable.
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, still more preferably 2 to 10% by mass, based on the total amount of the ink.

In the inkjet printing method of the present invention, a cross-linking agent described later can be used in order to further strengthen the adhesion between the fabric and the resin and improve the fastness of the image. Therefore, it is preferable that the resin has a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group or the like as a group capable of reacting with the crosslinkable group of the crosslinking agent.
It is also preferable not to use a cross-linking agent in the printing inkjet ink. It is also preferable that the colored fine particles of the inkjet ink for printing do not contain a cross-linking agent. Further, it is also preferable that the resin does not have a group capable of reacting with the crosslinkable group of the crosslinking agent.

In the colored resin particles of the ink of the present invention, it is preferable that the specific dye is present in the form of being coated with the resin. It is preferable that the polymer and the dye are not covalently bonded. Since the polymer and the dye are not covalently bonded, the motility 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 encapsulated in the polymer, that is, a core-shell structure. The core is made of the above-mentioned specific dye, and the shell is made of the above-mentioned 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 cross-linking agent.
As described above, in the inkjet printing method of the present invention, it is preferable to use a cross-linking agent in order to further strengthen the adhesion between the fabric and the resin and improve the fastness of the image. It is preferable that the resin and the components constituting the fabric are bonded by the cross-linking agent.
The cross-linking agent is preferably a compound having at least two cross-linking groups.
As the crosslinkable group contained in the crosslinking agent, a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group and the like are preferable.
Examples of the cross-linking agent include blocked isocyanate compounds, oxazoline compounds, and carbodiimide compounds. Among them, HDI (hexamethylene diisocyanate), H6XDI (hydrogenated xylylene diisocyanate), IPDI (isophorone diisocyanate), or H12MDI ( A blocked isocyanate compound in which a TMP (trimethylolpropane) adduct compound or an isocyanurate form of dicyclohexylmethane diisocyanate is blocked with a blocking agent is preferable, and the blocking agent is DEM (diethyl malonate) or DIPA (diisopropyl) based on the dissociation temperature. Amin), TRIA (1,2,4-triazole), DMP (3,5-dimethylpyrazole), MEKO (butanone oxime) can be preferably used. In addition, these blocked isocyanate-based compounds can also be used as oligomers in which a part of the isocyanate groups are reacted with polyols, polycarbonates, polyesters, polyethers and the like.
As the dissociation temperature of the cross-linking agent, a lower temperature is preferable from the viewpoint of cross-linking efficiency, while a higher temperature is preferable from the viewpoint of storage stability, and a balance between them 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.
Further, it is preferable that the cross-linking agent is blended with the ink as having water-soluble or self-emulsifying property by imparting a hydrophilic group. In this state, the viscosity of the blended ink can be made low, and the redispersibility can be made excellent.

The cross-linking agent is preferably present in the form of particles in the ink of the present invention. Crosslinking agents in the form of particles are called "crosslinking agent particles".

The cross-linking agent particles preferably have a volume average particle diameter (MV) of 200 nm or less from the viewpoint of improving ejection properties in inkjet.
The volume average particle size can be measured by the same method as the colored resin particles described above.

The cross-linking agent particles are not particularly limited, but for example, Elastron BN-77 (blocked isocyanate, volume average particle diameter 19 nm, dissociation temperature 120 ° C. or higher, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Elastron BN- 27 (blocked isocyanate, volume average particle size 108 nm, dissociation temperature 180 ° C. or higher, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Duranate WM44-70G (blocked isocyanate, volume average particle size 42 nm, dissociation temperature approx. 90 ° C., manufactured by Asahi Kasei Co., Ltd.), TRIXENE AQUA BI200 (blocked isocyanate, volume average particle size 94 nm, dissociation temperature 110-120 ° C., manufactured by BAXENDEN) and the like can be mentioned.

The content of the cross-linking agent in the ink is preferably 0.1 to 10% by mass, preferably 0.5, because it is necessary to blend a cross-linking functional group sufficient for reacting the resin and the fabric. It is more preferably ~ 8% by mass, and even more preferably 1-5% 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 inkjet 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 and adjust the color density. It is preferable because it can be raised. Only one kind of pigment may be used, or two or more kinds of pigments may be used.

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, either an aqueous dispersion of a pigment in which the pigment is dispersed in water using a dispersant or a self-dispersing pigment can be preferably used, but a self-dispersing pigment is preferable. Examples of the self-dispersing pigments that can be used include self-dispersing carbon black CAB-O-JET 200, 300, 400 (all manufactured by Cabot Corporation), BONJET CW-1 (500 μmol / g as a carboxy group), and CW. Examples thereof include commercially available products such as -2 (470 μmol / g as a carboxy group) (all manufactured by Orient Chemical Industries Co., Ltd.) and Aqua-Black 162 (approximately 800 μmol / g as a carboxyl group) of Tokai Carbon Co., Ltd.

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

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

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

The melting point of the wax is preferably in the range of 60 ° C. to 120 ° C., more preferably in the range of 60 ° C. to 100 ° C. from the viewpoint of improving stability and friction. While raising the melting point can improve the stability of the printing ink, not raising the melting point more than necessary is effective in improving the frictional property.
The melting point of wax can be measured with a general melting point measuring machine.

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 ejection property in inkjet.

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

Commercially available products may be used as the wax particles, and the wax particles are not particularly limited. For example, Polylon L-787 (manufactured by Chukyo Yushi Co., Ltd., polyethylene, nonion, melting point 102 ° C., volume average particle diameter 0. 1 μm), Hydrin-703 (manufactured by Chukyo Oil & Fat Co., Ltd., paraffin, anion, melting point 75 ° C., volume average particle size 0.1 μm), R108 (manufactured by Chukyo Oil & Fat Co., Ltd., paraffin, nonion, melting point 66 ° C., average particle size 0.2 μm) ), Celozol 524 (manufactured by Chukyo Oil & Fat Co., Ltd., carnauba, nonion, melting point 83 ° C., volume average particle diameter 0.07 μm), and more preferably R108 (manufactured by Chukyo Oil & Fat Co., Ltd., paraffin, nonion, melting point 66 ° C.). , Volume average particle diameter 0.2 μm), Celozol 524 (manufactured by Chukyo Oil & Fat Co., Ltd., carnauba, nonion, melting point 83 ° C., volume average particle diameter 0.07 μm). Carnauba, nonion, melting point 83 ° C., volume average particle size 0.07 μm).

<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 whitening agents, surface tension regulators, fungicides, antidrying agents, lubricants, and augmentations. Adhesives, UV absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, specific resistance regulators, rust inhibitors, inorganic pigments, anti-reduction agents, preservatives, fungicides, chelating agents, etc. Can be mentioned.

The ink of the present invention is preferably an inkjet ink (inkjet ink).
Further, the ink of the present invention is preferably an ink for printing, 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 colored resin particles with an aqueous organic solvent, water, and if necessary, a surfactant or the like to prepare an ink. Can be mentioned.

The ink of the present invention is also useful from the viewpoint of workability because it can directly print on a cloth to which a pretreatment agent has not been applied without bleeding.

When the ink of the present invention is used for inkjet (inkjet ink), the surface tension of the ink at 25 ° C. is preferably adjusted to 20 mN / m to 70 mN / m, and is 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 30 mPa · s or less, and particularly preferably 20 mPa · s or less. preferable. The viscosity is measured by controlling the viscosity to 25 ° C. using an E-type rotational viscometer.
Surface tension and viscosity can be determined by various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, anti-fading agents, fungicides, rust inhibitors. , Dispersant, surfactant and the like can be added.

[ink cartridge]
The ink cartridge of the present invention is an ink cartridge filled with the ink of the present invention (preferably an inkjet ink for printing).

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

[Ink set]
By using an ink set containing the ink of the present invention (preferably an inkjet ink for printing), a clearer image can be obtained when multicolor printing is performed. The ink set preferably contains black ink and at least one selected from cyan ink, magenta ink, and yellow ink, and contains all black ink, cyan ink, magenta ink, and yellow ink. Is preferable. Of these, since the black ink is the ink of the present invention, the image sharpness is particularly excellent.

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

The dye is not particularly limited, but the following dyes are particularly preferable. "CI" is an abbreviation for "color index". Further, the one described as "Disperse" is a disperse dye, and the one described as "Solvent" is an oil-soluble dye.

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 8,23,24,25,49,52,109,111,119,122,124,135,146,149,150,168,169,172,179,195,196,197,207,2222 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 can be mentioned.

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. It is preferably at least one selected from Pigment Green 36.

[Inkjet printing method]
The inkjet printing method of the present invention is an inkjet printing method including a step of directly printing the ink of the present invention (preferably an inkjet ink for printing) on a cloth by an inkjet method.
In the inkjet printing method of the present invention, the fabric may be a fabric pretreated with an aqueous pretreatment liquid containing a coagulant. That is, the inkjet printing method of the present invention may have a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to the fabric to obtain the pretreated fabric.
In the present invention, "directly printing" the inkjet ink for printing on the cloth by the inkjet method does not require a transfer step and does not require a step of applying the printing paste, and the inkjet ink for printing is directly applied to the cloth. Refers to being stamped.
The inkjet printing method of the present invention is a simple method and is useful without producing waste water and waste materials such as transfer paper.

(Pretreatment process)
The pretreatment step in the second aspect is a step of applying an aqueous pretreatment liquid containing a flocculant to the fabric to obtain the 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 aggregating agent contained in the aqueous pretreatment liquid is not particularly limited as long as it has an action of aggregating an aqueous dispersion of a dye, a resin or a pigment, and includes organic acids, polyvalent metal salts, and cationic compounds. It is preferably at least one selected.
In particular, when the flocculant is a cationic compound or a polyvalent metal salt and the colored resin particles have an anionic group (preferably an acid group), printing by the above inkjet printing method produces a high-concentration colored cloth. Obtainable. This is because the pretreated cationic compound or polyvalent metal salt stays on the surface of the fabric because it aggregates at the moment of contact with the ink containing the colored resin particles having anionic groups, resulting in the surface. It is considered that the amount of dye present in the ink increases and the concentration can be increased. The flocculant is more preferably a cationic compound.

≪Multivalent metal salt≫
A polyvalent metal salt is a compound composed of a divalent or higher 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 so on.

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

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

<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 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 100 to 220 ° C, more preferably 130 to 200 ° C. The heating time in the heat treatment step is preferably 20 seconds to 300 seconds, more preferably 30 to 240 seconds, and even more preferably 40 to 180 seconds.

<Post-processing>
The fabric colored with the inkjet ink for printing of the present invention is further improved in texture flexibility and toughness (particularly abrasion resistance) by padding the colored fabric with a post-treatment agent as necessary. A colored cloth can be obtained. Post-treatment agents for the purpose of softening include cationic surfactants, anionic surfactants, nonionic surfactants, dimethyl silicone oils, amino silicone oils, carboxy-modified silicone oils, hydroxy-modified silicone oils, and fatty acids. , Fatty acid amide, mineral oil, vegetable oil, animal oil, plasticizer and the like.
As post-treatment agents for the purpose of improving the smoothness of the surface of colored cloth, metal soap, paraffin wax, carnauba wax, microstalin wax, dimethyl silicone oil, aminosilicone oil, carboxy-modified silicone oil, hydroxy-modified silicone oil, etc. Can be mentioned.
In the padding treatment, these post-treatment agents are emulsified, heat-emulsified, or dispersed in an aqueous solvent by stirring with a mixer, and a colored cloth is dipped in the mixture, squeezed with a mangle or the like, dried, and heat-treated.
Further, by blending a small amount of resin emulsion as a fixing agent in the post-treatment agent, the abrasion 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 blended as a fixing agent in the post-treatment agent is not particularly limited, but is limited to acrylic acid ester resin emulsion, urethane resin emulsion, ethylene / vinyl acetate copolymer resin (EVA resin) emulsion, and silicone / acrylic resin emulsion. , Polyester resin emulsion and the like can be used, and in order to soften the texture of the colored cloth, it is preferable that the glass transition point of these resin emulsions is 0 ° C. or lower.

<Fabric>
The inkjet printing method of the present invention can be applied to various types of fabrics. For example, as the fabric (fiber type), synthetic fibers such as nylon, polyester and acrylonitrile, semi-synthetic fibers such as acetate and rayon, natural fibers such as cotton, silk and wool, and mixed fibers, woven fabrics and knitting thereof are used. Examples include non-woven fabrics.
Among these, the effect of the present invention is 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, sweatshirts, jerseys, pants, sweat suits, dresses, blouses and the like. It is also suitable for bedding, handkerchiefs and the like.

Hereinafter, the present invention will be described in more detail based on Examples, but the scope of the present invention will not be construed as being limited by the Examples shown below.

(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. 80 parts by mass of (HDI), 2 parts by mass of trimethylolpropane, and 98.4 parts by mass of ethyl acetate were charged, and 0.08 parts by mass of Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) was added as a catalyst. rice field. After replacing the reaction system with nitrogen gas, the reaction was carried out at 70 ° C. for 12 hours under stirring. , A urethane resin (U-1) having a residual isocyanate group at the end was synthesized. The presence of residual isocyanate groups was confirmed by potentiometric titration. Ethyl acetate was added thereto to make the solid content concentration 30% by mass. The polystyrene-equivalent weight average molecular weight of the obtained urethane resin (U-1) was 6400, and the acid value was 39 mgKOH / g.

(Synthesis of Colored Resin Particle Dispersion RU-1)
C. I. 17.6 parts by mass of a solution of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) dissolved in ethyl acetate at a concentration of 30% by mass, and 30% by mass of the obtained urethane resin (U-1). 3.2 parts by mass of the 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. To this, 47.4 parts by mass of a 1% aqueous sodium dodecyl sulfate solution was mixed, and the mixture was emulsified using a homogenizer (ED-1 manufactured by Nippon Seiki Co., Ltd.) at 16000 rpm for 12 minutes. After filtering the obtained emulsion using a 1 micron filter, the mixture is heated to 45 ° C. under the blast stirring condition, a part of the organic solvent and water is distilled off, and the mixture is filtered through a 0.8 micron filter to obtain a solid content concentration. A 20% by mass colored resin particle dispersion (RU-1) 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 colored resin particle dispersion RU-1 except that Solvent Black 3 was replaced with 11.4 parts by mass of a 30% by mass ethyl acetate solution and 9.4 parts by mass of a urethane resin (U-1) with a 30% by mass ethyl acetate solution. The colored resin particle dispersion RU-2 was synthesized using the same method as in the above.
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 13.9 parts by mass of a 30 mass% ethyl acetate solution and 6.9 parts by mass of a urethane resin (U-1) with a 30 mass% ethyl acetate solution. The colored resin particle dispersion RU-3 was synthesized using the same method as in the above.
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 with 14.9 parts by mass of a 30% by mass ethyl acetate solution and 5.9 parts by mass of a urethane resin (U-1) with a 30% by mass ethyl acetate solution. The colored resin particle dispersion RU-4 was synthesized using the same method as in the above.
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 with 18.2 parts by mass of a 30% by mass ethyl acetate solution and 2.6 parts by mass of a urethane resin (U-1) with a 30% by mass ethyl acetate solution. The colored resin particle dispersion RU-5 was synthesized using the same method as in the above.
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 with 18.9 parts by mass of a 30% by mass ethyl acetate solution and 2.1 parts by mass of a 30% by mass ethyl acetate solution of a urethane resin (U-1). The colored resin particle dispersion RU-6 was synthesized using the same method as in the above.
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 replaced with 19.3 parts by mass of a 30% by mass ethyl acetate solution and 1.5 parts by mass of a urethane resin (U-1) with a 30% by mass ethyl acetate solution. The colored resin particle dispersion RU-7 was synthesized using the same method as in the above.
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 with 10.4 parts by mass of a 30% ethyl acetate solution and 10.4 parts by mass of a urethane resin (U-1) with a 30% ethyl acetate solution. The colored resin particle dispersion X-1 was synthesized using the same method.
The acid value of the resin in the colored resin particle dispersion (X-1) was 39 mgKOH / g.

The dye / resin (mass ratio) and average particle size (MV) of the obtained colored resin particle dispersion were the values shown in Table 1 below. It also describes the resin or prepolymer used.

(Synthesis of resin A-1 having (meth) acrylate repeating unit)
78 g of ethyl acetate was heated to 75 ° C. under a nitrogen stream. 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 Wako Pure Chemical Industries, Ltd. V-65 as a polymerization initiator in 78 g of ethyl acetate was added to the solution. 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, ethyl acetate was added to adjust the concentration, and benzyl methacrylate / methacrylic acid (molar ratio 70/30). A 30 mass% ethyl acetate solution of the copolymerized polymer (A-1) (30 mass% ethyl acetate solution of the resin (A-1)) was obtained. The polystyrene-equivalent weight average molecular weight in GPC was 12000, and the dispersity was 1.8. The acid value of the obtained polymer was 113 mgKOH / g. ^{1 The} total amount of residual monomers determined by 1 H-NMR was 0.8% by mass with respect to the polymer.

The monomers shown in Table 2 below were used in the following molar ratios, and the following monomers were polymerized by the same method to obtain resins A-1 to A-6, respectively. 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-Metacloyloxyethyl 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)
Colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of resin A-1 was used instead of a 30% by mass ethyl acetate solution of urethane resin (U-1) and sodium hydroxide was used instead of triethylamine. Using the same method as 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)
Colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of resin A-2 was used instead of a 30% by mass ethyl acetate solution of urethane resin (U-1) and sodium hydroxide was used instead of triethylamine. Using the same method as 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)
Colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of resin A-3 was used instead of a 30% by mass ethyl acetate solution of urethane resin (U-1) and sodium hydroxide was used instead of triethylamine. Using the same method as 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)
Colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of resin A-4 was used instead of a 30% by mass ethyl acetate solution of urethane resin (U-1) and sodium hydroxide was used instead of triethylamine. Using the same method as 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)
Colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of resin A-5 was used instead of a 30% by mass ethyl acetate solution of urethane resin (U-1) and sodium hydroxide was used instead of triethylamine. Using the same method as 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)
Colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of resin A-6 was used instead of a 30% by mass ethyl acetate solution of urethane resin (U-1) and sodium hydroxide was used instead of triethylamine. Using the same method as 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)
Colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of resin A-1 was used instead of a 30% by mass ethyl acetate solution of urethane resin (U-1) and sodium hydroxide was used instead of triethylamine. Using the same method as 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)
Colored resin particle dispersion (except that a 30% by mass ethyl acetate solution of resin A-1 was used instead of a 30% by mass ethyl acetate solution of urethane resin (U-1) and sodium hydroxide was used instead of triethylamine. Using the same method as 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 Industry Co., Ltd.) 16.9 parts by mass, resin S-1 (formalin condensate of sodium naphthalene sulfonate (Kao Corporation, Demol N)) 3.1 parts by mass, 80 parts by mass of water was mixed and dispersed using a sand grinder. The obtained dispersion was filtered with a 1 micron filter and then with a 0.8 micron filter to obtain a colored resin particle dispersion RS-1 having a solid content concentration of 20%.

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

(Synthesis of colored resin particle dispersion X-3 for comparison)
C. I. Colored resin except 10 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industry Co., Ltd.) and 10 parts by mass of resin S-1 (formalin condensate of sodium naphthalene sulfonate (manufactured by Kao, Demor N)). Using the same method as 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.

The dye / resin (mass ratio) and average particle size (MV) of the obtained colored resin particle dispersion were the values shown in Table 3 below. The resins used are also shown in Table 3 below.

(Preparation of inkjet ink for printing)
The colored resin particle dispersion obtained above was obtained by mass (solid content) as shown in Table 4 below, 1.2 parts by mass (solid content) of the self-dispersing carbon black pigment CAB-O-JET 200 (manufactured by Cabot), Elastron BN-77 (blocked isocyanate, volume average particle size 19 nm, dissociation temperature 120 ° C. or higher, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 4.5 parts by mass (solid content), Surfinol 104 (manufactured by Nissin Chemical Co., Ltd.) 1 mass Parts (solid content), 3.5 parts by mass of carnauba wax (solid content), the solvent shown in Table 4 below and ultrapure water were mixed and prepared so that the total amount was 100 parts by mass. This is filtered with a cellulose acetate membrane filter (pore size: 0.8 μm), and the printing inkjet inks (BI-1) to (B1-26) and (HI-1) to (HI-5) shown in Table 3 below are used. Were prepared respectively.

The abbreviations in the table are listed below.
TET: Tetraethylene Glycol GLY: Glycerin DEG: Diethylene Glycol PG: Propylene Glycol

Examples 1-7, 10-32, Comparative Examples 1-14 (inkjet printing)
Catiomaster PD-7 (amine / epichlorohydrin condensation type ammonium cation polymer flocculant; manufactured by Yokkaichi Chemical Co., Ltd., solid content 50% by mass) (50 parts by mass), BYK348 (manufactured by Big Chemie Japan Co., Ltd.) (5) By mass), glycerin (100 parts by mass), and water (845 parts by mass) were mixed and stirred to prepare an aqueous pretreatment solution.
The prepared aqueous pretreatment liquid is applied to cotton cloth (with cotton broad sill, manufactured by Color Dyeing Co., Ltd., product code A02-01002) (referred to as "cotton" in the table below), polyester cloth (color dyeing Co., Ltd.) by the padding method. Co., Ltd., product code A02-01019) (referred to as "polyester" in the table below), and 65% polyester 35% cotton blend (blended polyester 65 / cotton 35 broad, manufactured by Color Dyeing Co., Ltd., product code A02-01030) Each fabric (referred to as "blended fabric" in the table below) was squeezed at a drawing ratio of 70% and dried for 24 hours to obtain a pretreated fabric. The drawing ratio (%) represents the residual amount (mass ratio) of the aqueous treatment liquid with respect to the fabric after the cloth containing the aqueous treatment liquid is squeezed.

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

(Heat treatment)
The obtained colored cloth is dried at 20 ° C. for 12 hours, and then heated using a heat press machine (desktop automatic flat press machine AF-54TEN type, manufactured by Asahi Textile Machinery Co., Ltd.) at 200 ° C. for 60 seconds to obtain ink. Was established.

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

<Color development>
The color development property was evaluated by the following criteria based on the 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

The obtained colored cloth was evaluated for washing resistance, sweat resistance, abrasion resistance, discharge stability and aging stability as follows.

<Wash resistance>
Washing resistance was evaluated based on JIS L-0844 A-2 (revised in 2011). The evaluation result of washing resistance shows that the larger the value, the better the robustness.
<Sweat resistance>
Sweat resistance was evaluated based on JIS L-0848 (revised in 2004). The evaluation result of sweat resistance shows that the larger the value, the better the robustness.
<Abrasion resistance>
The abrasion resistance was evaluated based on JIS L-0849 type II (revised in 2013). The evaluation result of abrasion resistance shows that the larger the value, the better the robustness.

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

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 printing)
The components shown in Table 6 below, 1 part by mass (solid content) of Surfinol 104 (manufactured by Nisshin Chemical Industry Co., Ltd.) and ultrapure water as a surfactant are mixed so that the total amount of ink is 100 parts by mass, and a cellulose acetate filter is used. The ink was filtered through (pore diameter: 0.8 μm), and the printing inkjet inks (BI-27) to (B1-34) shown in the table below were prepared.

The abbreviations in the table are listed below.
GLY: Glycerin PG: Propylene Glycol P1: Self-dispersing carbon black pigment CAB-O-JET 200 (manufactured by Cabot Corporation)
W1: Carnauba wax CL1: Elastron BN-77 (blocked isocyanate, volume average particle size 19 nm, dissociation temperature 120 ° C or higher, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

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

Examples IS-1 to IS-3, Comparative Example IS-1C
[Creation of inkjet ink (Qm)]
(Preparation of pigment dispersion)
3 g of a styrene-acrylic acid copolymer (John Krill 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 size of 0.5 mm were filled in a volume fraction 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 is placed in a three-necked flask, the internal temperature is 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 is added thereto for 3 hours. Dropped over. After the dropping, the mixture was heated under reflux for 5 hours, cooled to room temperature, and heated under reduced pressure to obtain a residue of the polymer. To this, 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. It 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 mass% aqueous solution of the aqueous binder, 2.9 g of PDX-7664A (trade name, manufactured by BASF), 10 g of triethylene glycol monobutyl ether, 5 g of 1,2-hexanediol, diethylene glycol 11 .2 g and 0.6 g of Orphine 465 (manufactured by Nisshin Kagaku Kogyo Co., Ltd., trade name) are mixed, ion-exchanged water is added thereto to prepare the total amount to 100 g, and the total amount is adjusted to 100 g, filtered through a 0.8 μm filter, and inkjet ink (Qm). ) Was obtained. The inkjet ink (Qm) is magenta ink.

[Creation of inkjet ink (Qc)]
C. I. Instead of Pigment Red 112, C.I. I. Inkjet ink (Qc) was prepared in the same manner as the inkjet ink (Qm) except that Pigment Blue 15: 4 was used. The inkjet ink (Qc) is cyan ink.

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

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

[Creation of ink set for inkjet printing]
Inkjet printing ink sets S1 to S3 and X1 were prepared by combining the inkjet inks shown in the table below.

(Ink set evaluation method)
(Preparation of aqueous pretreatment solution containing flocculant)
Catiomaster PD-7 (coagulant; manufactured by Yokkaichi Chemical Co., Ltd., solid content 50% by mass) (50 parts by mass), BYK348 (manufactured by Big Chemie Japan Co., Ltd.) (5 parts by mass), glycerin (100 parts by mass), Water (845 parts by mass) was mixed and stirred to prepare an aqueous pretreatment solution.
(Pretreatment process)
The above-prepared aqueous pretreatment liquid is applied to polyester cloth (polyester tropical (manufactured by Teijin Co., Ltd.), color dyeing company, product code A02-01019), cotton cloth (with cotton broad sill, color Co., Ltd.) by the padding method. Dyeing company, product code A02-01002), and polyester 65% cotton 35% blended fabric (blended polyester 65 / cotton 35 broad, manufactured by Color Dyeing Co., Ltd., product code A02-01030) with a squeezing ratio of 70%. It was dried for 24 hours. The drawing ratio (%) represents the residual amount (mass ratio) of the aqueous treatment liquid with respect to the fabric after the cloth containing the aqueous treatment liquid is squeezed.

(Inkjet printing, heat treatment and evaluation)
Inkjet printing ink sets S1 to S3 and X1 are loaded into an ink cartridge, and a polyester fabric (polyester tropical (polyester tropical (polyester tropical)) after the pretreatment step is used using an inkjet printer (Calario PX-045A manufactured by Seiko Epson Corporation, trade name). Teijin Co., Ltd.), Color Dyeing Co., Ltd., Product Code A02-01019), Cotton cloth after pretreatment process (with cotton broad sill, Color Dyeing Co., Ltd., Product Code A02-01002), and pretreatment Images were imprinted on the post-process polyester 65% cotton 35% blend (blended polyester 65 / cotton 35 broad, manufactured by Color Dyeing Co., Ltd., product code A02-01030), and dried at room temperature for 12 hours. ^{After drying, heat treatment is 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., trade name: desktop automatic flat press machine AF-54TEN type). A colored cloth was obtained.

The obtained colored cloth was visually evaluated for sensory analysis.
The case where all three types of fabrics were clear was evaluated on a scale of A, the case where two types were clear was evaluated on a scale of B, the case where only one type was clear was evaluated on C, and the case without a clear image was evaluated on a scale of D. The results are shown in Table 8 below.

When the ink set of the present invention was used, a clear image was obtained with all three types of fabrics as compared with the ink set for comparison. It is presumed that by using the black ink of the present invention, the effect of tightening the image of the color ink was exhibited and a clear image was obtained.

According to the present invention, various kinds of fabrics can be colored, and the color development property, ink jet ejection property, aging stability, and dyeing fastness (washing resistance, abrasion resistance, and sweat resistance) of the obtained image can be colored. ), An ink cartridge filled with the above ink, an ink set, an inkjet printer, and an inkjet 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 a Japanese patent application filed on June 26, 2018 (Japanese Patent Application No. 2018-121347), the contents of which are incorporated herein by reference.

Claims (20)

The colored resin particles contain 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) are contained. ) Is an ink having a mass ratio (dye (A)) / (resin (B)) of 1.2 or more.

In equation (1),
R _{101 to} R ₁₂₀ each independently represent a hydrogen atom or a substituent. The ink according to claim 1, wherein the mass ratio (dye (A)) / (resin (B)) of the dye (A) to the resin (B) is 2-9. 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. 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. The aqueous organic solvent contains 17% by mass or more of a solvent having a boiling point of 150 ° C. or higher at 1 atm consisting of only carbon atoms, hydrogen atoms and oxygen atoms, or from only carbon atoms, hydrogen atoms and oxygen atoms. The ink according to any one of claims 1 to 4, which contains 15% by mass or more of a solvent having a boiling point of 200 ° C. or higher at 1 atm with respect to the ink. The ink according to any one of claims 1 to 5, wherein the aqueous organic solvent contains tetraethylene glycol. The ink according to any one of claims 1 to 6, further containing a cross-linking agent. The ink according to any one of claims 1 to 7, further containing wax. The ink according to any one of claims 1 to 8, further containing a pigment. The ink according to any one of claims 1 to 9, wherein the ink is for inkjet. The ink according to any one of claims 1 to 9, wherein the ink is for printing. An inkjet printing method comprising a step of printing the ink according to any one of claims 1 to 11 on a fabric by an inkjet method. The inkjet printing method according to claim 12, further comprising a heat treatment step. The inkjet printing method according to claim 12 or 13, further comprising a pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to the fabric to obtain a pretreated fabric. The inkjet printing method according to claim 14, wherein the flocculant is an ammonium cationic polymer. The inkjet printing method according to any one of claims 12 to 15, wherein the fabric contains at least one of cotton and polyester. 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. An ink cartridge filled with the ink according to any one of claims 1 to 11. An inkjet printer filled with the ink according to any one of claims 1 to 11. A method for producing a colored resin particle aqueous dispersion in which colored resin particles containing a dye and a resin are dispersed in water, which comprises the following steps (1) and (2).
Step (1): A step of emulsifying a mixture containing the dye (a), the resin (b), the water (c), and the 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). However, the dye (a) and the resin (b) in the mixture of the step (1). 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 of the step (1) is 1. It is / 9 to 1/1.

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