WO2017110744A1

WO2017110744A1 - Aqueous ink and inkjet textile printing method

Info

Publication number: WO2017110744A1
Application number: PCT/JP2016/087801
Authority: WO
Inventors: 宏毅川嶋
Original assignee: コニカミノルタ株式会社
Priority date: 2015-12-25
Filing date: 2016-12-19
Publication date: 2017-06-29
Also published as: JPWO2017110744A1; CN108431144A

Abstract

The present invention relates to an aqueous ink for inkjet textile printing, which contains a compound represented by formula (1), a fixing resin, a water-soluble organic solvent, a pigment and water. The present invention also relates to an inkjet textile printing method which uses this aqueous ink. The present invention provides: an aqueous ink for inkjet textile printing, which is capable of forming images that have improved rubbing resistance, while suppressing texture change of a fabric after textile printing due to heat; and an inkjet textile printing method which uses the aqueous ink.

Description

Water-based ink and inkjet printing method

The present invention relates to a water-based ink and an ink jet textile printing method.

Fabric printing by an inkjet recording method (hereinafter, also simply referred to as “inkjet printing”) is an image forming method in which ink droplets are ejected from an inkjet head and landed on the fabric to form an image on the fabric.

Inkjet textile printing is suitable for producing small amounts of various images because it is not necessary to produce a plate. Inkjet textile printing uses less ink than is necessary for image formation, and therefore has little waste liquid and is excellent in environmental suitability.

In inkjet printing, water-based ink containing an acid dye, reactive dye or disperse dye is often used as a color material. However, when inkjet printing is performed with ink containing these dyes, additional processing is required before and after image formation, which increases the cost of image formation and requires a long time for image formation. There are challenges. For this reason, a method for ink-jet printing using a water-based ink containing a pigment, which does not require the additional treatment, has been developed.

However, unlike dyes, pigments are unlikely to enter the interior of the fibers constituting the fabric, so when printing is performed with ink containing pigments, the formed images may have low abrasion resistance. Therefore, a water-based ink for textile printing containing a pigment may contain a fixing resin in order to improve the fixability of the pigment to the fabric. The fixing resin forms a thin film on the surface of the fabric by being heated after droplets of water-based ink land on the surface of the fabric. It is considered that the water-based ink containing the fixing resin can improve the abrasion resistance of the image formed on the fabric by holding the coloring material in the film. A resin compound such as a fixing resin may be used after neutralizing acidic groups in order to improve dispersibility in ink.

However, resin compounds such as fixing resins may be oxidized and denatured by heat. If the resin landed on the surface of the fabric is modified by ink jet printing, the fabric may have a stiff texture. In order to prevent denaturation of the resin by this heat, a technique for adding an antioxidant to the ink is known. For example, Patent Document 1 discloses that a color filter inkjet ink containing a pigment and a thermosetting binder further contains a phenol-based antioxidant and a sulfur-based antioxidant so that the resin deteriorates during heating. It is described that yellowing of the ink material can be suppressed.

Note that Patent Document 2 describes that hydroquinone, which is an antioxidant, has an effect of suppressing the formation of bubbles in the ink and improving the ejection stability of the ink from the inkjet head.

JP 2010-237617 A JP 2003-311948 A

According to the ink of Patent Document 1, it is expected that denaturation of the resin due to heating can be suppressed. However, according to the knowledge of the present inventor, even when ink-jet printing is performed using a water-based ink containing a phenol-based antioxidant and a sulfur-based antioxidant as in Patent Document 1, the resin is modified during heating. The change in the texture of the fabric could not be sufficiently suppressed.

In addition, if the ink contains a large amount of resin, the viscosity of the ink increases and the ink jet head may not be ejected as droplets. Therefore, the water-based ink for ink jet printing can contain only a small amount of resin. Therefore, there has been a demand for development of a method for further improving the abrasion resistance with a small amount of fixing resin.

The present invention has been made in view of the above problems, and is a water-based ink for inkjet printing, which suppresses a change in the texture of the fabric after printing and improves the abrasion resistance of the formed image. It is an object of the present invention to provide a water-based ink that can be used, and an ink jet textile printing method using such a water-based ink.

In view of the above problems, the present invention relates to the following water-based ink and inkjet printing method.

[1] A water-based ink for inkjet printing, which contains a compound represented by the formula (1), a fixing resin, a water-soluble organic solvent, a pigment, and water.

(In the formula (1),
R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 8 carbon atoms. An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, and one functional group selected from the group consisting of a phenyl group,
R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
X is a divalent structure represented by a single bond, a sulfur atom or —CHR ⁶ —;
R ⁶ is a hydrogen atom or one functional group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 5 to 8 carbon atoms,
A is an alkylene group having 2 to 8 carbon atoms or a divalent structure represented by * —CO—R ⁷ —,
R ⁷ is a single bond or an alkylene group having 1 to 8 carbon atoms,
* Is a binding site with an oxygen atom,
One of Y and Z is one functional group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms and an aralkyloxy group having 7 to 12 carbon atoms,
The other of Y and Z is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )

[2] The aqueous ink according to [1], wherein the compound represented by the formula (1) is contained in an amount of 0.01% by mass to 3.0% by mass with respect to the total mass of the ink.
[3] The water-soluble organic solvent is one solvent selected from the group consisting of 1,2-alkanediol, 2-methyl-1,3-propanediol and 2-pyrrolidone, [1] or [2 ] Water-based ink as described in.
[4] The water-based ink according to any one of [1] to [3], wherein the surfactant is an acetylene glycol surfactant.
[5] The water-based ink according to any one of [1] to [4], wherein the fixing resin includes a polyacrylic resin or a polyurethane resin.
[6] An ink-jet printing method comprising forming an image on a fabric with the water-based ink according to any one of [1] to [5].

According to the present invention, a water-based ink for ink-jet printing, which can suppress a change in texture due to heat of a fabric after printing, and can improve the abrasion resistance of the formed image, and its An inkjet printing method using such a water-based ink is provided.

FIG. 1A is a side view illustrating an example of a configuration of a main part of a line recording type inkjet recording apparatus. FIG. 1B is a plan view illustrating an example of a configuration of a main part of a line recording type inkjet recording apparatus.

1. Water-based ink for inkjet printing The water-based ink for ink-jet printing according to the present invention (hereinafter also simply referred to as “ink of the present invention”) is represented by water, pigment, water-soluble organic solvent, fixing resin, and formula (1). A water-based ink containing the compound to be prepared. The ink of the present invention may further contain other components including an antioxidant, a surfactant and an antifungal agent.

In equation (1),
R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 8 carbon atoms. An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, and one functional group selected from a phenyl group,
R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
X is a divalent structure represented by a single bond, a sulfur atom or —CHR ⁶ —;
R ⁶ is a hydrogen atom or one functional group selected from an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 5 to 8 carbon atoms,
A is an alkylene group having 2 to 8 carbon atoms or a divalent structure represented by * —CO—R ⁷ —,
R ⁷ is a single bond or an alkylene group having 1 to 8 carbon atoms,
* Is a binding site with an oxygen atom,
One of Y and Z is one functional group selected from a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, and an aralkyloxy group having 7 to 12 carbon atoms,
The other of Y and Z is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

The ink of the present invention can suppress the change in the texture due to the heat of the fabric after printing, and can improve the abrasion resistance of the formed image when a fixing resin is contained. This is considered to be due to the following reasons.

Both the structure having an oxygen atom in the vicinity of the benzene ring of the compound represented by the formula (1) and the phosphorus atom have high activity of scavenging radicals. The compound represented by the formula (1) is considered to have a synergistic increase in the activity of scavenging radicals due to the presence of these structures and atoms in the same molecule. Therefore, since the ink containing the compound represented by the formula (1) captures radicals and is present only in a small amount even when heated, the resin is not easily modified by radicals, and the texture of the fabric due to the heat of the resin is not affected. It is thought that the change is suppressed. Further, even when the ink contains a fixing resin, the pigment is sufficiently fixed on the fabric without the fixing resin being modified, so that it is considered that the rub resistance of the formed image is sufficiently increased.

According to the knowledge of the present inventor, conventional antioxidants such as phenolic antioxidants and sulfur-based antioxidants described in Patent Document 1 and hydroquinone as in Patent Document 2, and neutralizing bases In the case of a water-based ink containing a resin neutralized with, the ink ejection stability may be deteriorated particularly after the ink has been stored for a long period of time. This is presumably because conventional antioxidants deteriorate and oxidize while stored in ink for a long period of time. This deteriorated and oxidized antioxidant is considered to act on the neutralized base that neutralizes the acidic group of the resin to peel the neutralized base from the resin and reduce the dispersion stability of the resin. On the other hand, the compound represented by the formula (1) is unlikely to deteriorate even when stored in ink for a long period of time, and thus is unlikely to cause a decrease in dispersion stability of the resin.

Hereinafter, the ink of the present invention will be described in more detail through a detailed description of each component.

1-1. Compound represented by Formula (1) The ink of the present invention contains a compound represented by Formula (1). As for the compound represented by Formula (1), only 1 type may be contained in the ink of this invention, and 2 or more types which have a different structure may contain.

In the compound represented by the formula (1), R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and 5 to 8 carbon atoms. And a functional group selected from a cycloalkyl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and a phenyl group.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group. , T-pentyl group, i-octyl group, t-octyl group and 2-ethylhexyl group.

Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the alkylcycloalkyl group having 6 to 8 carbon atoms include 1-methylcyclopentyl group, 1-methylcyclohexyl group and 1-methyl-4-i-propylcyclohexyl group.

Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, α-methylbenzyl group, and α, α-dimethylbenzyl group.

Among these, R ¹ , R ^2, and R ⁴ are each an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 8 carbon atoms. preferable. From the viewpoint of increasing the affinity with the fixing resin to make the fixing resin difficult to deteriorate and more sufficiently suppressing the change in the texture of the fabric due to the modification of the resin, R ¹ and R ⁴ are t-butyl groups, A t-alkyl group, a cyclohexyl group, or a 1-methylcyclohexyl group including a t-pentyl group and t-octyl group is more preferable, and a t-butyl group or a t-pentyl group is more preferable.

R ² is more preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms. From the viewpoint of producing a compound represented by the formula (1) by making it easy to obtain from a readily available raw material, R ² is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, It is more preferably an alkyl group having 1 to 5 carbon atoms, including an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group and a t-pentyl group, and a methyl group, a t-butyl group or A t-pentyl group is particularly preferred.

R ⁵ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and among them, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, i It is more preferably an alkyl group having 1 to 5 carbon atoms, including a -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and t-pentyl group.

In the compound represented by the formula (1), R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms which R ³ can take include an alkyl group having 1 to 8 carbon atoms which R ¹ , R ² , R ⁴ and R ⁵ can take.

R ³ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group.

In the compound represented by the formula (1), X is a divalent structure represented by a single bond, a sulfur atom or —CHR ⁶ —. R ⁶ is a hydrogen atom or one functional group selected from an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 5 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms that can be taken by R ⁶ include the carbon numbers that R ¹ , R ² , R ^4, and R ⁵ can take, respectively. An alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 5 to 8 carbon atoms are included.

X is a single bond, a methylene group, or a methylene group substituted with a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, or a t-butyl group. Is preferred.

In the compound represented by the formula (1), A is an alkylene group having 2 to 8 carbon atoms or a divalent structure represented by * —CO—R ⁷ —. R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms. The above * is a bonding site with an oxygen atom.

Examples of the alkylene group having 2 to 8 carbon atoms which A can take include ethylene group, propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group and 2,2-dimethyl-1,3-propylene. A group is included. When A is an alkylene group having 2 to 8 carbon atoms, A is preferably a propylene group.

Examples of the alkylene group having 1 to 8 carbon atoms which R ⁷ can take include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and 2,2-dimethyl- 1,3-propylene groups are included. When A is a divalent structure represented by * —CO—R ⁷ —, R ⁷ is preferably a single bond or an ethylene group.

In the compound represented by the formula (1), one of Y and Z is one selected from a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms and an aralkyloxy group having 7 to 12 carbon atoms. It is a functional group. Examples of the alkoxy group having 1 to 8 carbon atoms that Y and Z can take include a functional group in which oxygen is bonded to an alkyl group having 1 to 8 carbon atoms that R ¹ , R ² , R ⁴ and R ⁵ can take. A group is included. Examples of the aralkyloxy group having 7 to 12 carbon atoms that Y and Z can take include one end of the aralkyl group having 7 to 12 carbon atoms that R ¹ , R ² , R ⁴ and R ⁵ can take. Functional groups with oxygen attached are included.

In the compound represented by the formula (1), one of Y and Z other than the above is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Specific examples of the compound represented by the formula (1) include 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di -T-butyl-4-hydroxyphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4 , 8-Di-tert-butyl-6- [3- (3,5-di-tert-butyl-4-hydroxyl Enyl) propionyloxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10 -Dimethyl-4,8-di-t-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxa Phosphocine, 2,4,8,10-tetra-t-butyl- -(3,5-di-t-butyl-4-hydroxybenzoyloxy) -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10 -Tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 2 , 10-Dimethyl-4,8-di-t-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] -12H-dibenzo [d, g] [1, 3,2] dioxaphosphocine, 2,4,8,10-tetra-tert-butyl-6- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [D, g] [1,3,2] dioxaphosphocin, 2,1 -Diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3 2] Dioxaphosphocine and 2,4,8,10-tetra-t-butyl-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy ] -Dibenzo [d, f] [1,3,2] dioxaphosphine.

The compound represented by the formula (1) is produced, for example, by reacting the bisphenol represented by the formula (2), phosphorus trihalide, and the hydroxy compound represented by the formula (3). Can do.

In the formula (2), R ^1, R ^2, R ³ and X are the same as the R ^1, R ^2, R ³ and X in Formula (1).

In the formula ^{(2), R 4, R} 5, A, Y and Z are as defined above ^{^{R 4, R 5, A,}} Y and Z in Formula (1).

Examples of the phosphorus trihalide include phosphorus trichloride and phosphorus tribromide. The phosphorus trihalide is preferably phosphorus trichloride.

Examples of the method for producing the compound represented by the formula (1) include an intermediate produced by reacting the bisphenol represented by the formula (2) with the above phosphorus trihalide by a known method. A two-stage reaction method in which the intermediate compound and the hydroxy compound represented by the formula (3) are further reacted by a known method.

The ink of the present invention preferably contains the compound represented by the formula (1) in an amount of 0.002% by mass to 5.0% by mass with respect to the total mass of the ink. By setting the content of the compound represented by the formula (1) to 0.002% by mass or more, the effect of suppressing the change in the texture due to the heat and enhancing the abrasion resistance of the formed image is more preferable. To be played. By setting the content of the compound represented by the formula (1) to 5.0% by mass or less, the compound represented by the formula (1) is sufficiently dissolved in the ink, and the ejection stability due to the component that cannot be dissolved. It is possible to suppress the deterioration of the property and the precipitation of components that could not be dissolved on the surface of the formed image. From the standpoint of increasing both the effect of suppressing changes in texture due to heat and the effect of increasing the abrasion resistance of the formed image, the ink of the present invention contains 0.01% of the compound represented by formula (1). More preferably, it is contained in an amount of not less than 3.0% by mass and more preferably not less than 0.1% by mass and not more than 3.0% by mass.

1-2. Fixing Resin The ink of the present invention contains a fixing resin. Examples of the fixing resin include a polyacrylic resin and a polyurethane resin. Only one type of fixing resin may be contained in the ink of the present invention, or two or more types may be contained. From the viewpoint of sufficiently suppressing the change in texture due to heat and enhancing the ejection stability, it is preferable that the ink of the present invention contains both a polyacrylic resin and a polyurethane resin. The ink of the present invention may contain a fixing resin other than these.

The ink of the present invention preferably contains the fixing resin in an amount of 0.1% by mass to 20% by mass with respect to the total mass of the ink, and is contained in an amount of 1% by mass to 15% by mass. It is more preferable that it is contained in an amount of 2% by mass or more and 10% by mass or less.

From the viewpoint of further improving the dispersibility of the fixing resin in the ink, the fixing resin preferably has an acidic group. Since the compound represented by the formula (1) is deteriorated and is not easily oxidized as compared with the conventional oxidizing agent, the dispersion stability of the resin is lowered by acting on the neutralized base and peeling the neutralized base from the resin. Is considered to be difficult to occur. Examples of the acidic group include a carboxyl group, a sulfo group, and a phosphono group. In the present invention, the phosphono group includes a phosphate group. The polyacrylic resin is a structural unit derived from a (meth) acrylic monomer having a carboxyl group containing (meth) acrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid and fumaric acid It is preferable to have a structural unit derived from (meth) acrylic acid or methacrylic acid.

In the present invention, “(meth) acryl” means “acryl” and “methacryl”, “(meth) acrylate” means “acrylate” and “methacrylate”, and “(meth) acryloyl”. Means “acryloyl” and “methacryloyl”, “(iso or tertiary)” and “(iso)” both in the presence and absence of these groups, If not present, it indicates normal.

The acidic group is preferably at least partially neutralized with a neutralizing base. Examples of the neutralizing base include alkali metal hydroxides including lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates including lithium carbonate, sodium carbonate and potassium carbonate, alkali metal phosphates, monomethyl Alkylamines including amine, dimethylamine, trimethylamine, monoethylamine, diethylamine and triethylamine, ethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine, monopropanolamine, dipropanolamine, tripropanolamine , Isopropanolamine, trishydroxymethylaminomethane, and 2-amino-2-ethyl-1,3-propanediol (AEPD) Coleamines, choline, morpholine, N-methylmonoformin, cyclic amines including N-methyl-2-pyrrolidone and 2-pyrrolidone, and tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide Organic ammonium hydroxide containing is included. From the viewpoint of further improving the storage stability and ejection stability of the ink, the neutralizing base is preferably an alcoholamine, and more preferably ethanolamine or dimethylethanolamine.

1-2-1. Polyacrylic Resin Polyacrylic resin may be a commercially available product or may be synthesized and used. Examples of commercially available polyacrylic resins include BASF Corporation, JONCRYL741 (Tg: 15 ° C., styrene / acrylic), JONCRYL775 (Tg: 37 ° C., styrene / acrylic), JONCRYL537 (Tg: 49 ° C., Styrene / acrylic), and JONCRYL538 (Tg: 66 ° C., styrene / acrylic) (“JONCRYL” is a registered trademark of the company), manufactured by Toagosei Co., Ltd., Aron HD-5 (Tg: 45 ° C., acrylic) ( “Aron” is a registered trademark of the same company), and Movinyl 742N (Tg: 37 ° C., acrylic type) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (“Movinyl” is a registered trademark of the company). Only one type of polyacrylic resin may be contained in the ink of the present invention, or two or more types may be contained.

Preferred examples of the polyacrylic resin include polyacrylic polymer fine particles.

The average particle diameter of the polymer fine particles is preferably from 50 nm to 500 nm, and more preferably from 60 nm to 300 nm. By setting the average particle diameter of the polymer fine particles to 50 nm or more, the fixability of the pigment to the fabric can be further improved, and the abrasion resistance of the formed image can be further improved. By setting the average particle size of the polymer fine particles to 500 nm or less, the viscosity of the ink is not excessively increased, and a decrease in ejection stability from the inkjet head can be suppressed.

In the present invention, the average particle size of the particles is a z-average particle size measured with a dynamic light scattering particle size distribution analyzer (manufactured by Malvern, Zetasizer Nano S (“Zetasizer” is a registered trademark of the company)). .

From the viewpoint of further improving the fixability of the pigment and further improving the abrasion resistance of the formed image, the polymer fine particles have a glass transition temperature (hereinafter also simply referred to as “Tg”) of −10 ° C. or lower. Is preferred. From the above viewpoint, the Tg of the polymer fine particles is preferably −15 ° C. or lower, more preferably −20 ° C. or lower, further preferably −25 ° C. or lower, and −30 ° C. or lower. More preferably.

From the viewpoint of further improving the washing fastness of the printed fabric, the acid value of the polymer fine particles is preferably 100 mgKOH / g or less, more preferably 50 mgKOH / g or less, and 30 mgKOH / g or less. More preferably.

In the present invention, the acid value of the resin is the acid value determined by neutralization titration according to JIS K 0070.

In addition, from the viewpoint of further improving the washing fastness of the printed fabric, the polymer fine particles preferably have a weight average molecular weight of 100,000 or more, more preferably 200,000 or more.

In the present invention, the weight average molecular weight of the resin is a styrene equivalent molecular weight measured by GPC combined with a polystyrene gel column using a solvent obtained by adding 1 ml of THF to 1 mg of a measurement sample.

From the viewpoint of further improving the friction fastness at the time of dry friction and wet friction of the printed fabric, the polymer fine particles have a total mass of the structural unit derived from alkyl (meth) acrylate or cyclic alkyl (meth) acrylate. It is preferable to occupy 70% by weight or more. From the above viewpoint, the polymer fine particles contain 5% by weight or more of a constituent unit derived from styrene in addition to a constituent unit derived from the alkyl (meth) acrylate or cyclic alkyl (meth) acrylate in the total mass. It is preferable to occupy the weight% or less.

Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having 1 to 24 carbon atoms, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) Acrylate, t-butylcyclohexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate and tetrameth Rupiperijiru (meth) acrylates include.

Examples of the cyclic alkyl (meth) acrylate include cyclic alkyl (meth) acrylates having 3 to 24 carbon atoms, such as dicyclopentanyl (meth) acrylate and dicyclopentenyl (meth) acrylate. , Dicyclopentenyloxy (meth) acrylate and behenyl (meth) acrylate.

1-2-2. Polyurethane Resin A polyurethane-based resin may be a commercially available product, or may be synthesized and used. Examples of commercially available polyurethane-based resins include Acrit WBR-016U (Tg: 20 ° C.), Acryt WEM-321U (Tg: 20 ° C.), Acrit WBR-2018 (Tg: 20 ° C.), manufactured by Taisei Fine Chemical Co., Ltd. , ACRYT WBR-2000U (Tg: 45 ° C.), ACRYT WBR-601U (Tg: −30 ° C.) (“Akrit” is a registered trademark of the company), PUE-1000, PUE-1020A manufactured by Murayama Chemical Laboratory Co., Ltd. , PUE-1370, and PUE-800, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Superflex 650, Superflex 860, and Superflex 210 (“Superflex” is a registered trademark of the company), manufactured by Toagosei Co., Ltd., Neotan UE -1100 ("Neotan" is a registered trademark of the company), three U-coat UX-150, U-coat UWS-145, Vermarine UA-150 (Tg 36 ° C.), U-coat UA-368, and Euprene UXA-307 (“U-coat”, “Bermarin” and “Euprene” are all manufactured by Kasei Kogyo Co., Ltd. Company registered trademark), Sumika Covestro Urethane Co., Ltd., Implanil DLP-R (Tg 21 ° C.), Implanyl DLN (Tg-55 ° C.), Implanyl DLC-F (Tg-42 ° C.), Bihydrol (UHXP2648) (Tg-51 ° C.), and Dispacol U-53 (Tg-58 ° C.) (“Imperil”, “Bihydrol” and “Dispacol” are registered trademarks of Bayer), and Ube Industries, Ltd. UW-1005-E (Tg-30 ° C), and UW- 101-E (Tg69 ℃). Polyurethane resin to be included, in the ink of the present invention may be only one kind is contained, or two or more of these may be contained.

Examples of the preferred polyurethane-based resin include a resin having a structure represented by any one of formulas (4) to (7) (hereinafter also simply referred to as “polyurethane A”), and formula (9). A polyurethane-based resin having a structural unit derived from a polyol represented by the formula (10) or a structural unit derived from a polyol represented by the formula (10), and a structural unit derived from a polyisocyanate, (Hereinafter, also simply referred to as “polyurethane B”).

1-2-2-1. Polyurethane A
Polyurethane A is a resin having a structure represented by any one of formulas (4) to (7). Only one type of polyurethane A may be contained in the ink of the present invention, or two or more types may be contained.

In the formulas (4) to (7), R ⁸ is an aliphatic group or an aromatic group, and R ⁹ is — (CH ₂ ) _n2 —COOH or — (CH ₂ CH ₂ O) _n3 —CH ₃ . , N1 is an arbitrary natural number, n2 is an integer of 1 to 10, n3 is an integer of 1 to 100, and X ¹ is NH or O.

From the viewpoint of further improving the abrasion resistance of the formed image, the wash fastness of the printed fabric and the friction fastness of the printed fabric during dry friction and wet friction, polyurethane A is crosslinked in the resin. It is preferable to have.

Preferred examples of polyurethane A include a resin having a structure represented by formula (8).

In the formula (8), R ⁹ is an aliphatic group or an aromatic group, R ¹⁰ is a residue of a diol compound, and n4 is selected so that the weight average molecular weight of the resin is 3000 or more and 200000 or less. It is an arbitrary integer.

Examples of aliphatic groups represented by R ⁹ include divalents derived from isophorone diisocyanate (IPDI), hydrogenated m-xylene diisocyanate (H6XDI), hydrogenated diphenylmethane diisocyanate (H12MDI), and hexamethylene diisocyanate (HDI). Is included.

Examples of the aromatic group represented by R ⁹ include divalent groups derived from m-xylene diisocyanate (XDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate (MDI).

From the viewpoint of further improving the abrasion resistance of the formed image, R ₁ is preferably an aliphatic group.

Examples of the residue of the diol compound represented by R ¹⁰ include an alkylene group, a polyether group, a polyester group, a polycarbonate group, and a polycaprolactone group. From the viewpoint of further improving the abrasion resistance of the formed image, R ¹⁰ is preferably an alkylene group, a polyether group, a polyester group or a polycaprolactone group, an alkylene group having 1 to 30 carbon atoms, and 2 carbon atoms. More preferably, it is an alkyl ether group having 60 or less or an alkyl ester group having 1 to 30 carbon atoms.

1-2-2-2. Polyurethane B
The polyurethane B is a polyurethane-based resin having a structural unit derived from the polyol represented by the formula (9) or a structural unit derived from the polyol represented by the formula (10) and a structural unit derived from polyisocyanate. It is. One type of polyurethane B may be contained in the ink of the present invention, or two or more types may be contained.

From the viewpoint of further improving the abrasion resistance of the formed image, the wash fastness of the printed fabric, and the ejection stability of the ink of the present invention, the Tg of polyurethane B is preferably 30 ° C. or less, 25 It is more preferable that it is below ℃.

In addition, from the viewpoint of further improving the abrasion resistance of the formed image, the wash fastness of the printed fabric, and the ejection stability of the ink of the present invention, the acid value of polyurethane B is 100 mgKOH / g or less. Is more preferable, and 60 mgKOH / g or less is more preferable.

Further, from the viewpoint of further improving the abrasion resistance of the formed image, the washing fastness of the printed fabric, and the ejection stability of the ink of the present invention, the volume average particle measured by the dynamic light scattering method of polyurethane B The diameter is preferably 20 nm or more and 300 nm or less, and more preferably 30 nm or more and 200 nm or less.

In the formula (9), n5 is an integer of 1 to 6. From the viewpoint of further improving the abrasion resistance of the formed image, the wash fastness of the printed fabric, and the ejection stability of the ink of the present invention, n5 is preferably 2 or more and 4 or less.

In the formula (10), n6, n7 and n8 are each an integer of 0 or more selected so that n6 + n7 + n8 is an integer of 0 or more and 6 or less. From the viewpoint of further improving the abrasion resistance of the formed image, the wash fastness of the printed fabric, and the ejection stability of the ink of the present invention, n6 + n7 + n8 is preferably an integer of 0 or more and 3 or less.

Examples of the above polyisocyanates include diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,6-bis (isocyanato). Methyl) decahydronaphthalene, lysine triisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl ether diisocyanate, 3- (2'-isocyanatocyclohexyl) ) Propyl isocyanate, tris (phenyl isocyanate) thiophosphate, isopropylide Bis (cyclohexyl isocyanate), 2,2'-bis (4-isocyanatoenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 4,4 ', 4 "-triisocyanate-2,5-dimethoxy Phenylamine, 3,3'-dimethoxybenzidine-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diisocyanatobiphenyl, 4,4'-diisocyanato-3 , 3′-dimethylbiphenyl, dicyclohexylmethane-4,4′-diisocyanate, 1,1′-methylenebis (4-isocyanatobenzene), 1,1′-methylenebis (3-methyl-4-isocyanatobenzene), m -Xylylene diisocyanate, p-Xylylene Diisocyanate, 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis ((2-isocyanato-2- Propyl) benzene, 2,6-bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatomethyl) dicyclopentadiene, bis (isocyanatomethyl) tetrahydrothiophene, bis (isocyanatomethyl) thiophene, 2,5- Diisocyanate methylnorbornene, bis (isocyanatomethyl) adamantane, 3,4-diisocyanate selenophan, 2,6-diisocyanate-9-selenabicyclononane, bis (isocyanatomethyl) selenophan, 3,4-diisocyanate, -2, 5-diselenora Dimer acid diisocyanate, 1,3,5-tri (1-isocyanatohexyl) isocyanuric acid, 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-bis (isocyanatomethyl-4- Isocyanato-2-thiabutyl) -1,4-dithiane, 2,5-bis (3-isocyanate-2-thiapropyl) 1,4-dithiane, 1,3,5-triisocyanatocyclohexane, 1,3,5- Tris (isocyanatomethyl) cyclohexane, bis (isocyanatomethylthio) methane, 1,5-diisocyanate-2-isocyanatomethyl-3-thiapentane, 1,2,3-tris (isocyanatoethylthio) propane, 1,2 , 3- (Isocyanatomethylthio) propane, 1,1,6,6-tetrakis (isocyanatomethyl) -2,5- Thiahexane, 1,1,5,5-tetrakis (isocyanatomethyl) -2,4-dithiapentane, 1,2-bis (isocyanatomethylthio) ethane, and 1,5-diisocyanate-3-isocyanatomethyl-2, 4-dithiapentane, dimers by these bullet-type reactions, cyclized trimers thereof, adducts obtained by adding alcohol or thiol to these, and some or all of these isocyanate groups were changed to isothiocyanate groups Compounds are included.

Preferred examples of the polyisocyanate include a compound represented by the formula (11).

In formula (11), n9 is an integer of 3 or more and 10 or less. From the viewpoint of further improving the abrasion resistance of the formed image, the wash fastness of the printed fabric, and the ejection stability of the ink of the present invention, n9 is preferably an integer of 4 or more and 7 or less.

From the viewpoint of further improving the abrasion resistance of the formed image, the washing fastness of the printed fabric, and the ejection stability of the ink of the present invention, the polyurethane B is derived from the polyol represented by the formula (9). The value obtained by dividing the number of structural units by the number of structural units derived from the polyisocyanate is preferably 0.75 or less.

Polyurethane B may contain a structural unit derived from a polyol represented by formula (9) or a polyol other than the polyol represented by formula (10). Examples of the polyol represented by the above formula (9) or the polyol other than the polyol represented by the formula (10) include a polyol represented by the formula (12), a linear aliphatic glycol, an aliphatic branched glycol, and a fat. Cyclic glycols, polyfunctional glycols, polyester polyols, polycarbonate polyols, and polytetramethylene ether glycols are included. Among these, it is preferable that the structural unit derived from the polyol represented by Formula (12) is included.

In the formula (12), n10 is an integer of 3 to 10, and n11 is an integer of 2 to 14. From the viewpoint of further improving the abrasion resistance of the formed image, the wash fastness of the printed fabric, and the ejection stability of the ink of the present invention, n10 is preferably an integer of 5 or more and 7 or less.

Examples of the linear aliphatic glycol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-pentane. Diol, 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, and 1,9-nonanediol.
Examples of the aliphatic branched glycol include neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, -Butyl-2-ethyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, and 2-methyl-1,8-octanediol are included.
Examples of the alicyclic glycol include 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol.
Examples of the polyfunctional glycol include glycerin, trimethylolethane, trimethylolpropane, tributyrolpropane, pentaerythritol, and sorbitol.

The polyester polyol is a compound having a structural unit derived from glycols or ethers and a structural unit derived from a divalent carboxylic acid or an anhydride thereof formed by dehydration condensation.

Examples of glycols that can be a structural unit of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 2-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene Linear aliphatic glycols including glycol, polypropylene glycol, 1,8-octanediol, 1,2-octanediol, and 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dibutyl-1,3- Propanediol, and aliphatic branched glycols including 2-methyl-1,8-octanediol, 1,4-cyclohexanediol, alicyclic glycols including 1,4-cyclohexanedimethanol, and glycerin, trimethylolethane, Polyfunctional glycols including trimethylolpropane, tributyrolpropane, pentaerythritol, and sorbitol are included.

Examples of ethers that can be a structural unit of the polyester polyol include alkyl glycidyl ethers including n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether, and monocarboxylic acid glycidyl esters including versatic acid glycidyl ester. .

Examples of the divalent carboxylic acid or its anhydride that can be a structural unit of the polyester polyol include adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, Examples include glutaric acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, and anhydrides, dimer acid, castor oil and fatty acids thereof.

The polyester polyol may be a polyester polyol obtained by ring-opening polymerization of a cyclic ester compound.

Examples of commercially available polyester polyols include poly [3-methyl-1,5-pentanediol] -alt- (adipic acid) obtained by dehydration condensation of 3-methyl-1,5-pentanediol and adipic acid. ] (Kuraray Co., Ltd., Kuraray Polyol P2010).

Examples of the polycarbonate polyol include a structural unit derived from a polyhydric alcohol and a structural unit derived from dimethyl carbonate, a compound produced by the demethanol condensation reaction, a structural unit derived from a polyhydric alcohol, and diphenyl. These deethylene glycol condensation reactions having a structural unit derived from carbonate, a compound produced by these dephenol condensation reactions, and a structural unit derived from polyhydric alcohol and a structural unit derived from ethylene carbonate The compound produced by is included.

Examples of the polyhydric alcohol include 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl- Saturated or unsaturated glycols including 1,5-pentanediol, octanediol, 1,4-butynediol, dipropylene glycol, tripropylene glycol, and polytetramethylene ether glycol, and 1,4-cyclohexanediglycol And alicyclic glycols including 1,4-cyclohexanedimethanol.

Examples of commercially available polycarbonate polyols include PES-EXP815 made by Tosoh Corporation whose main component is 1,6-hexanediol.

Examples of the polytetramethylene ether glycol are obtained by adding tetrahydrofuran to a polyhydric alcohol containing ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, and neopentyl glycol by ring-opening polymerization. Compounds are included.

Examples of commercially available polytetramethylene ether glycol include PTXG-1800 manufactured by Asahi Kasei Co., Ltd. obtained from tetrahydrofuran and neopentyl glycol.

Examples of other commercial products of the above polyol include Actol EP 3033 (“Actocol” is a registered trademark of the company) manufactured by Mitsui Chemicals, Inc., PREMINOL 7003 and PREMINOL 7001 (“PREMINOL” are registered trademarks of the company), Asahi Glass Co., Ltd. ), Manufactured by ADEKA Corporation, and ADEKA polyether AM302 are included.

1-2-3. Other Fixing Resins Examples of the other fixing resins include polyester resins, polycarbonate resins, polyurea resins, polyacrylamide resins, and vinyl chloride / vinyl acetate copolymer resins.

The fixing resin is preferably used in combination according to the characteristics required for the image to be formed. Examples of these properties include abrasion resistance, water resistance, flexibility and texture. In particular, image scratch resistance and texture are important characteristics in textile printing applications, but they are generally contradictory characteristics, and both high abrasion resistance and good texture can be achieved with only one type of resin. It can be difficult to do. Therefore, it is preferable to use a combination of a plurality of resins in accordance with the material, thickness, usage, and the like of the fabric to be printed, and appropriately change the formulation. For example, texture is often emphasized in silk, nylon, wool, etc. used for high-quality clothes, and abrasion resistance may be emphasized in cotton, polyester, etc. used in T-shirts and work clothes. In addition, even if the cloth is the same material, a thin cloth is often more demanding not to impair the texture than a thick cloth. Thus, in textile printing applications, it is very important to be able to meet the required quality of various fabrics.

Therefore, a plurality of types of inks having different types and blending amounts of resins may be independently applied to the fabric. For example, printing can be carried out using a first ink containing a fixing resin capable of improving the texture and a second ink containing a fixing resin capable of improving the abrasion resistance.

For example, polyurethane resin and polyurea resin exhibit flexible properties and can exhibit a good texture when applied to a fabric. Therefore, the blending ratio of the polyurethane resin or polyurea resin and the resin other than the polyurethane resin or polyurea resin can be adjusted to easily adjust the abrasion resistance and texture of the image. For example, it is preferable to use a first ink containing a small amount (or substantially not containing) a polyurethane resin and a second liquid containing a polyurethane resin or a polyurea resin.

It is sufficient that at least one of the first ink and the second ink contains the compound represented by the formula (1) described above, and the ink containing the compound represented by the formula (1) is an inkjet. If it is applied to the fabric by the method, the other ink may be applied to the fabric by another method.

The fixing resin is a polymer and suppresses the drying of moisture contained in the ink. Therefore, from the viewpoint of improving the drying property, the amount of the fixing resin in the ink is preferably as small as possible. At this time, when a plurality of types of inks having different types and blending amounts of resins are used, only the necessary amount of fixing resin can be applied to each region in the image, so that the drying property is improved and the ink of the present invention is applied. The finished fabric can be dried in a shorter time. Therefore, the plurality of types of inks can be suitably used for applications that require drying of the ink in a shorter time, for example, high-speed and high-volume production of printed images, and single pass that facilitates high-speed and high-volume production. It can be suitably used for textile printing using a recording type printer.

On the other hand, when a plurality of types of inks having different types and blending amounts of resins are used, wetting and spreading of the ink applied to the fabric can be adjusted more easily. If the time from application of ink to drying differs between the areas included in the image, the degree of wetting and spreading of the droplets differs between the areas, which may cause a sense of incongruity of gloss and streak-like unevenness. Even at this time, if a plurality of types of inks having different types and blending amounts of resins are used, an amount of fixing resin capable of adjusting the wetting and spreading of the ink can be applied to each region in the image, so that the time until drying is increased. Even if it is longer, the ink is not excessively wetted and spread, and the above-mentioned glossy feeling and streaky unevenness can be efficiently suppressed. Therefore, the plurality of types of inks can be suitably used for textile printing using a scan recording type printer having a slower printing speed.

1-3. Water-soluble organic solvent The ink of the present invention contains a water-soluble organic solvent. Examples of water-soluble organic solvents include alcohols including methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol and tertiary butanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene Polyols including glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, and thiodiglycol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether Containing glycol ethers Ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, and tetramethyl Amines including propylene diamine, formamide, N, N-dimethylformamide, and amides including N, N-dimethylacetamide, and 2-pyrrolidone are included. As for the water-soluble organic solvent, only 1 type may be contained in the ink of this invention, and 2 or more types may be contained.

Among these, from the viewpoint of facilitating the adsorption or penetration of the compound represented by the formula (1) into the resin, enhancing the stability of the resin against heat, and further suppressing the change in the texture of the fabric due to the modification of the resin. The water-soluble organic solvent preferably contains a polyhydric alcohol or 2-pyrrolidone. Examples of preferred polyhydric alcohols include 1,2-hexanediol, 1,2-pentanediol, and 1,2-alkylene glycols including 1,4-methyl-1,2-pentanediol, 1,2-alkanediols. As well as 2-methyl-1,3-propanediol. Of these water-soluble organic solvents, 1,2-alkanediol, 2-methyl-1,3-propanediol and 2-pyrrolidone are more preferred.

In addition, from the viewpoint of increasing the solubility of the fixing resin in water, suppressing precipitation of the fixing resin during storage of the ink, and further improving the ejection stability of the ink of the present invention, the water-soluble organic solvent contains amines. It is preferable. Further, from the viewpoint of being less volatile and having less odor, and from the viewpoint of low reactivity and high stability, the water-soluble organic solvent is a tertiary monoester containing triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine and the like. More preferably, di- or trialkanolamine is included.

The ink of the present invention preferably contains the water-soluble organic solvent in an amount of 0.1% by mass to 70% by mass with respect to the total mass of the ink, and is 1.0% by mass to 60% by mass. More preferably, it is contained in an amount. The content of the water-soluble organic solvent can be set according to the type of the water-soluble organic solvent. For example, when the ink of the present invention contains 1,2-alkylene glycol, 1,2-alkylene glycol may be contained in an amount of 0.3% by mass to 30% by mass with respect to the total mass of the ink. Preferably, it is contained in an amount of 0.5 to 10% by mass. Further, when the ink of the present invention contains a glycol ether, the glycol ether is preferably contained in an amount of 0.1% by mass or more and 20% by mass with respect to the total mass of the ink, and 0.5% by mass or more. More preferably, it is contained in an amount of 10% by mass.

1-4. Pigment The ink of the present invention contains a pigment. The pigment may be dispersed by a dispersing resin. Examples of the pigment include known organic pigments and inorganic pigments. Examples of pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and azo pigments including chelate azo pigments, phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, As well as polycyclic pigments including quinophthalone pigments, dye lakes including basic dye-type lakes and acid dye-type lakes, and organic solvents including nitro pigments, nitroso pigments, aniline black and daylight fluorescent pigments, and carbon black Inorganic pigments are included. Only one type of pigment may be contained in the ink of the present invention, or two or more types of pigments may be contained.

From the viewpoint of enhancing the dispersibility of the pigment, the ink of the present invention may contain a dispersion resin.

From the viewpoint of further improving the ejection stability of the ink of the present invention, the maximum particle size of the pigment or the composite of the dispersion resin and the pigment is preferably less than 1.0 μm.

1-4-1. Dispersion Resin Examples of the dispersion resin include a dispersant having both the adsorptivity or affinity for the pigment and the affinity for water as the dispersion medium (hereinafter, also simply referred to as “dispersant”). Only one type of dispersion resin may be contained in the ink of the present invention, or two or more types may be contained.

From the viewpoint of further improving the dispersibility of the pigment and the dispersion resin in the ink, the dispersion resin preferably has an acidic group. Since the compound represented by the formula (1) is deteriorated and is not easily oxidized as compared with the conventional oxidizing agent, the dispersion stability of the resin is lowered by acting on the neutralized base and peeling the neutralized base from the resin. Is considered to be difficult to occur. Examples of the acidic group include a carboxyl group, a sulfo group, and a phosphono group.

The acidic group is preferably at least partially neutralized with a neutralizing base. Examples of the neutralizing base include a neutralizing base capable of neutralizing the acidic group of the fixing resin described above. From the viewpoint of further improving the storage stability and ejection stability of the ink, the neutralizing base is preferably an alcoholamine, and more preferably ethanolamine or dimethylethanolamine.

1-4-1-1. Dispersant Examples of the dispersant include hydroxyl group-containing carboxylic acid ester, long chain polyaminoamide and high molecular weight acid ester salt, high molecular weight polycarboxylic acid salt, long chain polyaminoamide and polar acid ester salt, Saturated acid ester, polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, Polyoxyethylene nonylphenyl ether and stearylamine acetate are included. Only one type of dispersant may be contained in the ink of the present invention, or two or more types may be contained.

From the viewpoint of further improving the dispersion stability of the pigment and the ejection stability of the ink of the present invention, the dispersant has a structure having the structure represented by the following formulas (13) to (16) and has a phosphate group-containing copolymer. It is preferably a coalescence.

In the formula (13), R ¹¹ is a hydrogen atom or a methyl group, M ⁺ is a proton, an alkali metal ion or an organic ammonium ion, and n12 and n13 are selected so as not to be 0 at the same time. Is an integer from 6.

In the formula (14), R ¹² is a hydrogen atom or a methyl group, R ¹³ is an alkyl group having 1 to 4 carbon atoms, and n14 and n15 are selected such that n14 + n15 is 2 to 30. Each is an integer of 0 or more and 30 or less.

In the formula (15), R ¹⁴ is a hydrogen atom or a methyl group.

In the formula (16), R ¹⁵ is a hydrogen atom or a methyl group.

The copolymer having a phosphate group may have a structural unit other than the structure represented by the formulas (13) to (16). Examples of such a structural unit include a structural unit derived from a hydrophobic polymerizable monomer and a structural unit derived from a hydrophilic polymerizable monomer.

Examples of the hydrophobic polymerizable monomer include an unsaturated ethylene monomer having an aromatic ring containing styrene, α-methylstyrene, 4-t-butylstyrene, and 4-chloromethylstyrene, methyl (meth) acrylate , Ethyl (meth) acrylate, n-butyl (meth) acrylate, dimethyl maleate, dimethyl itaconate, dimethyl fumarate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, Pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heicosyl (meth) acrylate, and docosyl (meth) acrylate Including alkyl (meth) acrylate, and 1- Butene, 3,3-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 1-octene, 3,3-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 1-nonene, 3,5,5-trimethyl-1-hexene, 1-decene, Has alkyl groups including 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, and 1-docosene Unsaturated ethylene monomer is included.

Examples of the hydrophilic polymerizable monomer include (meth) acrylic acid and its salt, maleic acid and its salt, monomethyl maleate, itaconic acid, monomethyl itaconic acid, fumaric acid, 4-styrenesulfonic acid, and 2- Anionic unsaturated ethylene monomers including acrylamido-2-methylpropanesulfonic acid, and 2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (Meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, acrylic De, N, N- dimethylacrylamide, N-t-butylacrylamide, include nonionic ethylenically unsaturated monomers containing N- octyl acrylamide, and N-t-octyl acrylamide.

From the viewpoint of further increasing the density of the formed image and further improving the dispersion stability of the pigment, the content of the structural unit represented by the above formula (13) in the copolymer having a phosphate group is as follows: It is preferably 10% by mass or more and 60% by mass or less, and more preferably 15% by mass or more and 50% by mass or less. From the viewpoint of further improving the dispersion stability of the pigment, the content of the structural unit represented by the formula (14) in the copolymer having a phosphate group is 5% by mass or more and 50% by mass or less. Preferably, it is 5 mass% or more and 40 mass% or less. The content of the structural unit represented by the formula (15) in the copolymer having a phosphate group is preferably 10% by mass or more and 70% by mass or less, and 20% by mass or more and 60% by mass or less. It is more preferable.

From the viewpoint of further increasing the density of the formed image and further improving the dispersion stability of the pigment, the viscosity at 25 ° C. of a 10% by mass solid content aqueous solution of the above copolymer having a phosphate group is 1. It is preferably 5 mPa · s or more and 30.0 mPa · s or less, and more preferably 1.7 mPa · s or more and 20.0 mPa · s or less.

The amount of the copolymer having a phosphoric acid group contained in the ink of the present invention is preferably 0.005 parts by mass or more and 5 parts by mass or less with respect to 1 part by mass of the pigment, and is preferably 0.005 parts by mass with respect to 1 part by mass of the pigment. The amount is more preferably 01 parts by mass or more and 2 parts by mass or less, and further preferably 0.02 parts by mass or more and 0.5 parts by mass with respect to 1 part by mass of the pigment.

1-4-1-2. Other Dispersing Resins The dispersing resin may be a resin other than the dispersant. Examples of the dispersion resin other than the dispersant include known resins that can be coated and dispersed with a pigment.

1-5. Other Components The ink of the present invention may contain other components including an antioxidant, a surfactant and an antifungal agent.

1-5-1. Antioxidants Examples of the above antioxidants include phenolic hydroxyl group-containing compounds, quinones including methoquinone (hydroquinone monomethyl ether), hydroquinone and 4-methoxy-1-naphthol, hindered amine antioxidants, 1,1- Diphenyl-2-picrylhydrazyl free radicals, N-oxyl free radical compounds, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates Thiourea derivatives, various sugars, phosphate antioxidants, nitrites, sulfites, thiosulfates, aromatic amines, phenylenediamines, imines, sulfonamides, urea derivatives, oximes, hydroxylamine derivatives, Dicyandiamide and polyalkylene Polycondensates of polyamines, phosphorus-containing compounds such as triphenyl phosphine, sulfur-containing compounds such as phenothiazine, a complexing agent to tetraazacyclododecane Anne based Len (TAA), and the like hindered amines.

Examples of the phenolic hydroxyl group-containing compound include
Phenol,
o-, m- or p-cresol (methylphenol), 2-t-butyl-4-methylphenol, 6-t-butyl-2,4-dimethylphenol, 2,6-di-t-butyl-4- Methylphenol, 2-t-butylphenol, 4-t-butylphenol, 2,4-di-t-butylphenol, 2-methyl-4-t-butylphenol, 4-t-butyl-2,6-dimethylphenol, or 2 , 2'-methylene-bis- (6-t-butyl-methylphenol), 4,4'-oxydiphenyl, 3,4-methylenedioxydiphenol (sesame oil), 3,4-dimethylphenol, benzcatechin ( 1,2-dihydroxybenzol), 2- (1'-methylcyclohexyl-1'-yl) -4,6-dimethylphenol, 2- or 4- (1 'Feniruechi-1'-yl) phenol, 2-t-butyl-6-methylphenol, 2,4,6-tris -t- butylphenol, 2,6-di -t- butylphenol, nonylphenol [CAS-Nr. 11066-49-2], octylphenol [CAS-Nr. 140-66-9], 2,6-dimethylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, 3,3 ', 5,5'-tetrabromobisphenol A, 2,6-di- t-Butyl-p-cresol, Kolesin manufactured by BASF Aktiengesellschaft, 3,5-di-tert-butyl-4-hydroxybenzoic acid methyl ester, 4-t-butylbenzcatechin, 2-hydroxybenzyl alcohol, 2-methoxy-4-methylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4-isopropylphenol, 6-isopropyl- m-cresol, n- Utadecyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1, 3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzol, 1,3,5-tris- (3,5-di-t-butyl -4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl-isocyanurate, 1,3,5-tris- (2 , 6-Dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate or pentaerythrit-tetrakis- [β- (3,5-di-tert-butyl-4-hydroxyphenyl) pro Onate], 2,6-di-t-butyl-4-dimethylaminomethylphenol, 6-s-butyl-2,4-dinitrophenol, Irganox 565, 1010, 1076, manufactured by Firma Ciba Specializenechemie 1141, 1192, 1222 and 1425, 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionic acid octadecyl ester. 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionic acid hexadecyl ester, 3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionic acid Octyl ester, 3-thia-1,5-pentanediol-bis- [3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 4,8-dioxa-1,11-undecanediol -Bis- [3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 4,8-dioxa-1,11-undecandiol-bis-[(3'-t-butyl-4 '-Hydroxy-5'-methylphenyl) propionate], 1,9-nonanediol-bis-[(3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] 1,7-heptanediamine-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionic acid amide], 1,1-methanediamine-bis [3- (3 ′, 5'-di-t-butyl-4'-hydroxyphenyl) propionic acid amide], 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionic acid hydrazide, 3- (3' , 5'-dimethyl-4'-hydroxyphenyl) propionic acid hydrazide, bis- (3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl) methane, bis- (3,5-di-t -Butyl-4-hydroxyphen-1-yl) methane, bis- [3- (1'-methylcyclohex-1'-yl) -5-methyl-2-hydroxyphen-1-yl] methane, bis- ( 3-t-butyl- -Hydroxy-5-methylphen-1-yl) methane, 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphen-1-yl) ethane, bis- (5-tert-butyl-4-) Hydroxy-2-methylphen-1-yl) sulfide, bis- (3-tert-butyl-2-hydroxy-5-methylphen-1-yl) sulfide, 1,1-bis- (3,4-dimethyl-2-) Hydroxyphen-1-yl) -2-methylpropane, 1,1-bis- (5-tert-butyl-3-methyl-2-hydroxyphen-1-yl) butane, 1,3,5-tris- [ 1 '-(3 ", 5" -di-t-butyl-4 "-hydroxyphen-1" -yl) methy-1'-yl] -2,4,6-trimethylbenzol, 1,1,4- Tris- (5'-t-butyl-4'-hydroxy Alkylphenols including cis-2'-methylphen-1'-yl) butane and t-butylcatechol,
aminophenols, including p-aminophenol,
Nitrosophenol including p-nitrosophenol and p-nitroso-o-cresol 2-methoxyphenol (guaiacol, benzcatechin monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether) Mono- or di-t-butyl-4-methoxyphenol, 3,5-di-t-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl Alcohol (syringa alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethylvanillin), 3-hydroxy-4-methoxybenzaldehyde (I Sovanillin), 1-((4-hydroxy-3-methoxyphenyl) ethanone (acetovanillin), eugenol, dihydroeugenol and isoeugenol, and the like, and α-, β-, γ-, δ- and ε- Tocopherols including tocopherol, tocol, α-tocopherol hydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran) and the like are included.

Examples of the quinones include hydroquinone, hydroquinone monomethyl ether (4-methoxyphenol), methylhydroquinone, 2,5-di-t-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethyl Hydroquinone 4-methylbenzcatechin, t-butylhydroquinone, 3-methylbenzcatechin, benzoquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, 4-ethoxyphenol, 4- Butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, tetramethyl-p-benzoquinone, diethyl-1,4-cyclohexanedione-2,5-dicarboxylate, Phenyl-p-benzoquinone, 2,5-dimethyl-3-benzyl-p-benzoquinone, 2-isopropyl-5-methyl-p-benzoquinone (thymoquinone), 2,6-diisopropyl-p-benzoquinone, 2,5-dimethyl -3-hydroxy-p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, embellin, tetrahydroxy-p-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2-amino-5-methyl-p- Benzoquinone, 2,5-bisphenylamino-1,4-benzoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 2-anilino-1,4-naphthoquinone, anthraquinone, N, N-dimethylindoaniline, N, N-diphenyl-p-benzoquinone diimine, 1,4-benzoquinone dioxime, celery Non, 3,3'-di-t-butyl-5,5'-dimethyldiphenoquinone, p-rosoleic acid (orine), 2,6-di-t-butyl-4-benzylidene-benzoquinone, and 2, 5-di-t-butyl-amylhydroquinone and the like are included.

Examples of the N-oxyl free radical compounds include compounds having at least one> NO— group, such as a nitroxyl- or N-oxyl-group, such as 4-hydroxy-2, 2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethyl -Piperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 2,2,6,6-tetramethyl-piperidine-N-oxyl, BASF Aktingesellschaff ウUvinul) 4040P, 4,4 ', 4 "-Tris- (2,2,6,6-tetramethyl-piperidine-N-oxyl Phosphite, 3-oxo-2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-oxyl-2 , 2,6,6-tetramethyl-4-trimethylsilyloxypiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate, 1-oxyl-2,2 , 6,6-Tetramethylpiperidin-4-yl-sebacate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-stearate, 1-oxyl-2,2,6,6- Tetramethylpiperidin-4-yl-benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl- (4-t-butyl) benzoate, bis- (1-o Syl-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, 1,10-decandi Acid-bis- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) ester, bis- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butyl malonate, bis- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis- (1-oxyl-2,2,6,6-tetramethylpiperidine- 4-yl) isophthalate, bis- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis- (1-oxyl-2,2,6,6-tetramethylpi Lysine-4-yl) hexahydroterephthalate, N, N′-bis- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipamide, N- (1-oxyl-2, 2,6,6-tetramethylpiperidin-4-yl) caprolactam, N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) dodecylsuccinimide, 2,4,6-tris- [N-butyl-N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] triazine, N, N′-bis- (1-oxyl-2,2,6,6- Tetramethylpiperidin-4-yl) -N, N'-bis-formyl-1,6-diaminohexane and 4,4'-ethylene-bis- (1-oxyl-2,2,6,6-tetramethyl) Piperazine-3 -On) and the like are included.

Examples of the aromatic amine and phenylenediamine include N, N-diphenylamine, N-nitroso-diphenylamine, nitrosodiethylaniline, p-phenylenediamine, N, N'-dialkyl-p-phenylenediamine, and N-phenyl-2. -Naphtylamine, iminodibenzyl, N, N'-diphenylbenzidine, N-phenyltetraaniline, acridone, 3-hydroxydiphenylamine, 4-hydroxydiphenylamine and the like. The two alkyl groups possessed by the N, N′-dialkyl-p-phenylenediamine may be the same or different, and may each independently be a straight chain or a molecular chain containing 1 to 4 carbon atoms. Examples of such N, N'-dialkyl-p-phenylenediamine include N, N'-di-iso-butyl-p-phenylenediamine, N, N'-di-iso-propyl-p-phenylenediamine Irganox 5057, N-phenyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N-phenyl-p-phenylenediamine, N, N'-, manufactured by Firma Ciba Spezialitaenchemie Di-s-butyl-p-phenylenediamine (Kerobit BPD manufactured by BASF Aktingesellschaft), N-phenyl-N'-isopropyl-p-phenylenediamine (Vulkanox 4010 manufactured by Bayer AG) And N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine and the like.

Examples of the imine include methylethylimine, (2-hydroxyphenyl) benzoquinoneimine, (2-hydroxyphenyl) benzophenoneimine, N, N-dimethylindoaniline, thionine (7-amino-3-imino-3H-phenothiazine) ), And methylene violet (7-dimethylamino-3-phenothiazinone).

Examples of the sulfonamides include N-methyl-4-toluolsulfonamide, Nt-butyl-4-toluolsulfonamide, Nt-butyl-N-oxyl-4-toluolsulfonamide, N , N′-bis (4-sulfanilamido) piperidine, 3-{[5- (4-aminobenzoyl) -2,4-dimethylbenzoylsulfonyl] ethylamino} -4-methylbenzolsulfonic acid, and the like.

The oxime may be aldoxime, ketoxime and amidoxime. Examples of the oxime include diethyl ketoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, benzaldehyde oxime, benzyl dioxime, dimethylglyoxime, 2-pyridine aldoxime, salicyl aldoxime, phenyl-2-pyridyl ketoxime, 1, 4-benzoquinone dioxime, 2,3-butanedione dioxime, 2,3-butanedione monooxime, 9-fluorenone oxime, 4-t-butyl-cyclohexanone oxime, N-ethoxy-acetimidic acid ethyl ester, 2,4 Aliphatic or aromatic oximes, including dimethyl-3-pentanone oxime, cyclododecanone oxime, 4-heptanone oxime and di-2-furanylethanedione dioxime, and alkyl halogenides, Triflate, - sulfonates, - tosylates, - carbonate, - sulfates, - such as phosphates, and the like reaction products of alkyl transfer agent and the oxime.

Examples of the hydroxylamine include N, N-diethylhydroxylamine and compounds described in International Publication No. 2003/099757.

Examples of the urea derivative include urea and thiourea.

Examples of the phosphorus-containing compound include triphenylphosphine, triphenylphosphite, hypophosphorous acid, trinonylphosphite, triethylphosphite, diphenylisopropylphosphine, and the like.

Examples of the sulfur-containing compound include sulfur-containing natural substances such as diphenyl sulfide, phenothiazine, and cysteine.

Examples of complexing agents based on tetraazaannulene (TAA) include Chem. Soc. Rev. 1998, 27, 105-115, dibenzotetraaza [14] ring, porphyrin and the like are included.

Examples of the hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3 , 5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino ], Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidinyl Benzoate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl- 4-piperi /Β,β,β′,β′-tetramethyl-3-9-[2,4,8,10-tetraoxaspiro(5.5)undecane]diethyl}-1,2,3,4-butane Tetracarboxylate, poly {[6-N-morpholyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [( 2,2,6,6-tetramethyl-4-piperidyl) imino]}, and [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2 , 6,6-tetramethyl-4-piperidyl) imino] propionamide and the like. Examples of commercially available hindered amines include LA-77, LA-57, and LA-67 (above, manufactured by ADEKA), TINUVIN 123, and TINUVIN 152 (above, manufactured by Ciba Japan), and the like. .

The antioxidant may be a metal salt such as carbonic acid, hydrochloric acid, dithiocarbamic acid, sulfuric acid, salicylic acid, acetic acid, stearic acid, ethylhexanoic acid (a circle of copper, manganese, cerium, nickel, chromium, etc.).

In addition, since the ink of the present invention contains a pigment, the antioxidant is preferably a phenol-based antioxidant or a sulfur-based antioxidant.

Such a phenol-based antioxidant is preferably one capable of scavenging radicals generated from amines liberated by thermal decomposition of the dispersion resin. For example, phenol having at least one group represented by the following formula (17) It is preferable that it is a type | system | group compound.

In formula (17), R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In Chemical Formula ^{(17), R 16} and ^{R 17} are each independently a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Examples of the branched alkyl group include i-propyl group, i-butyl group, t-butyl group and the like. Of these, a methyl group and a t-butyl group are preferable, and R ¹⁶ is more preferably a t-butyl group from the viewpoint of radical stability.

The molecular weight of the phenolic compound is preferably 600 or more, more preferably 1000 or more and 3000 or less, from the viewpoint of increasing the boiling point and the decomposition temperature.
Moreover, it is preferable that melting | fusing point of the said phenolic compound is 150 degrees C or less, and it is more preferable that it is 50 to 140 degreeC.

Examples of the phenol-based antioxidant include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (molecular weight 531) (manufactured by API Corporation, Tominox SS), And Ciba Japan Co., Ltd., IRGANOX 1076), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (molecular weight 1178) (manufactured by API Corporation, Minox TT, Ciba Japan Co., Ltd., IRGANOX 1010, etc.), N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) (molecular weight 637) (Ciba・ Japan Co., Ltd., IRGANOX 1098, etc.) Liethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] (molecular weight 587) (manufactured by API Corporation, Tominox 917, Ciba Japan Co., Ltd., IRGANOX 245, etc.) 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetra Oxaspiro [5,5] -undecane (molecular weight 741) (Sumitomo Chemical Co., Ltd., Sumilizer GA-80, etc.), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate] (molecular weight 643) (Ciba Japan Co., Ltd., IRGANOX 1035, etc.), And 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (molecular weight 639) (Ciba Japan, IRGANOX 259, etc.) .

Further, such a sulfur-based antioxidant is not particularly limited as long as it is capable of decomposing a peroxide generated based on a radical generated from an amine liberated by thermal decomposition of the dispersion resin. 18) to sulfides represented by formula (20) are preferable.

In formula (18), each R ¹⁸ is independently an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

In formula (19), R ¹⁹ , R ²⁰ and R ²¹ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or 6 to 30 carbon atoms. The following aryl groups.

In formula (20), R ²² is each independently an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

In the above chemical formulas (18) to (20), the alkyl group having 1 to 30 carbon atoms is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or 6 to 20 carbon atoms. The alkyl-substituted cycloalkyl group is preferably. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and t-butyl group. T-pentyl group, i-octyl group, t-octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group , Nonadecyl group, icosyl group and the like. Examples of the cycloalkyl group having 5 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the alkyl substituted cycloalkyl group having 6 to 20 carbon atoms include 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-methyl-4-i-propylcyclohexyl group and the like.

の The aralkyl group having 7 to 30 carbon atoms in the above chemical formulas (18) to (20) is preferably an aralkyl group having 7 to 20 carbon atoms. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group and the like.

例 Examples of the aryl group having 6 to 30 carbon atoms in the above chemical formulas (18) to (20) include phenyl group, naphthyl group, anthryl group and the like. Of these, a phenyl group is preferred.

The molecular weight of the sulfur-based antioxidant is preferably 500 or more, more preferably 500 or more and 1300 or less, from the viewpoint of increasing the boiling point and the decomposition temperature.

Examples of commercially available sulfur-based antioxidants include dimyristyl 3,3′-thiodipropionate (molecular weight 571) (Sumitomo Chemical Co., Sumilizer TPM, etc.), pentaerythrityl tetrakis (3-lauryl thiopro). Pionate) (molecular weight 1162) (Sumitomo Chemical Co., Ltd., Sumilizer TP-D), distearyl 3,3′-thiodipropionate (molecular weight 683) (Sumitomo Chemical Co., Ltd., Sumilizer TPS), dilauryl 3,3 '-Thiodipropionate (molecular weight 515) (Sumitomo Chemical Co., Ltd., Sumilizer TPL-R, etc.) and the like are included.

The content of the antioxidant is preferably 0.01% by mass or more and less than 10.0% by mass, and preferably 0.1% by mass or more and 5% by mass with respect to the total solid content of the ink of the present invention. More preferably, it is 0.0 mass% or less.

Moreover, it is preferable that it is 10 mass parts or more and 1000 mass parts or less with respect to 100 mass parts of whole quantity of the said phenolic compound, and content of the said sulfur type antioxidant is 30 mass parts or more and 300 mass parts or less. It is more preferable.

1-5-2. Surfactants Examples of the above surfactants include cationic surfactants, anionic surfactants, amphoteric surfactants (betaine surfactants) and nonionic surfactants (nonionic surfactants). ) Is included. Only one type of surfactant may be contained in the ink of the present invention, or two or more types may be contained.

Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts.

Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt, N-acyl glutamate, alkyl ether carboxylate, Acylated peptides, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl sulfoacetates, α-olefin sulfonates, N-acyl methyl taurines, sulfated oils, higher grades Alcohol sulfate, secondary higher alcohol sulfate, alkyl ether sulfate, secondary higher alcohol ethoxy sulfate, polyoxyethylene alkylphenyl ether sulfate, monoglyculate, fatty acid alkylolamide sulfate, alkyl ether Phosphoric acid Steal salts and alkyl phosphate salts are included.

Examples of the amphoteric surfactants include carboxybetaine type surfactants, sulfobetaine type surfactants, aminocarboxylates, and imidazolinium betaines.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxy Propylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid Ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, poly Oxyethylene fatty acid amides, polyoxyethylene alkylamines, alkylamine oxides, acetylene glycol surfactants, and acetylene alcohol surfactants are included.

Changes in texture due to heat of the fabric after printing are more sufficiently suppressed, and in particular, a decrease in ink ejection stability is further suppressed when a resin neutralized with a neutralizing base is contained. From the viewpoint, the surfactant is preferably an acetylene glycol surfactant.

Examples of commercially available acetylene glycol surfactants include Air Products & Chemicals, Surfinol 104, Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol 104BC, Surfinol, Surfinol 104PA, Surfy Nord 104PG-50, Surfinol 104S, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol 485, Surfinol SE, Surfinol SE-F, Surfinol 504, Surfinol 61, Surfinol DF37, Surfinol CT111 , Surfinol CT121, Surfinol CT131, Surfinol CT136, Surfinol TG, and Surfinol GA (" -Finol "is a registered trademark of the same company, manufactured by Nissin Chemical Industry Co., Ltd., Olphine B, Olphine Y, Olphine P, Olphine A, Olphine STG, Olphine SPC, Olphine E1004, Olphin E1010, Olphine PD-001, Olphine PD-002W Orphin PD-003, Orphin PD-004, Orphin EXP. 4001, Olfine EXP. 4036, Olfine EXP. 4051, Orphine AF-103, Orphine AF-104, Orphine AK-02, Orphine SK-14, and Orphine AE-3 (“Olfin” is a registered trademark of the same company), and acetylenol E00, manufactured by Kawaken Fine Chemical Co., Ltd. Acetylenol E00P, acetylenol E40, and acetylenol E100 (“acetylenol” is a registered trademark of the same company) are included.

1-5-3. Antifungal Agent Examples of the antifungal agent include aromatic halogen compounds, methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, and 1,2-benzisothiazolin-3-one. Only one type of antifungal agent may be contained in the ink of the present invention, or two or more types of antifungal agents may be contained.

1-6. Physical properties of the ink of the present invention From the viewpoint of further improving the ejection properties of the ink, the viscosity of the ink of the present invention at 25 ° C. is preferably 1 mPa · s or more and 40 mPa · s or less, preferably 5 mPa · s or more and 40 mPa · s or less. More preferably, it is 5 mPa · s or more and 20 mPa · s or less. The viscosity of the ink can be measured with an E-type viscometer (for example, V-25, manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 20 rpm.

The surface tension at 25 ° C. of the ink of the present invention is preferably 25 mN / m or more and 50 mN / m or less. If the surface tension is 25 mN / m or more, image bleeding is less likely to occur. When the surface tension is 50 mN / m or less, the ink of the present invention more easily penetrates into the fabric. The viscosity of the ink can be measured by, for example, CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.

1-7. Preparation of Ink of the Present Invention The ink of the present invention can be prepared, for example, by mixing the compound represented by the formula (1), the fixing resin, the water-soluble organic solvent, the pigment and water under heating. The obtained mixed liquid is preferably filtered through a predetermined filter. At this time, a pigment dispersion in which the pigment and the dispersion resin are dispersed in water may be prepared in advance, and the remaining components may be added thereto and mixed while heating.

The compound represented by the formula (1) may be mixed with the fixing resin or the dispersion resin in advance, or may be added to the pigment dispersion, or may be added at the time of mixing under the heating. Good.

2. Inkjet printing method The inkjet printing method of the present invention is an inkjet printing method characterized in that an image is formed on a fabric with the above-described ink of the present invention. The inkjet printing method of the present invention can be carried out in the same manner as a known inkjet printing method using an inkjet ink containing a pigment, except that the above-described ink of the present invention is an inkjet printing ink.

For example, the ink jet textile printing method of the present invention includes a step (image forming step) of discharging the ink droplets of the present invention from the recording head toward the fabric. The inkjet textile printing method of the present invention may further include a step of heating the fabric landed with the ink (heating step).

In addition, the ink jet textile printing method of the present invention may include a step of applying to the fabric a pigment flocculant, a pretreatment agent, an ultraviolet absorber, an antioxidant, a penetrating ink and the like, which will be described later, before the image forming step, A step of applying corona treatment to the fabric may be included before the image forming step. In addition, in the ink jet textile printing method of the present invention, the step of applying the ink containing the fixing resin (the first ink or the second ink described above) to the fabric is performed before the image forming step or after the image forming step and heating. It may be included before the process.

Further, the ink jet textile printing method of the present invention may include a step of applying a fixing agent described later to the fabric after the image forming step. The step of applying the fixing agent to the fabric is preferably included after the image forming step. Further, the step of applying the fixing agent to the fabric may be included before the heating step or after the heating step. However, from the viewpoint that the fixing resin and the fixing agent can be simultaneously dried and fixed by heating, the step of applying the fixing agent to the fabric is preferably included before the heating step. When the step of applying the fixing agent to the fabric is included after the heating step, it is preferable to further perform heating for drying and fixing the fixing agent. The heating for drying and fixing the fixing agent can be performed in the same manner as the heating step described later.

2-1. Image Forming Step The image forming step is a step of forming an image by ejecting the ink droplets of the present invention from the recording head toward the fabric. For example, an image can be formed by ejecting ink droplets from a recording head and landing on the fabric while moving the fabric relative to a head carriage on which a plurality of recording heads are mounted. When an image is formed using a plurality of color inks including the ink of the present invention, the ink droplets for each color may be ejected separately or simultaneously.

When using a plurality of colors of ink, it is preferable to use three primary colors of cyan, magenta and yellow. From the viewpoint of expressing a wider color gamut, the above-mentioned plurality of colors of ink may include black and gray inks, and may have special colors such as green, orange, blue, red, violet, silver, and gold. It may contain ink. When an image is formed on a dark-colored fabric, white ink may be landed on the fabric first, and then other color inks may be landed on the fabric.

2-2. Step of Applying Fixing Agent The step of applying fixing agent is a step of applying a fixing agent for fixing a pigment to the surface of the fabric landed with the ink of the present invention. The fixing agent can be a natural or synthetic polymer such as tannin. The fixing agent may be applied to the surface of the fabric by an inkjet method using a solution or dispersion containing the fixing agent, or may be applied to the surface of the fabric by a pad method, a coating method, a spray method, or the like.

2-3. Heating process In the heating process, particularly when the ink of the present invention contains a fixing resin, the cloth landed with the ink is heated to form a fixing resin film on the surface of the cloth. In this process, the pigment is held and fixed. The heating conditions at this time may be such that the pigment is sufficiently fixed. For example, it is preferable to heat at 100 ° C. to 180 ° C. for 3 minutes to 15 minutes. Heating can be performed by application of warm air and pressure bonding using a heated roller.

2-4. Other Steps The ink jet textile printing method of the present invention may include a step of cleaning the nozzles while stopping the discharge of the water-based ink.

When the fixing resin contained in the ink of the present invention is fixed to the nozzle of the inkjet head, there is a possibility that a phenomenon such as clogging of the nozzle or bending of the droplet flying direction may occur. On the other hand, by cleaning the nozzles, it is possible to suppress the fixing resin from sticking to the nozzles, and it is possible to suppress clogging of the nozzles and bending of the flying direction of the droplets.

Cleaning may be performed by wiping the nozzle discharge surface with an ink absorbing member such as a polyester cloth, or the ink absorbing member contains a cleaning liquid, and the fixing resin is dissolved or swollen with the cleaning liquid to fix from the nozzle. The resin may be removed.

The cleaning liquid contains water and an organic solvent. The cleaning liquid may further contain other components such as an antifungal agent.

The organic solvent is preferably selected so that the average SP value is less than 15 from the viewpoint of facilitating dissolution of a fixed substance such as a fixing resin, and the dispersion stability of the pigment that the ink may contain is preferably selected. From the viewpoint of improvement, the average SP value is preferably selected to be 10 or more. From the above viewpoint, the organic solvent contained in the cleaning liquid is preferably selected so that the average SP value is 10 or more and less than 15, and more preferably 10.5 or more and 13 or less. More preferably, it is selected to be 10.6 or more and 12 or less.

Examples of the organic solvent include glycol monoalkyl ether, polyhydric alcohol, cyclic amide, lactone, cyclic carbonate, cyclic sulfone and sulfoxide.

The glycol ether alkyl ether is a monoalkyl ether of glycol. Examples of the glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, and dipropylene glycol. Of these, diethylene glycol, triethylene glycol, and propylene glycol are preferred.

The SP value of the glycol ether alkyl ether can be adjusted by the number of carbons in the main chain part of the glycol and the number of carbons in the alkyl ether part. From the viewpoint of the viscosity of the organic solvent and the solubility in water, the total number of carbon atoms in the glycol ether alkyl ether is preferably 4 or more and 10 or less, and more preferably 4 or more and 7 or less.

Examples of the glycol ether alkyl ether include: diethylene glycol monomethyl ether (11.2), diethylene glycol monoethyl ether (10.9), diethylene glycol monopropyl ether (10.7), diethylene glycol monobutyl ether (10.5), triethylene Glycol monomethyl ether (10.8), triethylene glycol monoethyl ether (10.6), triethylene glycol monopropyl ether (10.5), tetraethylene glycol monomethyl ether (10.6), tetraethylene glycol monoethyl ether (10.4), propylene glycol monomethyl ether (10.4), propylene glycol monoethyl ether (10.9), dipropylene glycol Methyl ether (9.6), and dipropylene glycol monopropyl ether (8.6) and the like (values in parentheses unless (otherwise otherwise represent the SP value, the same is less)). Of these, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and propylene glycol monoethyl ether are preferred because of their low odor and good detergency.

The polyhydric alcohol can be selected from compounds in which two or more hydroxyl groups are substituted on a linear or branched alkylene chain having 4 to 6 carbon atoms. Examples of the polyhydric alcohol include 1,4-butanediol (15.0), 1,5-pentanediol (14.2), 1,6-hexanediol (13.5), and 1,2-hexane. Diol (13.4), 2-methyl-2,4-pentanediol (13.1), 3-methyl-1,5-pentanediol (13.4) and the like are included. Of these, 2-methyl-2,4-pentanediol (13.1) is preferred.

Examples of the cyclic amide include 2-pyrrolidone (12.6), N-methylpyrrolidone (11.5), N-ethylpyrrolidone (11.1), 2-piperidone (12.0), and ε-caprolactam (11.6) and the like are included. Of these, N-methylpyrrolidone is preferred.

Examples of the lactone include γ-butyrolactone (10.5), δ-valerolactone (10.2), and ε-caprolactone (10.0). Of these, γ-butyrolactone is preferred.

Examples of the cyclic carbonate include propylene carbonate (10.5) and ethylene carbonate (11.2). Of these, propylene carbonate is preferred.

Examples of the cyclic sulfone and sulfoxide include sulfolane and dimethyl sulfoxide (12.9). Of these, dimethyl sulfoxide is preferred.

Among these, glycol monoalkyl ether is preferable from the viewpoint of easy adjustment of the average SP value of the organic solvent contained in the cleaning liquid to the above range, good detergency, and safety and odor. 4 or more and 10 or less glycol monoalkyl ether is preferable.

The content ratio of the glycol monoalkyl ether, polyhydric alcohol, cyclic amide, lactone, cyclic carbonate, cyclic sulfone and sulfoxide relative to the whole organic solvent is preferably 60% by mass or more, and more preferably 80% by mass or more. More preferred is 100% by mass.

The organic solvent contained in the cleaning liquid may further contain another organic solvent as long as the average SP value of the whole organic solvent satisfies the above range.

In order to improve the dispersion stability of the pigment that can be contained in the water-based ink when the cleaning liquid and the water-based ink are mixed, there is a difference between the SP value of the organic solvent in the cleaning liquid and the SP value of the organic solvent in the ink. It is preferable that it is a certain value or more. Specifically, the difference between the SP value of the organic solvent in the cleaning liquid and the SP value of the organic solvent in the ink can be 3.0 or more, preferably 5.5 or more.

The organic solvent preferably includes an organic solvent having a surface tension at 25 ° C. of 25 mN / m or more and 35 mN / m or less, and all of the organic solvents have a surface tension at 25 ° C. of 25 mN / m or more and 35 mN / m or less. It is more preferable that Since the cleaning liquid containing such an organic solvent tends to lower the surface tension, the cleaning liquid easily penetrates into a fixed object such as a pigment or a resin, and good detergency is easily obtained.

Among the organic solvents described above, examples of organic solvents having a surface tension at 25 ° C. of 25 mN / m or more and 35 mN / m or less include diethylene glycol monoethyl ether (31.8), diethylene glycol monobutyl ether (33.6), diethylene glycol Alkylene glycol monoethers such as propylene glycol monomethyl ether (28.8), tripropylene glycol monomethyl ether (30.0), and propylene glycol monomethyl ether (27.1), and 1,2-hexanediol (28. 1), and polyhydric alcohols such as 2-methyl-2,4-pentanediol (27.0), etc. (in this paragraph, the values in parentheses represent the surface tension value (mN / m)).

The surface tension of the organic solvent is, for example, New Experimental Chemistry Course Vol. 18 (Interface and Colloid), edited by the Chemical Society of Japan, published by Maruzen Co., Ltd. 68 to 117, and can be measured by a vertical plate method (Wilhelmy method). Specifically, the surface tension of the organic solvent can be measured in a 25 ° C. atmosphere using a surface tension meter CBVP type A-3 (Kyowa Science Co., Ltd.).

The content of the organic solvent contained in the cleaning liquid is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more with respect to the entire cleaning liquid. . By setting the content ratio of the organic solvent to a certain value or more, the fixed matter on the nozzle surface of the ink jet recording head can be sufficiently dissolved. The content ratio of the organic solvent can be 60% by mass or less with respect to the entire cleaning liquid.

The cleaning liquid may further contain additives such as surfactants, preservatives, and antifungal agents as necessary. Examples of the surfactant include dialkyl sulfosuccinates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, Examples include amphoteric surfactants including alkylamine salts, quaternary ammonium salts, and betaines, silicone surfactants, and fluorosurfactants. Examples of the preservatives and antifungal agents include, but are not limited to, aromatic halogen compounds (eg, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazoline. -3-one (eg, PROXELGXL) and the like are included.

In addition, when the fixing resin is a resin containing an anionic group, the fixing resin can be dissolved by adding a base to the cleaning liquid. Further, when the fixing resin is a resin containing a cationic group, the fixing resin can be dissolved by adding an acid to the cleaning liquid.

Further, cleaning liquids described in JP 2000-328093 A, JP 2005-7703 A, JP 2011-156818 A, JP 2009-233911 A, and the like may be used.

Further, in order to prevent the fixing resin from sticking due to drying of the ink, humidified air or steam may be continuously or intermittently applied to the nozzles of the inkjet head or in the vicinity thereof during or before or after the vapor image forming process. .

2-5. Cloth The cloth is not limited as long as it can be printed with the ink of the present invention, but cotton, hemp, wool, silk, viscose rayon, cupra rayon, polynosic, vinylon, nylon, acrylic, polyurethane, rayon polyurethane, polyester and acetate are used. It is preferable that the fiber contains. From the viewpoint of further improving the fixability of the pigment, the fiber radius is preferably 10d to 100d.

The ink jet textile printing method of the present invention has an advantage that it can be printed regardless of the type of fabric because an ink containing a fixing resin is used. In particular, in an ink jet printing method using a conventional ink jet ink for dyeing containing a dye as a coloring material, the dye is likely to be fixed to one fiber when printing on a fabric such as a mixed spun or woven fabric containing a plurality of fibers. However, there is a problem that it is difficult to fix to another fiber and the fixability to a fabric is low. However, according to the ink jet textile printing method of the present invention, an image having high fixability can be formed on a fabric including a plurality of fibers.

In particular, when the ink of the present invention contains a polyester resin or a polyurethane resin, these resins have a high affinity for polyester fibers, and therefore, when printed on fabrics containing polyester fibers (including blended or interwoven fabrics), the fixing properties are improved. A higher image can be formed.

When an image is formed on a fabric containing a plurality of fibers, it is selected from reactive dyes, acid dyes, disperse dyes, sublimation dyes and the like together with the ink of the present invention and has high fixability to the fibers contained in the fabric. It is also preferable to use an ink containing a dye in combination.

The fabric may be preliminarily provided with an agent for aggregating the pigment (hereinafter also simply referred to as “pigment aggregating agent”).

The pigment flocculant only needs to have an action of aggregating the pigment. For example, when the pigment is an anionic dispersed pigment, the pigment flocculant can be an acid or a cationic compound. Only one type of these pigment flocculants may be contained, or two or more types may be contained in combination.

Acid can agglomerate the anionic dispersed pigment by pH fluctuation. Examples of such acids include formic acid, acetic acid, propionic acid, isobutyric acid, oxalic acid, fumaric acid, malic acid, citric acid, malonic acid, succinic acid, maleic acid, benzoic acid, 2-pyrrolidone-5-carboxylic acid Examples include acid, lactic acid, acrylic acid and derivatives thereof, methacrylic acid and derivatives thereof, acrylamide and derivatives thereof, sulfonic acid derivatives, and phosphoric acid and derivatives thereof. The acid is preferably an organic acid. An organic acid is highly compatible with other components (such as a cross-linking agent) contained in the first treatment liquid, and is difficult to become a salt even when the first treatment liquid is dried on the substrate. It has excellent transparency and is difficult to discolor the formed image.

The cationic compound can aggregate the anionic dispersion pigment by salting out. Examples of the cationic compound include polyvalent metal salts, cationic surfactants, and cationic resins. Preferred examples of the polyvalent metal salt include water-soluble salts such as calcium salts, magnesium salts, aluminum salts, and zinc salts. As the cationic surfactant (also referred to as cationic surfactant), for example, aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts and the like are preferable. Can be mentioned. Examples of the cationic resin include polyallylamine, polyvinylamine, polyethyleneimine, and polydiallyldimethylammonium chloride.

In addition, when using an acid, it is preferable that the addition amount of an acid is the quantity which adjusts the pH of a process liquid to below the neutralization equivalent of the anion component contained in the ink of this invention. Further, when the anionic component is an acrylic acid group, the first dissociation constant of the acid is preferably 3.5 or less from the viewpoint of making image bleeding more difficult.

The fabric may be pre-applied with a pretreatment agent containing a water-soluble polymer. The pretreatment agent is preferably applied to the surface of the fabric on the side where the ink of the present invention lands. The pretreatment agent may be applied by an inkjet method, or may be applied by a pad method, a coating method, a spray method, or the like.

Examples of the water-soluble polymer include natural water-soluble polymers and synthetic water-soluble polymers. Examples of natural water soluble polymers include starches including corn and wheat, cellulose derivatives including carboxymethylcellulose, methylcellulose and hydroxyethylcellulose, polysaccharides including sodium alginate, guar gum, tamarind gum, locust bean gum and gum arabic, And protein substances including gelatin, casein and keratin. Examples of the synthetic water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, and an acrylic acid polymer.

The pretreatment agent preferably further contains a pH adjuster. From the viewpoint of forming a clear image at a higher density, the pH adjuster is more preferably an acid. Examples of pH adjusters that are acids include citric acid, malic acid and tartaric acid.

The pretreatment agent may further contain optional components including a reduction inhibitor, a chelating agent, and a preservative as necessary. Examples of the reduction inhibitor include sodium m-nitrobenzenesulfonate. Examples of chelating agents include aminopolycarboxylates, hydroxycarboxylates, polycarboxylates, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid and diethylenetriaminepentaacetic acid. Examples of preservatives include aromatic halogen compounds including isopropyl N- (3-chlorophenyl) carbamate, methylene dithiocyanate and 1,2-benzisothiazolin-3-one.

The fabric may be pretreated with a corona treatment. By performing the corona treatment, the fixability of the image is enhanced. This is presumably because polar groups having high affinity with the fixing resin are formed on the surface of the fabric by corona treatment. The corona treatment is preferably performed on the surface of the fabric on the side where the ink of the present invention lands.

The fabric may be preliminarily provided with a known ultraviolet absorber and antioxidant. These substances can improve the storage stability of the image, in particular, can suppress the decrease in color and density of the image, and can also suppress the decrease in the abrasion resistance of the image. This is presumed to be because these substances suppress the photobleaching and ozone fading of the pigment and prevent the fixing resin from being decomposed by light, ozone, nitrogen oxide (NO _X ), sulfur oxide (SO _X ), etc. Is done.

Examples of the antioxidant include the above-described ultraviolet absorber that the ink of the present invention may contain.

Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, hydroxyphenyl triazine compounds, and cyanoacrylate compounds.

Examples of UV absorbers that are benzophenone compounds include 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2-hydroxy- 4-Benzyloxy-benzophenone, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4 -Methoxy-benzophenone, 2,2 ', 4,4'-tetrahydroxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, and the like.

Examples of UV absorbers that are benzotriazole compounds include 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t- Butyl-5'-methylphenyl) benzotriazole, 2- (3,5-di-t-pentyl-2-hydroxyphenyl-2-benzotriazole, 2- (2-benzotriazol-2-yl) -4-methyl- 6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-4-octyloxyphenyl) -2-benzotriazole, 2- (2-hydroxy-5-t-octyl) Phenyl) -2-benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-butyl) Phenyl) and the like benzotriazole.

Examples of UV absorbers that are salicylate compounds include 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, phenyl salicylate and salicylic acid-4-t-butylphenyl. Etc. are included.

Examples of ultraviolet absorbers that are hydroxyphenyltriazine compounds include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- ( 2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- ( 2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2- (2- Hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2,4-diphenyl 6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, and 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1 , 3,5-triazine and the like.

Examples of the ultraviolet absorber that is a cyanoacrylate compound include 2-ethylhexyl 2-cyano-3,3-diphenylacrylate and ethyl-2-cyano-3,3-diphenylacrylate.

The fabric may be pre-applied with penetrating ink in order to increase the permeability of the pigment into the fabric. The penetrating ink can be, for example, an aqueous solution containing a water-soluble organic solvent such as glycerin and ethylene glycol that has high permeability to the fabric. The penetrating ink may be applied to the surface of the fabric on the side where the ink of the present invention lands, or may be applied to the surface on the opposite side. The penetrating ink may be applied by an inkjet method, or may be applied by a pad method, a coating method, a spray method, or the like.

2-6. Inkjet recording apparatus The inkjet printing method of the present invention can be performed using an inkjet recording apparatus that performs printing using an inkjet ink.

The ink jet recording apparatus may be a single pass recording method (line recording method) or a scan recording method. The recording method may be selected according to the required image resolution and recording speed, but the single pass recording method is preferable from the viewpoint of high-speed recording.

FIG. 1A and FIG. 1B are diagrams illustrating an example of a configuration of a main part of an ink jet recording apparatus of a single pass recording method. 1A is a side view, and FIG. 1B is a plan view. As shown in FIG. 1A, the inkjet recording apparatus 10 includes a head carriage 13 that houses a plurality of ejection recording heads 11, an ink tank 17 that stores degassed ink, an ink tank 17, and a head carriage 13. And an ink flow path 15 communicating with each other.

The head carriage 13 is fixedly arranged so as to cover the entire width of the fabric 20 and accommodates a plurality of ejection recording heads 11. Each head carriage 13 accommodates ejection recording heads 11 of different colors.

The ink in the ink tank 17 is supplied to the recording head 11 through the ink flow path 15.

The number of ejection recording heads 11 arranged in the conveyance direction of the fabric 20 is set according to the nozzle density of the ejection recording head 11 and the resolution of the print image. For example, when an image having a resolution of 1440 dpi is formed using the recording head 11 having a droplet amount of 2 pl and a nozzle density of 360 dpi, the four ejection recording heads 11 may be arranged so as to be shifted with respect to the conveyance direction of the fabric 20. Good. Further, when an image having a resolution of 720 × 720 dpi is formed by using the ejection recording head 11 having a droplet amount of 6 pl and a nozzle density of 360 dpi, the two ejection recording heads 11 may be arranged in a shifted manner. dpi represents the number of ink droplets (dots) per 2.54 cm.

The ink jet recording apparatus includes a plurality of ejection recording heads 11, ink flow paths 15, and ink tanks 17 when applying a plurality of inks (the first ink or the second ink described above) to a fabric. Alternatively, a padding unit, a coating unit, and a spray for applying one of the first ink and the second ink may be provided.

The ink jet recording apparatus may have an agitation mechanism for preventing the precipitation of the pigment in the ink tank 17 or the ink flow path 15. Further, the ink jet recording apparatus may have a filter for suppressing nozzle clogging due to pigment aggregates or the like in the ink flow path 15 or the like.

The ink jet recording apparatus may have a deaeration module in order to suppress a decrease in ejection stability due to gas adhering to the pigment surface. The degassing module can degas the ink by hollow fiber or ultrasonic irradiation.

The ink jet recording apparatus may include a cleaning unit that cleans the surface of the ink jet recording head having the nozzle aperture. The cleaning unit may be a wipe unit having an ink absorbing member that absorbs ink and a function of supplying a cleaning liquid containing an organic solvent to the ink absorbing member, a blade wipe, or the like. Specific examples of the configuration of the wipe unit include the configuration described in International Publication No. 2012/117742.

The cleaning means cleans the nozzle surface while the water-based ink discharge is stopped. For example, the nozzle surface of the wipe unit can be cleaned by rubbing the nozzle surface of the recording head with a polyester cloth impregnated with a cleaning liquid.

2-7. Inkjet printing system The inkjet recording apparatus may constitute an inkjet printing system together with a drying device provided on the downstream side of the inkjet printing apparatus and a control unit that controls the drying device.

The above-mentioned drying device only needs to heat the fabric landed with ink, and the heating conditions at this time can be, for example, 100 ° C. or more and 180 ° C. or less and 3 minutes or more and 15 minutes or less. Heating can be performed by application of warm air and pressure bonding using a heated roller.

The drying device may have a solvent collecting device for preventing the organic solvent contained in the ink of the present invention from being released out of the system. The solvent collecting device can be a device that cools and collects the organic solvent evaporated by the heat of drying.

The ink jet textile printing system includes a pigment flocculant application device that applies an application liquid containing a pigment flocculant to a fabric, a pretreatment agent application device that applies a pretreatment agent to the fabric, an application liquid containing an ultraviolet absorber or an antioxidant. An apparatus for applying an ultraviolet absorbent or the like applied to the fabric, a penetrating ink applying apparatus for applying penetrating ink to the fabric, or the like may be provided on the upstream side of the ink jet recording apparatus.

The inkjet textile printing system may have a fixing agent applying device that applies a fixing agent to the fabric on the downstream side of the inkjet recording device. The ink jet textile printing system preferably has a fixing agent application device on the downstream side of the ink jet recording device and on the upstream side of the drying device.

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 these descriptions.

In the following examples, the average particle size of the particles is z-average measured by a dynamic light scattering particle size distribution analyzer (Zelizer Nano S (“Zetasizer” is a registered trademark of the company) manufactured by Malvern). The particle size. The acid value of the resin is an acid value determined by neutralization titration according to JISK に 0070. Moreover, the weight average molecular weight of resin is a styrene conversion molecular weight measured by GPC which combined the polystyrene gel column using the solvent which added 1 ml of THF with respect to 1 mg of measurement samples.

[Production of resin]
(Resin 1)
60 parts of 3-methyl-pentanediol / 1,6-hexanediol (mole% ratio: 30/70) copolymer polycarbonate diol having a number average molecular weight calculated from the hydroxyl value of 2,000, number average molecular weight calculated from the hydroxyl value Is 1,9-nonanediol / 2-methyl-1,8-octanediol (molar ratio: 15/85) copolymerized polycarbonate diol 140 parts, ethylene glycol 12.7 parts, 2,4′- 77.5 parts of a mixture of diphenylmethane diisocyanate and 4,4′-diphenylmethane diisocyanate and 677 parts of N, N-dimethylformamide were charged and reacted at 70 ° C. for 15 hours in a dry nitrogen atmosphere to obtain a polyurethane resin solution. After adding 3 times the amount of ion-exchanged water to the resin solids weight and emulsifying with a homogenizer, N, N-dimethylformamide was removed to obtain an aqueous dispersion of polyurethane resin 1.

(Resin 2)
Acrylic WBR-016U (“Acryt” is a registered trademark of the company) manufactured by Taisei Fine Chemical Co., Ltd. was used as an aqueous dispersion of polyurethane resin 2. This resin had a weight average molecular weight of 45,000, an acid value of 7 mgKOH / g, and a Tg of 20 ° C.

(Resin 3)
In ion-exchanged water, 45 parts of ethyl acrylate, 30 parts of butyl acrylate, 5 parts of tetrahydrofurfuryl acrylate, 25 parts of methyl acrylate and 5 parts of acrylic acid were polymerized, and the pH was adjusted to 8 to 8.5 with sodium hydroxide. And filtered through a 0.3 μm filter to obtain an aqueous dispersion of polyacrylic resin 3. This resin had a weight average molecular weight of 150,000, an acid value of 20 mgKOH / g, and a Tg of −15 ° C.

[Preparation of pigment dispersion]
As a dispersant, 15 parts of DISPERBYK-190 ("DISPERBYK" is a registered trademark of the company, comb-type block polymer dispersant 40% solids) manufactured by Big Chemie Co. was added to 65 parts of ion-exchanged water and mixed. In the solution thus obtained, C.I. I. 20 parts of Pigment Blue-15: 3 was added, premixed, and then dispersed using a sand grinder filled with 50% by volume of 0.5 mm zirconia beads to obtain a cyan pigment dispersion having a pigment concentration of 20%. .

The z-average particle size of the dispersed particles contained in the obtained cyan pigment dispersion was measured with a dynamic light scattering particle size distribution meter (manufactured by Malvern, Zetasizer Nano S), and all were 120 nm.

[Preparation of water-based ink for inkjet printing]
To the ion-exchange water, an aqueous dispersion of the resin, a water-soluble organic solvent, a surfactant, other components, and the compound of formula (1) are sequentially added and stirred until uniform, and then the pigment dispersion is added. In addition, after further stirring until uniform, the mixture was filtered through a 0.3 μm filter, and water-based inks 1 to 16 for ink jet printing having the compositions shown in Tables 1 and 2 (hereinafter referred to as the respective inks). Simply referred to as “ink 1” to “ink 16”).

(Water-soluble organic solvent)
HD: 1,2-hexanediol MPD: 2-methyl-1,3-propanediol 2P: 2-pyrrolidone TEGBE: triethylene glycol butyl ether Gly: glycerin EG: ethylene glycol TEA: triethanolamine

(Compound of formula (1))
Compound of formula (1): 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] Dioxaphosphepine) Phosphonate (Sumitomo Chemical Co., Ltd., Sumilizer GP (“Smilizer” is a registered trademark of the company))

(Antioxidant)
Antioxidant 1: n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (phenolic antioxidant, manufactured by BASF, IRGANOX 1076, “IRGANOX” is a product of BASF Societas European registered trademark)
Antioxidant 2: Distearyl 3,3′-thiodipropionate (Sulfur-based antioxidant, manufactured by Sumitomo Chemical Co., Ltd., Sumilizer TPS)

(Surfactant)
Surfactant 1: Acetylene glycol surfactant (acetylene glycol (Surfinol 465 (Air Products and Chemicals, Surfynol is a registered trademark of the company))
Surfactant 2: Acetylene glycol surfactant (acetylene glycol (Surfinol 104, manufactured by Air Products and Chemicals)
Surfactant 3: Nonionic surfactant (Polyoxyethylene lauryl ether (manufactured by Kao Corporation, Emulgen 147))

(Antidepressant)
Antifungal agent: 1,2-benzisothiazolin-3-one (Arch UK Biosize, Proxel GXL)

Tables 1 and 2 show the compositions of ink 1 to ink 16. In Tables 1 and 2, the unit of each number is% by mass, and the numbers of the pigment, dispersant, and fixing resin are% by mass in terms of solid content.

[Evaluation]
(Texture)
With an ink jet printer (made by Konica Minolta Co., Ltd., Nassenger-V, “Nassenger” is a registered trademark of Konica Minolta IJ Co., Ltd.) using inks 1 to 16 at a printing rate of 100% Duty at 540 dpi × 720 dpi A 15 cm × 15 cm rectangle was printed on a 50 d thick polyester fiber. Then, it processed for 10 minutes in 130 degreeC hot air environment, and produced the printed matter by each ink. Then, each printed matter was touched by hand and sensory evaluation was performed.

◎: Very soft and good ○: Soft and good △: Slightly stiff, but acceptable level ×: Large stiff, unacceptable level

(Discharge stability)
After storing the inks 1 to 16 at 60 ° C. for 2 weeks, a 15 cm × 15 cm rectangle was continuously printed 10 times in the same manner as the printed matter, and the image was observed to check for ink ejection failure. The presence and the number of faint lines (image defects) were examined.

◎: No image defect is observed. ○: One image defect is observed. △: Two or three image defects are observed. ×: Four or more image defects are observed.

The results of the above evaluation for each of inks 1 to 16 are shown in Table 3.

Water-based inks for ink-jet printing containing water, pigments, water-soluble organic solvents, fixing resins and compounds represented by formula (1) are less likely to cause the printed fabric to become stiff and cause nozzle clogging. It was difficult. (Ink 1 to Ink 13).

In particular, water-based inks for ink-jet printing containing 1,2-alkanediol, 2-methyl-1,3-propanediol or 2-pyrrolidone as a water-soluble organic solvent are less likely to cause the printed fabric to become stiff. The nozzles were less likely to be clogged (by comparison between ink 1 to ink 7 and ink 8).

In addition, the water-based ink for ink-jet printing containing an acetylene glycol-based surfactant is less likely to cause the printed fabric to be stiff, and more difficult to cause nozzle clogging (Ink 1 to Ink 7 and the ink). Comparison with 13).

In addition, the water-based ink for inkjet printing, in which the fixing resin is a polyacrylic resin or a polyurethane-based resin, is less likely to cause the printed fabric to become stiff and less likely to cause nozzle clogging (ink). 1 to Ink 7 and a comparison of Ink 10 and Ink 9).

Further, the water-based ink for ink jet printing in which the content of the compound represented by the formula (1) is 0.01% by mass or more and 3.0% by mass or less is difficult to cause the printed fabric to be stiff, and the nozzle It was possible to make it difficult to cause clogging of the ink (by comparing the inks 2 to 4 with the inks 1 and 5).

In addition, the water-based ink for ink-jet printing containing both the polyacrylic resin and the polyurethane-based resin as the fixing resin is less likely to cause the printed fabric to be stiff and to cause nozzle clogging. Can be made compatible to a higher degree (by comparison between ink 11 and inks 1 to 8 and ink 10).

Also, the water-based ink for ink jet printing containing amines as the water-soluble organic solvent was less likely to cause nozzle clogging (comparison between ink 3 and ink 12).

Also, the water-based ink for inkjet printing containing an acetylene glycol surfactant as a surfactant was less likely to cause nozzle clogging (comparison between ink 3 and ink 13).

On the other hand, the ink not containing the compound represented by the formula (1) is more likely to be stiff on the printed fabric and easily clogged nozzles even if the same amount of surfactant is contained. (Ink 14 to Ink 16).

This application claims priority based on Japanese Patent Application No. 2015-254967 filed on December 25, 2015, and the contents described in the claims and specification of the application are incorporated herein by reference. Incorporated.

The ink of the present invention can be suitably used for dyeing a fabric by being discharged from an ink jet recording apparatus included in an ink jet textile printing system.

DESCRIPTION OF SYMBOLS 10 Inkjet recording apparatus 11 Ejection recording head 13 Head carriage 15 Ink flow path 17 Ink tank 20 Fabric

Claims

A water-based ink for inkjet printing, comprising a compound represented by formula (1), a fixing resin, a water-soluble organic solvent, a pigment, and water.

(In the formula (1),
R 1 , R 2 , R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 8 carbon atoms. An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, and one functional group selected from the group consisting of a phenyl group,
R 3 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
X is a divalent structure represented by a single bond, a sulfur atom or —CHR 6 —;
R 6 is a hydrogen atom or one functional group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 5 to 8 carbon atoms,
A is an alkylene group having 2 to 8 carbon atoms or a divalent structure represented by * —CO—R 7 —,
R 7 is a single bond or an alkylene group having 1 to 8 carbon atoms,
* Is a binding site with an oxygen atom,
One of Y and Z is one functional group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms and an aralkyloxy group having 7 to 12 carbon atoms,
The other of Y and Z is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )
The water-based ink according to claim 1, wherein the compound represented by the formula (1) is contained in an amount of 0.01% by mass or more and 3.0% by mass or less with respect to the total mass of the ink.
The aqueous system according to claim 1 or 2, wherein the water-soluble organic solvent is one solvent selected from the group consisting of 1,2-alkanediol, 2-methyl-1,3-propanediol, and 2-pyrrolidone. ink.
The water-based ink according to any one of claims 1 to 3, wherein the surfactant is an acetylene glycol surfactant.
5. The water-based ink according to claim 1, wherein the fixing resin includes a polyacrylic resin or a polyurethane resin.
An ink-jet textile printing method comprising forming an image on a fabric with the water-based ink according to any one of claims 1 to 5.