JP2016210921A - Ink composition and printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment ink composition excellent in discharge properties of ink, in particular, in discharge properties after having been left open, and to provide an inkjet printing method and a dying method using the same.SOLUTION: There is provided an ink composition which contains a pigment, water, a polymer dispersant, an urethane resin, a water-soluble organic solvent, and a nonionic surface organic solvent, is used for inkjet printing, and contains at least one compound represented by a formula (4) and polyoxyethylene polyoxypropylene polyoxybutylene glycol having a specific structure, as the water-soluble organic solvents.SELECTED DRAWING: None

Description

  The present invention relates to an ink composition used for ink jet printing containing a pigment, water, a polymer dispersant, a urethane resin, a water-soluble organic solvent, and a nonionic surfactant, an ink jet printing method using the ink composition, and a dyeing method. About.

  Inkjet recording methods have become widespread as business and household recording (printing) methods as the information industry becomes more digital. Since the inkjet recording method can record high-quality and high-definition images, the application is not limited to paper, and in recent years, it is also used in the field of textile printing.

  Generally, when ink is printed on a fiber using a pigment as a coloring material, the pigment does not penetrate and dye inside the fiber, but remains on the fiber in a form that adheres to the fiber. It is known that a binder component is necessary for fixing. However, when a large amount of binder component is added to the ink, for example, the amount of the solvent added for the purpose of moisturizing is reduced, so that the drying property of the ink is accelerated, and the discharge failure of the printer or the discharge failure after being left open, There is a problem of clogging of the head, and there is a strong demand for improvement.

  Patent Documents 1 and 2 disclose the problem of ejectability caused by inkjet inks using pigments.

Japanese Patent No. 3837333 Japanese Patent No. 5376810

  It is an object of the present invention to provide a pigment ink composition having excellent ink discharge properties, particularly discharge properties after being left open, and an ink jet printing method and dyeing method using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the ink composition containing a pigment, water, a polymer dispersant, a urethane resin, a water-soluble organic solvent, and a nonionic surfactant, The present inventors have found that the problems can be solved and have completed the present invention. That is, the present invention relates to the following 1) to 11).

1)
An ink composition used for inkjet printing, comprising a pigment, water, a polymer dispersant, a urethane resin, a water-soluble organic solvent, and a nonionic surfactant, wherein the water-soluble organic solvent includes at least one of the following formulas: An ink composition comprising the compound represented by (4) and at least one compound represented by the following formula (5).

[In the above formula (4),
EO represents an ethyleneoxy group, PO represents a propyleneoxy group, BO represents a butyleneoxy group,
The order in which EO, PO and BO are combined is arbitrary,
m1, m2, m3, n1, n2, n3, q1, q2 and q3 represent 0 or an integer of 1 or more, but all are not 0, and m1 to m3, n1 to n3, and q1 The sum total of ˜q3 is an average value larger than 0 and not larger than 100. ]

[In the above formula (5),
EO represents an ethyleneoxy group, PO represents a propyleneoxy group, BO represents a butyleneoxy group,
The order in which EO, PO and BO are combined is arbitrary,
j, k, and p represent 0 or an integer of 1 or more, but they are not all 0, and the sum of j, k, and p is 1 to 10 on average. ]
2)
The polymer dispersant is represented by a mixture of an organic tellurium compound represented by the following formula (1) and an organic ditellurium compound represented by the following formula (2), or the following formula (1), as a polymerization initiator. A and B obtained by copolymerization by a living radical polymerization method using any one of a mixture of an organic tellurium compound, an azo polymerization initiator and an organic ditellurium compound represented by the following formula (2): It is an AB block polymer which is a polymerized polymer, wherein the monomer constituting the A block is one or more kinds of monomers represented by the following formula (3), and the monomer constituting the B block is benzyl methacrylate and / or benzyl The ink composition as described in 1) above, which is an acrylate.

(In the formula (1),
R ₁ represents a C1-C8 alkyl group, an aryl group, a substituted aryl group, or an aromatic heterocyclic group.
R ₂ and R ₃ represent a hydrogen atom or a C1-C8 alkyl group.
R ₄ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group. )

(In the formula (2), R ₁ represents the same meaning as R ₁ in the formula (1).)

(In the formula (3),
R ₅ represents a hydrogen atom or an alkyl group which may have 4 carbon atoms, and R ₆ represents a hydrogen atom or a methyl group. )
3)
The content of the pigment, polymer dispersant, urethane resin, water-soluble organic solvent, and nonionic surfactant in the total mass of the ink composition is 1 to 15 mass%, 0.1 to 15 mass%, 1 The ink composition according to 1), which is ˜20 mass%, 10 to 45 mass%, 0.01 to 5 mass%, and the balance is water.
4)
The ink composition according to 1) or 3), wherein the urethane resin is a polycarbonate-based urethane resin.
5)
The ink composition according to 1) or 3), wherein the water-soluble organic solvent includes polyglyceryl ether and C2-C6 diol.
6)
The ink composition according to any one of 1) to 5), wherein a surface tension is 20 to 40 mN / m and a viscosity is 2 to 10 mPa · s at 25 ° C.
7)
An ink-jet printing method in which printing is performed by ejecting the droplets of the ink composition according to any one of 1) to 6) according to a recording signal and attaching the droplets to a recording material.
8)
7) The recording material according to 7), wherein the recording material is a fiber selected from the group consisting of polyester, cellulose, polyamide, and natural fibers, a mixed fiber containing these fibers, or a fabric containing these fibers. Inkjet printing method.
9)
An ink jet dyeing method in which dyeing is performed by subjecting a recording material printed by the ink jet textile printing method according to 7) or 8) to a steaming or baking process.
10)
The inkjet dyeing method according to 9), wherein a processing temperature of the steaming or baking process is 80 to 250 ° C., and a processing time is 10 seconds to 30 minutes.
11)
A dyed product dyed by the inkjet dyeing method according to 9) or 10).

  According to the present invention, it is possible to provide a pigment ink composition having excellent ink discharge properties, particularly discharge properties after being left open, and an ink jet printing method and dyeing method using the same.

  In this specification, unless otherwise specified, in this specification, “%” and “parts” including examples and the like are both described on a mass basis.

[Pigment]
The pigment is not particularly limited, and a known pigment can be used. As pigments, inorganic pigments, organic pigments, extender pigments and the like are known.

Examples of the inorganic pigment include carbon black, metal oxide, hydroxide, sulfide, ferrocyanide, and metal chloride. Among these, carbon black is preferable as the black pigment.
There are various types of carbon black, such as thermal black and acetylene black obtained by pyrolysis method; oil furnace black, gas furnace black, lamp black, gas black, and channel black obtained by incomplete combustion method. It is done.

Among these, as carbon black, acetylene black, oil furnace black, gas furnace black, lamp black, channel black and the like are preferable.
Specific examples of the carbon black, for example, Raven760ULTRA, Raven780ULTRA, Raven790ULTRA, Raven1060ULTRA, Raven1080ULTRA, Raven1170, Raven1190ULTRA II, Raven1200, Raven1250, Raven1255, Raven1500, Raven2000, Raven2500ULTRA, Raven3500, Raven5000ULTRA II, Raven5250, Raven5750, Raven7000 (or, (Manufactured by Columbia Carbon Co.); Monarch700, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monar h1300, Monarch1400, Regal1330R, Regal1400R, Regal1660R, MoguL L (above, manufactured by Cabot Corporation); Color Black FW1, Color Black FW2, 160 Black, FW200C, Color Black FW2C, Color Black FW2C, Color Black FW2C , Printex U, Printex V, Printex 140U, Printex 140V, SpecIal Black 4, SpecIal Black 4A, SpecIal Black 5, Special Black 600, MA, 8 MA, and more 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300 (manufactured by Mitsubishi Chemical Corporation);

Moreover, it is preferable to use a metal oxide as a white pigment. Examples of the metal oxide include zinc oxide, titanium oxide, and zirconia oxide, and titanium oxide is preferable. Examples of the type of titanium oxide include rutile type and anatase type. Titanium oxide may be used as a powder as it is, or may be silicon dioxide, aluminum oxide, zirconia oxide, zinc oxide, or an organic substance having a hydroxyl group, etc. whose surface is treated. Of these, surface-treated titanium oxide is preferred.
Specific examples of the titanium oxide include, for example, DUAWHITE TCR-52, TITON R-32, TIATONE R-7E, TITON R-21, TITONE R-62N, TITONE R-42 (above, manufactured by Sakai Chemical Industry Co., Ltd.); TIPAQUE CR-50, TIPAQUE CR-50-2, TIPAQUE CR-58, TIPAQUE CR-60, TIPAQUE CR-80, TIPAQUE CR-90 (above, manufactured by Ishihara Sangyo Co., Ltd.); TITANIX JA-600A, TITANIX JR-605 (Above, manufactured by Teika Corporation); ST-455, ST-455WB, ST-457SA, ST-457EC (above, manufactured by Titanium Industry Co., Ltd.);

Examples of the organic pigment include an azo pigment having at least one azo group in the molecule, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, a dioxazine pigment, a perylene pigment, a perinone pigment, a thioindigo pigment, an anthraquinone pigment, and a quinophthalone. Pigments.
Specific examples of the organic pigment include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 24, 55, 73, 74, 75, 83, 93, 94, 95, 97, 98, 108, 114, 128, 129, 138, 139, 150, 151, 154, 155, 180, 185, 193, 199, 202, etc. yellow pigments; C.I. I. Pigment Red 5, 7, 12, 48, 48: 1, 57, 88, 112, 122, 123, 146, 149, 166, 168, 177, 178, 179, 184, 185, 202, 206, 207, 254, Red pigments such as 255, 257, 260, 264, 272; I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 25, 60, 66, 80, and the like; C.I. I. Pigment Violet 19, 23, 29, 37, 38, 50 and the like violet pigments; C.I. I. Pigment Orange 13, 16, 36, 34, 43, 68, 69, 71, 73 and the like orange-brown pigments; C.I. I. Pigment Green 7, 36, 54, etc. green pigments; C.I. I. Pigment Black 1 or the like; a black pigment;

  Examples of the extender pigment include silica, calcium carbonate, talc, clay, barium sulfate, and white carbon. These extender pigments may be used alone, but are usually used in combination with an inorganic pigment or an organic pigment.

As the pigment, a single pigment is usually used. However, if necessary, two or more kinds of pigments may be used in combination. As an example, a combination example of an organic pigment and an extender pigment; an organic pigment and an inorganic pigment; In addition to organic pigments and inorganic pigments, extender pigments can also be used in combination for improving fluidity.
Further, two or more pigments selected from inorganic pigments and organic pigments can be used in combination for adjusting the hue of the dyed product. The hue adjustment here is carried out for the purpose of obtaining a dyed product with shades; expanding the color gamut of dyeing; For this purpose, several kinds of organic pigments can be used together to adjust the desired hue.

[Polymer dispersant]
The polymer dispersant is a mixture of the organic tellurium compound represented by the formula (1) and the organic ditellurium compound represented by the formula (2) or the organic tellurium represented by the formula (1) as a polymerization initiator. It is an AB block polymer obtained by copolymerizing by a living radical polymerization method using any of a mixture of a compound, an azo polymerization initiator, and an organic ditellurium compound represented by the formula (2). The AB block polymer means a polymer in which the A polymer and the B polymer are chemically bonded, and A and B mean polymerized polymers of different monomers.

Formula (1), _{R 1} represents an alkyl group of C1-C8, aryl group, substituted aryl group or an aromatic heterocyclic group. R ₂ and R ₃ represent a hydrogen atom or a C1-C8 alkyl group. R ₄ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group.

In the above formula (1), in R ₁ , examples of the C1-C8 alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n Examples thereof include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms such as -pentyl, n-hexyl, n-heptyl and n-octyl, preferably carbon atoms Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably methyl, ethyl or n-butyl.
As the aryl group, phenyl, naphthyl and the like can be mentioned, and preferably phenyl can be mentioned.
Examples of the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group represented by —CORa (Ra = an alkyl group having 1 to 8 carbon atoms, an aryl group, Examples thereof include an alkoxy group having 1 to 8 carbon atoms, an aryloxy group), a sulfonyl group, a trifluoromethyl group, and the like, and preferably a trifluoromethyl-substituted phenyl group. These substituents may be substituted one or two, and are preferably substituted at the para or ortho position.
Furthermore, examples of the aromatic heterocyclic group include a pyridyl group, a pyrrole group, a furyl group, and a thienyl group.

In the above formula (1), in R ₂ or R ₃ , examples of the C1-C8 alkyl group include the same alkyl groups described in the above R ₁ .

In R ₄ , examples of the aryl group, substituted aryl group, and aromatic heterocyclic group in R ₄ include the same groups as those represented by R ₁ in the formula (1). it can.
Examples of the acyl group include formyl, acetyl, benzoyl and the like.
Examples of the amide group include carboxylic acid amides such as acetamide, malonamide, succinamide, maleamide, benzamide, and 2-fluamide, thioamides such as thioacetamide, hexanedithioamide, thiobenzamide, and methanethiosulfonamide, selenoacetamide, hexanediselenoamide, Examples include selenoamides such as selenobenzamide and methaneselenosulfonamide, N-substituted amides such as N-methylacetamide, benzanilide, cyclohexanecarboxanilide, and 2,4′-dichloroacetanilide.
Examples of the oxycarbonyl group include a group represented by -COORb (Rb = H, an alkyl group having 1 to 8 carbon atoms, an aryl group). Specific examples include carboxy, methoxycarbonyl, Examples thereof include ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl, phenoxycarbonyl and the like. Of these, methoxycarbonyl and ethoxycarbonyl are preferable.

In the formula (1), as a preferred organic tellurium compound, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ and R ₃ are hydrogen atoms or 1 to carbon atoms. A compound that represents an alkyl group of Formula ₄ and in which R ₄ is an aryl group, a substituted aryl group, or an oxycarbonyl group.
Particularly preferably, R ₁ represents an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ Is represented by a phenyl group, a substituted phenyl group, a methoxycarbonyl group, or an ethoxycarbonyl group.

  Specific examples of the organic tellurium compound are as follows. (Methylterranylmethyl) benzene, (1-methylterranylethyl) benzene, 1-chloro-4- (1-methylterranylethyl) benzene, 1-trifluoromethyl-4- (1-methylterranylethyl) Benzene, 3,5-bis-trifluoromethyl-1- (1-methylterranylethyl) benzene, 1,2,3,4,5-pentafluoro-6- (1-methylterranylethyl) benzene, 2 -Methyl terranyl propionitrile, (2-methyl teranyl propyl) benzene, methyl 2-methyl teranyl-2-methyl-propinate, ethyl 2-methyl terranyl-2-methyl-propinate, 2-methyl terranyl-2-methyl-propio A nitrile etc. can be mentioned. Further, in the above, all compounds in which the methyl terranyl moiety is changed to ethyl terranyl, n-butyl terranyl, n-octyl terranyl or the like are also included. In addition, all of the organic tellurium compounds described in International Publication No. 2004/014962 (page 4, line 25 to page 7, line 18) can be exemplified.

  The said organic tellurium compound can obtain the polymer of the target number average molecular weight by adjusting the usage-amount suitably. The preferred amount used is a value obtained by dividing the mass (unit is gram) of the raw material vinyl monomer by the number average molecular weight of the target polymer (the unit of the amount used is the number of moles). It is preferable to use an amount of about 3 to 3 times.

  Depending on the type of vinyl monomer to be polymerized, in addition to the organic tellurium compound represented by the formula (1) used as the polymerization initiator, a ditelluride compound represented by the formula (2) may be further added. Also good.

Specific examples of the ditelluride compound include dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, di-n-butylditelluride, di-sec- Butyl ditelluride, di-tert-butyl telluride, dicyclobutyl telluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis- (p-nitrophenyl) ditelluride, bis -(P-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride, dipyridyl ditelluride and the like can be mentioned.
Dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride, and diphenyl ditelluride are preferable.
Particularly preferred are dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride and di-n-butyl ditelluride.
When the ditelluride compound represented by the formula (2) is used, it is preferably 0.01 to 100 mol, more preferably 0 with respect to 1 mol of the organic tellurium compound represented by the formula (1) used as the polymerization initiator. .1 to 10 mol, more preferably 0.1 to 5 mol.

  The polymerization initiator used in the polymerization step in the present invention may be an azo polymerization initiator in addition to the organic tellurium compound. The azo polymerization initiator is not particularly limited as long as it is an initiator used for ordinary radical polymerization. For example, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2- Methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2 '-Azobisisobutyrate (MAIB), 4,4'-azobis (4-cyanovaleric acid) (ACVA), 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'- Azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylamidinop) Pan) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′- And azobis (N-cyclohexyl-2-methylpropionamide).

These azo polymerization initiators are preferably selected as appropriate according to the reaction conditions.
For example, in the case of low temperature polymerization (40 ° C. or lower), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), In the case of medium temperature polymerization (40-80 ° C.), 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), dimethyl-2,2 In the case of '-azobisisobutyrate (MAIB), 1,1'-azobis (1-acetoxy-1-phenylethane), high temperature polymerization (over 80 ° C), 1,1'-azobis (1-cyclohexanecarbonitrile) ) (ACHN), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methyl) Le propionamide), it is preferable to use 2,2'-azobis (2,4,4-trimethylpentane).
In the reaction using an aqueous solvent, 4,4′-azobis (4-cyanovaleric acid) (ACVA), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (2-methylamidino) is used. Propane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]. It is preferable to use it.

  When the azo polymerization initiator is used, it is preferably 0.01 to 100 mol, more preferably 0.1 to 10 mol, still more preferably relative to 1 mol of the organic tellurium compound of the formula (1) used as the polymerization initiator. It is desirable to use at a ratio of 0.1 to 5 mol.

  A mixture of the organic tellurium compound represented by the formula (1) and the organic ditellurium compound represented by the formula (2), or the organic tellurium compound represented by the formula (1), an azo polymerization initiator, and the formula When a polymer dispersant is prepared using any of the mixture of organic ditellurium compounds represented by (2) as a polymerization initiator, it is characterized by containing an organic tellurium compound in the polymer dispersant component. The total amount of tellurium in the dispersant can be measured by using a known metal measuring method such as an analytical method or an atomic absorption method.

In the present invention, the monomer constituting the A polymer is a monomer represented by the formula (3), and the monomer constituting the B polymer is benzyl methacrylate and / or benzyl acrylate.
In formula (3), R ₅ represents a hydrogen atom or an alkyl group that may have 4 carbon atoms, and R ₆ represents a hydrogen atom or a methyl group. In addition, it is preferable that R ₅ is a hydrogen atom and R ₆ is a methyl group, or R ₅ is an n-butyl group and R ₆ is a monomer that is a methyl group. The combination is a particularly preferable embodiment. The monomer constituting the B polymer is at least one monomer selected from benzyl methacrylate and benzyl acrylate, and more preferably benzyl methacrylate.

  The acid value of the polymer dispersant is preferably 90 to 200 mgKOH / g. More preferably, it is 100-150 mgKOH / g, and 100-120 mgKOH / g is the most preferable. If the acid value is too small, there is a problem in that the solubility in water or a liquid medium is lowered.

  The weight average molecular weight of the polymer dispersant is preferably 10,000 to 60,000. More preferably, it is 10000-40000, and 15000-30000 is the most preferable. If the weight average molecular weight is too small, the stability of the dispersion is lowered.

The amount of the polymeric dispersant to be used is generally represented by a numerical value called a limiting ratio. This division ratio can be obtained by the following equation.
Ratio = polymer dispersant / pigment

  The limiting ratio is preferably 0.1 to 1.0, more preferably 0.1 to 0.6, and particularly preferably 0.2 to 0.4. If the limiting ratio is too small, the stability of the dispersion may be reduced, or the image of the printed matter may be deteriorated.

  In order to dissolve the polymer dispersant in water, it is necessary to use a neutralizing agent. Examples of the neutralizing agent include alkali metal hydroxides, alkaline earth metal hydroxides, aliphatic amine compounds, and alcohol amine compounds.

  Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of the alkaline earth metal hydroxide include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and strontium hydroxide, preferably an alkaline earth metal hydroxide, and more preferably water. Lithium oxide and sodium hydroxide.

  Examples of the alcohol amine compound include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine and N-methyldiethanolamine, preferably tertiary amine. More preferably, it is triethanolamine.

  Examples of the aliphatic amine compound include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, dimethylamine and trimethylamine, with ammonia or triethylamine being preferred.

  These neutralizing agents can be used alone or in combination.

  A desired amount of the neutralizing agent can be used. When neutralization is performed with the theoretical equivalent of the acid value of the polymer dispersant, the degree of neutralization is 100%, and the neutralizing agent can be used in excess of the theoretical amount. The degree of neutralization is preferably 50 to 200%, more preferably 80 to 150%, and most preferably 100 to 120%.

  Further, when a polymer dispersant having an acid value exceeding 200 mgKOH / g is used, by using a neutralization degree lower than 100% neutralization degree, the same performance as when a low acid value dispersant is used is used. May be obtained.

  As the pigment, a microencapsulated pigment obtained by coating the surface of the pigment with a polymer dispersant can be used, or a pigment that is not microencapsulated can be used. Among these, it is preferable to use a microencapsulated pigment whose pigment surface is coated with a polymer dispersant.

  Examples of the method for coating the surface of the pigment with the polymer dispersant include known methods. The methods are roughly classified into two methods, a physical / mechanical method and a chemical method. Among the latter chemical methods, Non-Patent Document 1 in which a surface precipitation method, a kneading method, an interfacial polymerization method, and the like are proposed, respectively, discloses in detail the performance of the microencapsulated pigment. Here, the surface precipitation method is a method for precipitating a polymer dispersant on the pigment surface by utilizing pH adjustment or a difference in solubility in a medium, and includes an acid precipitation method, a phase inversion emulsification method, and the like. The interfacial polymerization method is a method in which a monomer, oligomer, or pigment derivative is adsorbed on the pigment surface and then a polymerization reaction is performed, and is also referred to as a surface polymerization method. Any of the above methods can be used, but among these, the surface precipitation method is preferable, and a phase inversion emulsification method is more preferable.

The pigment whose surface is coated with the polymer dispersant usually has an average particle size of 200 nm or less, preferably 50 nm to 150 nm, and more preferably 60 nm to 120 nm. As a result, the dispersion stability and the ejection stability are excellent, and the print density of the recorded image can be increased.
The average particle diameter can be measured using, for example, a laser light scattering method.

On the other hand, examples of a method for dispersing the pigment include a method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, and the like. Among these, a sand mill (bead mill) is preferable. In addition, the pigment dispersion using a sand mill (bead mill) is prepared by using beads with a small system (0.01 mm to 1 mm diameter) under conditions where the dispersion efficiency is increased by increasing the filling rate of beads. It is desirable.
By dispersing under such conditions, the particle size of the pigment can be reduced, and a dispersion with good dispersibility can be obtained. It is also preferable to remove components such as pigments having a large particle size by filtration and / or centrifugation after the dispersion is prepared. In addition, for the purpose of suppressing foaming during the preparation of the dispersion, an extremely small amount of the antifoaming agent such as the above-mentioned silicone or acetylene glycol may be added. However, as the antifoaming agent, there is one that inhibits dispersion and micronization, and it is preferable to use a defoaming agent that does not affect the stability after dispersion or dispersion.

[Urethane resin]
The urethane resin is often sold in the form of a latex (emulsion) and can be easily purchased. Specific examples thereof include, for example, Permarin UA-150, 200, 310, 368, 3945, Yukot UX-320 latex (manufactured by Sanyo Chemical Co., Ltd.), Hydran WLS-201, 210, HW-312B latex ( As mentioned above, DIC Corporation), Superflex 150, 170, 470 (above, Daiichi Kogyo Seiyaku Co., Ltd.) etc. are mentioned, Most of which are liquids which emulsified resin with a solid content of 30 to 60%.
As the urethane resin, any of the latexes described above can be used, but among them, it is preferable to use a polycarbonate-based urethane resin. Examples of such resins include Permarin UA-310, 3945 and U-coat UX-320, with U-coat UX-320 being preferred. A urethane resin may use a single thing and may use 2-3 types together.

[Water-soluble organic solvent]
The ink composition contains at least one compound represented by the formula (4) and the formula (5).
In formula (4), all of EO, PO, and BO are oxygen atoms in “CH ₂ O” or “H—CO” shown on the left side of the parentheses in formula (4), and EO, PO, and BO are Bond with the carbon atom that has it. Similarly, a hydrogen atom represented by “—H” on the right side of the parenthesis is bonded to an oxygen atom of EO, PO, and BO.
In Formula (4) and Formula (5), the order in which EO, PO, and BO are combined is arbitrary, and can be combined in any order. That is, an arbitrary combination selected from EO, PO, and BO is randomly combined; one of EO, PO, and BO is combined; and a combination of a plurality of EO is combined with PO And / or a combination of a plurality of BOs combined in a block form;
In formula (4), the sum of m1 to m3, n1 to n3, and q1 to q3 is an average value and is usually greater than 0 and 100 or less, preferably 0.5 to 75, more preferably 5 to 60, and even more preferably 10 ~ 30.
As a compound represented by Formula (4), any two of m1 to m3, n1 to n3, and q1 to q3 are 0, and the remaining one is an average value that is usually larger than 0 and 100 or less, 0. 5-75 are preferable, 5-60 are more preferable, and 10-30 are still more preferable. Among them, compounds in which m1 to m3 or n1 to n3 are not 0 are preferable.
The compound represented by Formula (4) is a polyoxyalkylene adduct of glycerin. The compound can be synthesized or obtained as a commercial product.
As an example of a commercial product, Sanyo Chemical Industries, Ltd. Sannix GP series (glycerin polyoxypropylene adduct); Aoki Yushi Kogyo Co., Ltd. Brannon GL series (glycerin polyoxyethylene adduct); Uniloop 50TG-32 manufactured by Oil Co., Ltd. (polyoxyethylene and polyoxypropylene adduct of glycerin, polyoxyethylene addition mol number 24, polyoxypropylene addition mol number 24), Wilbride S-753 (glycerin polyoxyethylene, Polyoxypropylene and polyoxybutylene adduct, polyoxyethylene addition mole number 8, polyoxypropylene addition mole number 5, polyoxypropylene addition mole number 16); and the like.
The total content of the compound represented by formula (4) in the total mass of the ink composition is usually 0.1% to 30%, preferably 0.1% to 20%.

In the above formula (5), EO, PO, and BO are all oxygen atoms in “CH ₂ O” or “H—CO” shown at the left end of formula (5), and carbon contained in EO, PO, and BO. Bond with atoms. Similarly, the hydrogen atom represented by “—H” shown at the right end is bonded to the oxygen atom of EO, PO, and BO.
In formula (5), the sum total of j, k, and p is an average value normally 1-10, Preferably it is 3-8, More preferably, it is 3-6, More preferably, it is 3 or 4, Especially preferably, it is 3.
As a compound represented by Formula (5), any two of j, k, and p are 0, and the remaining one is an average value, and 1-10, 3-8 are preferable normally, and 3-6 are More preferably, 3 or 4 is more preferable, and 3 is particularly preferable. Among them, compounds in which j or k is not 0 are preferable, and compounds in which j is not 0 are more preferable.

  Examples of the water-soluble organic solvent that can be used in combination with the compounds represented by formula (4) and formula (5) include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, and tertiary butanol. C1-C4 monools such as ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, 1,3-pentanediol, 1,5-pentanediol, 1 C2-C6 diols such as 1,2-hexanediol and 1,6-hexanediol; C3-C6 triols such as glycerin, hexane-1,2,6-triol and trimethylolpropane; N, N-dimethylformamide, N, Carboxylic acid amides such as N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyro Heterocyclic ureas such as dong, 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyrimido-2-one; acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentane-4- Ketones or keto alcohols such as ON; linear or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; di-C2-C3 alkylene glycols or thioglycols such as diethylene glycol, dipropylene glycol and thiodiglycol; polyethylene glycol; Poly C2-C3 alkylene glycol (preferably liquid) having a repeating unit of 11 or more and a molecular weight of about 20000 or less, such as polypropylene glycol; polyglyceryl ether such as diglycerin, triglycerin, polyglycerin; Polyoxy C2-C3 alkylene polyglyceryl ethers such as xylethylene polyglyceryl ether and polyoxypropylene polyglyceryl ether; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), tri C1-C4 alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether; cyclic esters or carbonates such as γ-butyrolactone and ethylene carbonate; dimethyl sulfoxide; acetic acid; It is done.

[Nonionic surfactant]
Examples of the nonionic surfactant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether. Ether type: polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc. Ester series; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, Acetylene glycol (alcohol) type such as 1,5-dimethyl-1-hexyn-3-ol; trade name Surfinol 104, 105PG50, 82, 420, 440, 465, 485, DF-110D, Olfin STG Polyglycol ether type (for example, TergItol15-S-7 manufactured by SIGMA-ALDRICH); and the like. The nonionic surfactants can be used alone or in combination, and are preferably surfinol-based, more preferably surfinol 420.

Examples of the content of each component in the total mass of the ink composition used for inkjet printing include the following ranges.
Pigment: Usually 1 to 15%, preferably 1 to 10%, more preferably 1 to 7%.
Polymer dispersing agent: Usually 0.1 to 15%, preferably 0.1 to 9%, more preferably 0.2 to 6%.
Urethane resin: usually 1 to 20%, preferably 3 to 15%, more preferably 3 to 12%.
Water-soluble organic solvent: Usually 10 to 45%, preferably 15 to 38%, more preferably 20 to 35%.
Nonionic surfactant: Usually 0.01 to 5%, preferably 0.05 to 3%, more preferably 0.1 to 2.5%.
In addition, the remainder other than the above is water.

  The method for preparing the ink composition is not particularly limited. Usually, after preparing an aqueous pigment dispersion containing a pigment and a polymer dispersant, a urethane resin, a water-soluble organic solvent, a nonionic surfactant, and The ink composition is prepared by adding other components as necessary.

  In preparing the ink composition, ink preparation agents other than those described above can be used as appropriate. Examples thereof include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, antioxidants, and surfactants. Hereinafter, these ink preparation agents will be described.

  Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and salts thereof. .

Examples of preservatives include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, iodopropargyl, haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzothiazole. , Isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, Examples include benzyl bromacetate and inorganic salt compounds.
Specific examples of the organic halogen compound include, for example, sodium pentachlorophenol. Specific examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide. Specific examples of the isothiazoline-based compound include, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazoline-3- ON, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium Examples include chloride. Specific examples of other antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, trade names of Proxel GXL (S) and Proxel XL-2 (S) manufactured by Arch Chemical Co., Ltd.

As the pH adjuster, any substance can be used as long as it can control the pH of the ink within a range of, for example, 5 to 11 without adversely affecting the prepared ink. For example, the same materials as those listed above in “Neutralizing agent used for neutralizing polymer dispersant” can be used.
Other specific examples include, for example, alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium bicarbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; disodium phosphate and the like And the like.

  Specific examples of the chelating reagent include, for example, disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.

  Specific examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Specific examples of the water-soluble ultraviolet absorber include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

  Specific examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamine or polyimine.

  As the antioxidant, for example, various organic and metal complex antifading agents can be used. Specific examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic rings. It is done.

  Regarding all the components contained in the ink composition, the content thereof, and the like, a combination of preferable ones is more preferable, and a combination of more preferable ones is further preferable. The same applies to a combination of a preferable one and a more preferable one, a more preferable one, and a more preferable one.

  The ink-jet printing method is a method of performing printing by discharging droplets of the ink composition in accordance with a recording signal and attaching them to a recording material. There is no restriction | limiting in particular about the ink nozzle of the inkjet printer used in the case of textile printing, According to the objective, it can select suitably.

  The textile printing method is a known method, for example, a charge control method for ejecting ink using electrostatic attraction force; a drop-on-demand method (pressure pulse method) using vibration pressure of a piezo element; Either an acoustic ink jet method that irradiates ink using a radiation pressure instead of a beam; an ink jet method that discharges ink using the radiation pressure; a thermal ink jet method that heats ink to form bubbles and uses the generated pressure; Can be used.

Examples of the recording material in the ink-jet printing method include fibers selected from the group consisting of polyester, cellulose, polyamide, and natural fibers, or fabrics containing these fibers.
Examples of the polyester fiber include a fiber mainly composed of polyethylene terephthalate.
Examples of the cellulose fiber include cotton, cotton, rayon, triacetate fiber, and diacetate fiber.
Examples of polyamide fibers include nylon fibers.
Examples of natural fibers include silk and wool.
The fiber may be a single material fiber or a mixed fiber thereof. These fibers may be provided with an ink receiving layer (bleeding prevention layer). This method of forming the ink receiving layer on the fiber is a publicly known and publicly available technique, and the fiber having the ink receiving layer can be obtained from the market. In addition, it is possible to appropriately select constituent components, a forming method, and the like from publicly known and publicly used techniques and to provide an ink receiving layer on the fiber. The ink receiving layer is not particularly limited as long as it has the function.

The ink jet dyeing method is a method of dyeing a recording material printed by the ink jet textile printing method by performing a steaming or baking process.
As the steaming treatment, for example, in a high-temperature steamer, it is usually 80 to 250 ° C., preferably 170 to 180 ° C., usually 10 seconds to 30 minutes, preferably about 10 minutes. This method is sometimes called wet heat fixation or the like.
Moreover, as a baking (thermosol) process, it can dye by the process normally about 80-250 degreeC, Preferably it is 190-210 degreeC, Usually 10 second-30 minutes, Preferably it is about 60-180 second. This method is sometimes called dry heat fixing.
In this way, a dyed product dyed by the ink jet dyeing method is obtained. The dyed material means a recording material dyed by the ink jet dyeing method.

In order to print on a fiber by the inkjet printing method, for example, a container containing the ink composition is set at a predetermined position of an inkjet printer for printing capable of transporting a fabric, and a recording material is printed by the inkjet printing method. You can print on
In the inkjet printing method, full-color printing can be performed by selecting the type of pigment contained in the ink composition and using it as an ink set. For example, it may be used as an ink set of four colors of yellow, red, blue, and black, and if necessary, it is appropriately selected from pigments of each color such as green, violet, orange to brown, etc. It can also be used as an ink set.

The ink composition has good ink filling into the ink jet head, and can perform stable discharge without bending or rubbing during printing. Further, in both cases of continuous printing and intermittent printing, it is possible to perform good discharge without clogging the nozzles.
Further, the storage stability during storage is good, and the redispersibility is very good even when the ink composition has been dried by losing moisture or the like in the ink composition.
Also, in dyeing fibers, there is no bleeding and high color development, and in full color printing, adjacent colors are not mixed and high quality.
Moreover, it is excellent also in various fastness after dyeing | staining, for example, various light resistance, such as sweat, water resistance, and various washing fastness.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by the following example.

[Synthesis Example 1]
In a glove box substituted with nitrogen, a flask equipped with a stirrer was charged with 90 g (511 mmol) of benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.00 g (6.67 mmol) of BTEE, 1.22 g (3.33 mmol) of DBDT, 2, 0.33 g (2.00 mmol) of 2′-azobis-isobutyronitrile (trade name: AIBN, manufactured by Otsuka Chemical Co., Ltd., hereinafter referred to as “AIBN”) and 90 g of methoxypropanol were charged and reacted at 60 ° C. for 16 hours. The polymerization rate was 99.6%, Mw was 16,200, and PDI was 1.41.
To the resulting solution, 45 g (317 mmol) of butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 25 g (290 mmol) of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.22 g (1.33 mmol) of AIBN and 70 g of methoxypropanol were added. The reaction was carried out at ° C for 22 hours. The polymerization rate was 99.1%.
After completion of the reaction, the reaction solution was poured into 5 L of heptane, and the precipitate was suction filtered and dried to obtain 138.2 g (yield 86%) of block copolymer A as a white powder. The acid value was 104. Mw and PDI were measured after methyl esterifying the carboxylic acid component in the block copolymer, and Mw was 24,300 and PDI was 1.49.
[Preparation Example 1]
The polymer dispersant (7.5 parts) obtained in Synthesis Example 1 was dissolved in 2-butanone (20 parts). A solution prepared by dissolving 0.6 part of sodium hydroxide in ion-exchanged water (46 parts) was added to this solution, and the mixture was stirred for 1 hour to obtain an emulsion. To the resulting liquid, C.I. I. Pigment Black 7 (manufactured by Eponic Degussa, Nerox 305, 25 parts) was added, and dispersion treatment was performed for 15 hours using a sand grinder at 1500 rpm. The obtained liquid was diluted with ion exchange water, and the beads for dispersion were separated by filtration. A portion of 2-butanone and water in the mother liquor obtained was distilled off under reduced pressure with an evaporator and concentrated to obtain a dispersion having a solid content of 12.0%. This is designated as “Dispersion 1”. The solid content in the aqueous solution was determined by a dry weight method using MS-70 manufactured by A & D Corporation. The average particle diameter of the pigment contained in the dispersion 1 was 100 nm, and the viscosity of the dispersion at 25 ° C. was 3.5 mPa · s.

[Example 1]
Each component shown in the following Table 1 was mixed, and impurities were separated by filtration with a 3 μm membrane filter to obtain the ink composition of Example 1 used for the evaluation test. The resin content in the ink composition was adjusted to 6%.

[Comparative Examples 1 and 2]
Comparative ink compositions of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1 except that each component shown in Table 1 below was used.
In addition, the addition amount of the water-soluble organic solvent or the like was appropriately adjusted so that each of the inks of Examples and Comparative Examples had a viscosity in the range of 5 to 6 mPa · s.

[Dischargeability test after leaving open]
Using an industrial inkjet printing printer, inkjet printing was performed for 10 seconds, and then printing was stopped. After leaving for 30 minutes, inkjet printing was started again, the state of printing immediately after the start was visually confirmed, and evaluation was performed according to the following three evaluation criteria AC. The results are shown in Table 1 below.
In Table 1, “Dischargeability” means the dischargeability test result after being left open.
A: No rubbing is observed on the printed part.
B: Slight rubbing is observed in the printed portion.
C: Scratch is clearly observed in the printed portion.

  As is apparent from the results in Table 1, Example 1 exhibited superior dischargeability after being left open compared to the comparative examples.

  The ink composition of the present invention is extremely useful as an ink for ink jet textile printing because of its excellent dischargeability after being left open.

Claims (11)

An ink composition used for inkjet printing, comprising a pigment, water, a polymer dispersant, a urethane resin, a water-soluble organic solvent, and a nonionic surfactant, wherein the water-soluble organic solvent includes at least one of the following formulas: An ink composition comprising a compound represented by (4) and a compound represented by the following formula (5).

[In the above formula (4),
EO represents an ethyleneoxy group, PO represents a propyleneoxy group, BO represents a butyleneoxy group,
The order in which EO, PO and BO are combined is arbitrary,
m1, m2, m3, n1, n2, n3, q1, q2 and q3 represent 0 or an integer of 1 or more, but all are not 0, and m1 to m3, n1 to n3, and q1 The sum total of ˜q3 is an average value larger than 0 and not larger than 100. ]

[In the above formula (5),
EO represents an ethyleneoxy group, PO represents a propyleneoxy group, BO represents a butyleneoxy group,
The order in which EO, PO and BO are combined is arbitrary,
j, k, and p represent 0 or an integer of 1 or more, but they are not all 0, and the sum of j, k, and p is 1 to 10 on average. ] The polymer dispersant is represented by a mixture of an organic tellurium compound represented by the following formula (1) and an organic ditellurium compound represented by the following formula (2), or the following formula (1), as a polymerization initiator. A and B obtained by copolymerization by a living radical polymerization method using any one of a mixture of an organic tellurium compound, an azo polymerization initiator and an organic ditellurium compound represented by the following formula (2): It is an AB block polymer which is a polymerized polymer, wherein the monomer constituting the A block is one or more kinds of monomers represented by the following formula (3), and the monomer constituting the B block is benzyl methacrylate and / or benzyl The ink composition according to claim 1, which is an acrylate.

(In the formula (1),
R ₁ represents a C1-C8 alkyl group, an aryl group, a substituted aryl group, or an aromatic heterocyclic group.
R ₂ and R ₃ represent a hydrogen atom or a C1-C8 alkyl group.
R ₄ represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group. )

(In the formula (2), R ₁ represents the same meaning as R ₁ in the formula (1).)

(In the formula (3),
R ₅ represents a hydrogen atom or an alkyl group which may have 4 carbon atoms, and R ₆ represents a hydrogen atom or a methyl group. )   The content of the pigment, polymer dispersant, urethane resin, water-soluble organic solvent, and nonionic surfactant in the total mass of the ink composition is 1 to 15 mass%, 0.1 to 15 mass%, 1 The ink composition according to claim 1, wherein the ink composition is -20% by mass, 10-45% by mass, 0.01-5% by mass, and the balance is water.   The ink composition according to claim 1 or 3, wherein the urethane resin is a polycarbonate-based urethane resin.   2. The ink composition according to claim 1, wherein in the formula (5), p is 0, and the sum of j and k is 1 to 10 on average.   The ink composition according to any one of claims 1 to 5, which has a surface tension of 20 to 40 mN / m and a viscosity of 2 to 10 mPa · s at 25 ° C.   An ink-jet printing method in which printing is performed by ejecting droplets of the ink composition according to any one of claims 1 to 6 according to a recording signal and attaching the droplets to a recording material.   The recording material according to claim 7, wherein the recording material is a fiber selected from the group consisting of polyester, cellulose, polyamide, and natural fiber, a mixed fiber containing these fibers, or a fabric containing these fibers. Inkjet printing method.   An ink jet dyeing method for dyeing a recording material printed by the ink jet textile printing method according to claim 7 or 8 by performing a steaming or baking treatment.   The inkjet dyeing | staining method of Claim 9 whose processing temperature of the said steaming or baking process is 80-250 degreeC, and processing time is 10 second-30 minutes.   A dyed product dyed by the ink jet dyeing method according to claim 9 or 10.