JP2019167494A - Ink and fiber printing method - Google Patents

Abstract

To provide a pigment ink that allows an image having high color development to be printed on a white fiber without requiring pretreatment ink or white ink and only by using a color ink, and a fiber printing method using the same.SOLUTION: The present invention provides an ink containing a pigment, a dispersant, an urethane resin, a water-soluble organic solvent, a nonionic surfactant, and water, the water-soluble organic solvent at least containing two C2-C6 alkanediols each having a boiling point of 200°C±15°C, and a C3-C6 alkanetriol with a boiling point of 300°C±15°C.SELECTED DRAWING: None

Description

  The present invention relates to a color ink, particularly a color ink used for fibers, and a textile printing method using the same.

  Conventionally, hand-drawing and screen printing have been mainstream in textile printing methods. Recently, however, fiber printing methods (inkjet printing) using an ink jet printer are increasing.

  Examples of the colorant used for inkjet printing include water-soluble dyes. Such a dye has a mechanism for causing a colorant to penetrate into the inside of the fiber to develop a color, has a clear hue, and has a wide color gamut that can be reproduced. On the other hand, water-soluble dyes have low light resistance; it requires fixing after the dye is attached to the fiber and washing with water, etc .; and the disadvantage of complicated treatment of the dye waste liquid generated by washing and the like. Have. For this reason, attention has been paid to the use of a water-insoluble colorant in place of the water-soluble dye.

  Ink-jet printing using a water-insoluble colorant, a fiber to which an ink containing a colorant is attached is dried by heat treatment, and the colorant is fixed on the surface of the fiber to develop a color. For this reason, if the drying property of the ink by the heat treatment is low, the ink does not dry, and the colorant gradually penetrates into the inside of the fiber, so that the color developability deteriorates. Regarding this problem, it is important to improve the drying property of the ink.

Japanese Patent Application Laid-Open No. 07-119047 JP 2000-226781 A

  An object of the present invention is to provide a pigment ink capable of obtaining an image having high color developability even when only a color ink is used without using a pre-treatment ink or a white ink on a white background fiber, and using the same The provision of a textile printing method.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using an ink containing a pigment, water, a dispersant, a urethane resin, a water-soluble organic solvent, and a nonionic surfactant, and completed the present invention. It was.
That is, the present invention relates to the following 1) to 10).
1)
An ink containing a pigment, a dispersant, a urethane resin, a water-soluble organic solvent, a nonionic surfactant, and water,
An ink containing at least two types of C2-C6 alkanediol having a boiling point of 200 ° C. ± 15 ° C. and C3-C6 alkanetriol having a boiling point of 300 ° C. ± 15 ° C. as the water-soluble organic solvent.
2)
The dispersant is 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 an organic tellurium represented by the following formula (1) as a polymerization initiator. A polymer obtained by copolymerizing by a living radical polymerization method using any one of a mixture of a compound, an azo polymerization initiator and an organic ditellurium compound represented by the following formula (2), wherein A and B are different from each other The AB block polymer is a monomer that constitutes the A block is one or more monomers represented by the following formula (3), and the monomer that constitutes the B block is selected from benzyl methacrylate and benzyl acrylate The ink as described in 1) above, which is one or more types of monomers.

(In the above 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 above formula (2), _{R 1} represents the same meaning as _{R 1} in the formula (1).)

(In the above 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, dispersant, urethane resin, water-soluble organic solvent, and nonionic surfactant in the total mass of the ink is 1 to 15% by mass, 0.1 to 15% by mass, and 1 to 20% by mass, respectively. 10 to 45% by mass, 0.01 to 5% by mass, and the remainder is water.
4)
The ink according to 1) or 3), wherein the urethane resin is a polycarbonate-based urethane resin.
5)
The ink according to 1) or 3), wherein the water-soluble organic solvent further contains an alkylene oxide adduct of polyglycerol.
6)
An ink-jet printing method in which printing is performed by ejecting the ink droplets according to any one of 1) to 5) according to a recording signal and attaching the ink droplets to a recording material.
7)
6) The recording material according to 6), 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.
8)
An ink jet dyeing method for dyeing a recording material printed by the ink jet textile printing method described in 6) or 7) above by baking.
9)
The inkjet dyeing method according to 8) above, wherein the baking treatment temperature is 130 to 250 ° C., and the treatment time is 10 seconds to 30 minutes.
10)
A dyed product dyed by the ink jet dyeing method according to 8) or 9).

  According to the present invention, there is no need for pretreatment ink or white ink on a white background fiber, and even when only a color ink is used, a pigment ink capable of obtaining an image having high color developability, and a fiber using the same We could provide printing method.

  In this specification, unless otherwise specified, “parts” and “%” including examples are described on a mass basis. “CI” means a color index.

[Water-insoluble colorant]
In this specification, the water-insoluble colorant means a colorant having a solubility in water at 25 ° C. of usually 3 g / liter or less, preferably 1 g / liter or less, more preferably 500 mg / liter or less, and further preferably 100 mg / liter or less. Is mentioned.
Such colorants include C.I. I. Disperse, C.I. I. Colorants selected from Solvent and pigments. Of these, pigments are preferred. Examples of the pigment include inorganic pigments, organic pigments, extender pigments, and the like.

Examples of the inorganic pigment include carbon black, metal oxide, hydroxide, sulfide, ferrocyanide, metal chloride and the like. Among these, carbon black is preferable as the black pigment.
Examples of carbon black include thermal black, acetylene black, oil furnace black, gas furnace black, lamp black, gas black, and channel black. Among these, acetylene black, oil furnace black, gas furnace black, lamp black, and channel black are preferable.
Specific examples of carbon black include, for example, the Raven series manufactured by Columbian Carbon; the Monarch series, Regal series, and Mogul series manufactured by Cabot; the Color Black series, the Printex series, the Special Black series manufactured by Degussa; Examples include MA series and MCF series manufactured by the company.

A metal oxide is preferably used as the white pigment. Examples of the metal oxide include zinc oxide, titanium oxide, and zirconia oxide, and titanium oxide is preferable. Examples of the titanium oxide include rutile type and anatase type. Titanium oxide can be used as it is as a powder. Alternatively, the surface can be treated with silicon dioxide, aluminum oxide, zirconia oxide, zinc oxide, an organic compound having a hydroxy group, or the like. Among these, surface-treated titanium oxide is preferable.
Specific examples of titanium oxide include, for example, DUAWHITE series and TITON series manufactured by Sakai Chemical Industry Co., Ltd .; Typeix series manufactured by Ishihara Sangyo Co., Ltd .; TITANIX series manufactured by Teika Co., Ltd .; ST series manufactured by Titanium Industry Co., Ltd. Can be mentioned.

Examples of organic pigments include azo pigments having at least one azo group in the molecule, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments. Can be mentioned. Among these, C.I. I. Pigments selected from pigments are preferred.
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; I. Pigment Red 5, 7, 12, 48, 48: 1, 57, 88, 112, 122, 123, 146, 149, 150, 166, 168, 177, 178, 179, 184, 185, 202, 206, 207, 254, 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; I. Pigment violet 19, 23, 29, 37, 38, 50; C.I. I. Pigment orange 13, 16, 34, 36, 43, 68, 69, 71, 73; I. Pigment Green 7, 36, 54; and C.I. I. Pigment black 1, 7 and the like.

  Examples of the extender pigment include silica, calcium carbonate, talc, clay, barium sulfate, and white carbon.

  Examples of the water-insoluble colorant include C.I. I. Pigments selected from pigments and carbon black are preferred; I. Pigment yellow, C.I. I. Pigment Red, C.I. I. Pigment blue, C.I. I. Pigment violet, C.I. I. Pigment orange and C.I. I. More preferred are pigments selected from CI Pigment Green.

As the water-insoluble colorant, a single colorant is usually used. However, if necessary, two or more water-insoluble colorants may be used in combination. As an example, a combination example of organic pigment and extender pigment; organic pigment and inorganic pigment; In addition to organic pigments and inorganic pigments, extender pigments can also be used in combination for improving fluidity.
Furthermore, two or more colorants 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.

[Dispersant]
The dispersant is a mixture of the organic tellurium compound represented by the above formula (1) and the organic ditellurium compound represented by the above formula (2) as a polymerization initiator, or the organic tellurium compound represented by the above formula (1), It is an AB block polymer obtained by copolymerizing by a living radical polymerization method using any one of a mixture of an azo polymerization initiator and an organic ditellurium compound represented by the above 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.

In the above 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 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, n-octyl, etc., preferably carbon atoms Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably methyl, ethyl or n-butyl.
Examples of the aryl group include phenyl, naphthyl and the like, and preferably phenyl.
Moreover, as a substituted aryl group, the phenyl group which has a substituent, the naphthyl group which has a substituent, etc. are mentioned. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by -CORa (Ra is a C1-C8 alkyl group, an aryl group, a C1-C8 alkoxy group, an aryloxy group). Group, sulfonyl group, trifluoromethyl group, etc. Among them, trifluoromethyl group is preferable, and the number of these substituents is usually 1 or 2, and substituted at the para-position or ortho-position. Preferably it is.
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).
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 include ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl, phenoxycarbonyl and the like. Of these, methoxycarbonyl and ethoxycarbonyl are preferable.

In the above formula (1), as preferred organic tellurium compounds, R ₁ is a C1-C4 alkyl group, R ₂ and R ₃ are a hydrogen atom or a C1-C4 alkyl group, R ₄ is an aryl group, a substituted aryl group, or oxy It is a compound that is a carbonyl group.
More preferably, R ₁ is a C1-C4 alkyl group, R ₃ and R ₄ are a hydrogen atom or a C1-C4 alkyl group, and R ₅ is a phenyl group, a substituted phenyl group, a methoxycarbonyl group, or an ethoxycarbonyl group. is there.

  Specific examples of the organic tellurium compound include, for example, (methylterranylmethyl) benzene, (1-methylterranylethyl) benzene, 1-chloro-4- (1-methylterranylethyl) benzene, 1-trifluoro Methyl-4- (1-methylteranylethyl) benzene, 3,5-bis-trifluoromethyl-1- (1-methylteranylethyl) benzene, 1,2,3,4,5-pentafluoro-6 -(1-methylterranylethyl) benzene, 2-methylterranylpropionitrile, (2-methylterranylpropyl) benzene, methyl 2-methylterranyl-2-methyl-propinate, ethyl 2-methylterranyl-2-methyl- Examples include propinate and 2-methylterranyl-2-methyl-propionitrile. In addition, 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 generally a value obtained by dividing the mass of the raw material vinyl monomer (unit: grams) by the number average molecular weight of the target polymer (unit of use amount 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 above formula (1) used as the polymerization initiator, a ditelluride compound represented by the above formula (2) may be further added. You can also.

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.
Of these, dimethylditelluride, diethylditelluride, di-n-propylditelluride, di-n-butylditelluride, diphenylditelluride are preferred; dimethylditelluride, diethylditelluride, di-n -Propyl ditelluride and di-n-butyl ditelluride are more preferable.
When the ditelluride compound represented by the above formula (2) is used, the amount used is usually 0.01 to 100 mol, preferably 0 when the total amount of the organic tellurium compound represented by the above formula (1) is 1 mol. 0.1 to 10 mol, more preferably 0.1 to 5 mol.

  As the polymerization initiator, in addition to the organic tellurium compound, an azo polymerization initiator may be used. 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), 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), dimethyl-2,2 during medium temperature polymerization (40-80 ° C.) '-Azobisisobutyrate (MAIB), 1,1'-azobis (1-acetoxy-1-phenylethane), 1,1'-azobis (1-cyclohexanecarbonitrile for high temperature polymerization (over 80 ° C) ) (ACHN), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methyl) Le propionamide), 2,2'-azobis (2,4,4-trimethylpentane), it is preferably used, respectively.
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 using the azo polymerization initiator, the amount used is usually 0.01 to 100 mol, preferably 0.1 to 10 mol, more preferably when the total amount of the organic tellurium compound of the above formula (1) is 1 mol. 0.1 to 5 mol.

  A mixture of an organic tellurium compound represented by the above formula (1) and an organic ditellurium compound represented by the above formula (2), or an organic tellurium compound represented by the above formula (1), an azo polymerization initiator, and the above formula When a dispersant is prepared using any of the mixture of organic ditellurium compounds represented by (2) as a polymerization initiator, the prepared dispersant contains an organic tellurium compound. For this reason, the tellurium total amount in a dispersing agent can be measured by using well-known metal measuring methods, such as an ICP emission spectrometry and an atomic absorption method.

The monomer constituting the A block in the dispersant is one or more monomers represented by the above formula (3), and the monomer constituting the B block 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. Among them, a monomer in which R ₅ is a hydrogen atom and R ₆ is a methyl group; or a monomer in which R ₅ is an n-butyl group and R ₆ is a methyl group is preferable. It is more preferable to use these two types of monomers in combination.
The monomer constituting the B block is one or more monomers selected from benzyl methacrylate and benzyl acrylate, and preferably benzyl methacrylate.

  The acid value of the dispersant is usually 90 to 200 mgKOH / g, preferably 100 to 150 mgKOH / g, more preferably 100 to 120 mgKOH / g. By setting it as such an acid value, the dispersibility with respect to water or the mixture of a water-soluble organic solvent and water becomes favorable, and there exists a tendency for the coloring property when a recording material is colored to improve.

  The weight average molecular weight of the dispersant is preferably 10,000 to 60,000. More preferably, it is 10000-40000, and 15000-30000 is still more preferable. By setting it as such a weight average molecular weight, stability of a dispersion liquid improves.

  The amount of the dispersant to be used with respect to the total mass of the pigment is preferably 0.1 to 1, more preferably 0.1 to 0.6, and particularly preferably 0.2 to 0.4 on the mass basis. By using this amount, the stability of the dispersion is improved and the image quality of the recorded image tends to be improved.

  For the purpose of uniformly dispersing the dispersant in water, a neutralizer can be used. Examples of the neutralizing agent include alkali metal hydroxides, alkaline earth metal hydroxides, aliphatic amine compounds and alkanolamine 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 alkanolamine compound include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine and N-methyldiethanolamine. Among these, tertiary alkanolamine is preferable, and triethanolamine is more preferable.

  Examples of the aliphatic amine compound include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, dimethylamine and trimethylamine. Among these, ammonia or triethylamine is preferable.

  The amount of the neutralizing agent used is not particularly limited. The neutralization degree is 100% when neutralized with the theoretical equivalent of the acid value of the dispersant, and the neutralizing agent can be used in excess of the theoretical equivalent. The degree of neutralization is usually 50 to 200%, preferably 80 to 150%, more preferably 100 to 120%.

  When a dispersant having an acid value exceeding 200 mgKOH / g is used, the same effect as when a dispersant having a lower acid value than that of the acid value is used by setting the neutralization degree to be lower than 100% neutralization degree. There are times when you can get.

Examples of the method for coating the surface of the pigment with the dispersant include known methods. The methods are roughly classified into two methods, a physical / mechanical method and a chemical method. Among the chemical methods of the latter, Non-Patent Document 1, in which a surface precipitation method, a kneading method, an interfacial polymerization method, and the like are proposed, discloses the performance of the microencapsulated pigment in detail. Here, the surface precipitation method is a method for precipitating a dispersant on the pigment surface by utilizing a 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 the phase inversion emulsification method is more preferable.
In the present specification, “coating the dispersant on the surface of the pigment” includes both coating the dispersant on all of the pigment surface and part of the pigment surface.

The average particle size of the pigment dispersed by the dispersant is usually 10 nm to 200 nm, preferably 50 nm to 150 nm, more preferably 60 nm to 120 nm. By setting such an average particle diameter, 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 obtained, for example, by measuring the dispersion using a laser light scattering method.

Examples of the 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 is preferable. In addition, the pigment dispersion using a sand mill is preferably prepared by using beads having a small diameter (0.01 mm to 1 mm diameter) and increasing the dispersion efficiency by increasing the filling rate of the beads. .
By dispersing under such conditions, the pigment particle size can be reduced, and a dispersion having good dispersibility can be obtained.
It is also preferable to remove the solid component having a large particle size from the prepared dispersion by a method selected from filtration and centrifugation.
Further, when foaming is severe in the preparation of the dispersion, an extremely small amount of an antifoaming agent such as silicone or acetylene glycol can be added. However, since there are antifoaming agents that inhibit pigment dispersion and micronization, it is preferable to select the type of antifoaming agent as appropriate.

[Urethane resin]
The urethane resin is often marketed 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 Kasei Co., Ltd.), Hydran WLS-201, 210, HW-312B Latex. (Above, manufactured by DIC Corporation), Superflex 150, 170, 470 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like. Many of them are emulsions containing 30-60% solids.
Of these, polycarbonate urethane resin is preferred. Specific examples of such a resin include, for example, Permarin UA-310, 3945; U-coat UX-320, among which U-coat UX-320 is preferable.

[Water-soluble organic solvent]
Examples of the water-soluble organic solvent include C1-C4 monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; ethylene glycol, propylene glycol, 1, C2-C6 alkanes such as 3-propanediol, 1,2- or 1,4-butanediol, 1,3-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol Diol; C3-C6 alkanetriol such as glycerin, hexane-1,2,6-triol, trimethylolpropane; carboxylic acid amide such as N, N-dimethylformamide, N, N-dimethylacetamide; 2-pyrrolidone, N- Methyl-2-pyrrolidone, 1,3-dimethyli Heterocyclic ureas such as dazolidin-2-one and 1,3-dimethylhexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone and 2-methyl-2-hydroxypentan-4-one; Linear or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; di- or tri-C2-C3 alkylene glycols or thioglycols such as diethylene glycol, triethylene glycol, dipropylene glycol and thiodiglycol; tetraethylene glycol, polyethylene Poly C2-C3 alkylene glycol having a repeating unit of 4 or more and a molecular weight of about 20000 or less, such as glycol (preferably having a molecular weight of 2000, 2000, 1540, etc.) or polypropylene glycol. (Preferably in liquid form); polyglyceryl ethers such as diglycerin, triglycerin and polyglycerin; polyglycerin alkylene oxide adducts; polyoxyC2-C3 alkylene polyglyceryl ethers such as polyoxyethylene 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), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, etc. C1-C4 alkylate of polyhydric alcohol Γ-butyrolactone, cyclic esters or carbonates such as ethylene carbonate; dimethyl sulfoxide; acetic acid and the like.

The ink has at least three kinds of water-soluble organic compounds, two kinds of C2-C6 alkanediol having a boiling point of 200 ° C. ± 15 ° C. and C3-C6 alkanetriol having a boiling point of 300 ° C. ± 15 ° C. Contains solvent. Examples of such alkanediols include ethylene glycol and propylene glycol; and examples of such alkanetriols include glycerin.
The total content of these two types of C2-C6 alkanediol and C3-C6 alkanetriol in the total mass of the ink is usually 10 to 45%, preferably 20 to 45%, more preferably 30 to 40%. It is.
The content ratio of these two types of C2-C6 alkanediol and C3-C6 alkanetriol is usually 5/1 to 2/1, preferably 4/1 to 3/1, more preferably 3/1 to 2. .5 / 1.

The ink preferably further contains a polyglycerol alkylene oxide adduct, preferably a diglycerol C2-C4 alkylene adduct. Examples of the diglycerin C2-C4 alkylene adduct include SC-P400, SC-P750, SC-P1000, SC-P1200, SC-P1600; SC-E450, SC-E750, SC- manufactured by Sakamoto Pharmaceutical Co., Ltd. E1000, SC-E1500, SC-E2000, SC-E3000, SC-E4500; Unilube DGP-700, DGP-700F manufactured by NOF Corporation;
The content of the polyglycerol alkylene oxide adduct in the total mass of the ink is usually about 0.5% to 2.5%, preferably about 1% to 2%.

[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 A polyglycol ether type (for example, TergItol-S-7 manufactured by SIGMA-ALDRICH) and the like. Of these, acetylene glycol surfactants are preferred.
Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,4,7,9-tetramethyl-5-decyne-4,7- Preferred are surfactants selected from diols, 2,4-dimethyl-5-decyn-4-ol, and 2,4-dimethyl-5-decyn-4-ol or their alkylene oxide adducts. Examples of the alkylene oxide include C2-C4 linear, branched, and cyclic alkylene oxides. Of these, linear or branched alkylene oxides are preferred.
Examples of such surfactants include Olfin series (104, E1010, etc.) manufactured by Air Products, and Surfynol series (420, 440, 465, 61, etc.) manufactured by Nissin Chemical Industry Co., Ltd.

Examples of the content of each component in the total mass of the ink include the following ranges.
Pigment: Usually 1 to 15%, preferably 1 to 10%, more preferably 1 to 7%.
Dispersant: 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 20 to 45%, more preferably 30 to 40%.
Nonionic surfactant: Usually 0.01 to 5%, preferably 0.05 to 3%, more preferably 0.1 to 2.5%.
The remainder other than the above is water.

  As said water, what has little content of impurities, such as various metal ions and an inorganic substance, is preferable. Examples of such water include ion exchange water.

  There is no restriction | limiting in particular in the preparation method of the said ink, A well-known method can be used. As an example, after preparing an aqueous pigment dispersion containing a pigment and a dispersant, there is a method of adding and mixing a urethane resin, a water-soluble organic solvent, a nonionic surfactant, and other components as necessary. Can be mentioned.

  The ink can further contain an ink preparation agent other than those described above, if necessary. 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 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.

  The ink-jet printing method is a method in which ink droplets are ejected according to a recording signal and adhered 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 above-mentioned 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 above fiber may be a single material fiber or a blended 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 baking.
As the baking (thermosol) treatment, the dyeing can be performed by a treatment of usually 130 to 250 ° C., preferably 170 to 210 ° C., usually 10 seconds to 30 minutes, preferably 60 to 180 seconds. This method is sometimes called dry heat fixing.
In this way, a dyed product dyed by the inkjet dyeing method is obtained. The dyed product means a recording material dyed by the ink jet dyeing method.

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

Of all the components described above, one of them can be used alone, or two or more of them can be used in combination.
About all the above-mentioned matters, a combination of preferable ones is more preferable, and a combination of more preferable ones is further preferable. The same applies to combinations of preferable and more preferable, combinations of more preferable and more preferable.

The ink described above has good ink filling into the ink jet head, and can perform stable ejection without bending or rubbing during printing. In addition, it is possible to perform good discharge without clogging the nozzles, both when discharging continuously and when discharging intermittently.
Further, the storage stability during storage is good, and the redispersibility is very good even when the ink has been dried by losing moisture or the like in the ink.
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.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the examples.
“Water” used in the examples is ion-exchanged water.
In Examples, when it was necessary to measure the content of the colorant in the dispersion, it was determined by a dry weight method using MS-70 manufactured by A & D Corporation. The content of the colorant is the content of only the colorant converted from the total content of solids contained in the dispersion.
When ink jet recording was necessary, an industrial ink jet evaluation apparatus (expandable coating apparatus EV2500: manufactured by Ricoh Co., Ltd.) was used.

[Synthesis Example 1]: Synthesis of a dispersant.
According to “[Synthesis Example 3] Synthesis of Block Copolymer A” of International Publication No. 2013/115071, 138 g of a dispersant having an Mw of 24,300 and a PDI of 1.49 was obtained. In the obtained dispersant, the monomer constituting the A block is benzyl methacrylate, the monomer constituting the B block is a monomer represented by the formula (2), R ₁ is a hydrogen atom, and R ₂ is a methyl group And a monomer in which R ₁ is an n-butyl group as a C4 alkyl group and R ₂ is a methyl group.

[Preparation Example 1]: Preparation of a dispersion containing a colorant.
The dispersant (6.3 parts) obtained in Synthesis Example 1 was dissolved in 2-butanone (20 parts) to obtain a solution. To this solution, a solution obtained by dissolving 0.47 parts of sodium hydroxide in water (51.45 parts) was added and stirred for 1 hour to obtain an emulsion. To the resulting liquid, C.I. I. Pigment Yellow 155 (21 parts) was added, and the mixture was dispersed with a sand grinder for 15 hours under water cooling to obtain a liquid. The obtained liquid was diluted with ion exchange water, and the beads for dispersion were separated by filtration to obtain a filtrate. This separation was performed in a two-ply manner so that the glass filter paper GA100 manufactured by Advantech was on top and GC50 was on the bottom. A 2-butanone and a part of water in the obtained filtrate were distilled off under reduced pressure with an evaporator to obtain a dispersion having a colorant content of 12%. This is referred to as “DP1”.

[Preparation Examples 2 to 4] Preparation of a dispersion containing a colorant.
DP2 to DP4, which are dispersions of Preparation Examples 2 to 4, were prepared in the same manner as Preparation Example 1 except that the components used in Preparation Example 1 were replaced with the components and amounts used in Table 1 below. Obtained. In addition, the numerical value of each component is “parts”, and the amount of water added was adjusted so that the total content of the colorant in each dispersion was 12%.

Abbreviations and the like in Table 1 below represent the following meanings.
PY155 = C.I. I. Pigment Yellow 155.
PR122 = C. I. Pigment Red 122.
PB15: 4 = C. I. Pigment Blue 15: 4.
CB = carbon black.
Dp = Dispersant prepared in Preparation Example 1 above.
MEK = 2-butanone.
NaOH = sodium hydroxide.

[Examples 1-4]: Preparation of ink.
After mixing each component of Table 2 below and stirring sufficiently, the ink of Examples 1-4 used for an evaluation test was obtained by filtering with a 5-micrometer membrane filter. The numerical value of each component is “parts”, and the amount of water added was adjusted so that the total was 100 parts.

Abbreviations in Table 2 below have the following meanings.
UX320 = Yukot UX-320 (solid content 40%).
PG = propylene glycol.
GL = glycerin.
EG = ethylene glycol.
DGA = SC-P1000.
TEA = triethanolamine.
SF420 = Surfinol 420.
SF104 = Surfinol 104PG50.
DF110 = Surfinol DF-110D.
GXL = Proxel GXL (S).

[Preparation Example 5]: Preparation of fiber for evaluation test.
In order to prepare a fiber having a solid color image, a 100% cotton T-shirt (Toms Heavyweight, white fabric) was used. Each of the inks of Examples 1 to 4 was printed on this fiber using an industrial inkjet evaluation apparatus (expandable coating apparatus EV2500: manufactured by Ricoh Co., Ltd.). The printing condition is 1 pass (100% solid) and 2 passes (200% solid) at a head temperature of 25 ° C. and a resolution of 600 × 600 dpi. Subsequently, the fiber to which the ink was adhered was subjected to a heat treatment at 170 ° C. for 1 minute using a heat press machine to obtain an evaluation test fiber to which the ink of Examples 1 to 4 was adhered.

[Color measurement conditions]
When color measurement is necessary for the fiber for the evaluation test obtained as described above, an X-Rite colorimeter, Gretag Macbeth Spectrolino is used, the observation light source is D65, the observation field is 2 °, The color was measured under the condition that the density was ANSI T. Further, the colorimetry was performed using the CIE / L * a * b * color system.

[Print density evaluation test]
Density values were measured for the fibers for the evaluation test. The larger the Density value, the higher the print density and the better the color developability. The evaluation results are shown in Table 2 above.

  According to the present invention, there is no need for pretreatment ink or white ink on a white background fiber, and even when only a color ink is used, a pigment ink capable of obtaining an image having high color developability, and a fiber using the same We could provide printing method. For this reason, the ink of the present invention is extremely useful as an ink for various types of recording, particularly for inkjet recording, particularly for inkjet textile printing.

Claims (10)

An ink containing a pigment, a dispersant, a urethane resin, a water-soluble organic solvent, a nonionic surfactant, and water,
An ink containing at least two types of C2-C6 alkanediol having a boiling point of 200 ° C. ± 15 ° C. and C3-C6 alkanetriol having a boiling point of 300 ° C. ± 15 ° C. as the water-soluble organic solvent. The dispersant is 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 an organic tellurium represented by the following formula (1) as a polymerization initiator. A polymer obtained by copolymerizing by a living radical polymerization method using any one of a mixture of a compound, an azo polymerization initiator and an organic ditellurium compound represented by the following formula (2), wherein A and B are different from each other The AB block polymer is a monomer that constitutes the A block is one or more monomers represented by the following formula (3), and the monomer that constitutes the B block is selected from benzyl methacrylate and benzyl acrylate The ink according to claim 1, wherein the ink is one or more monomers.

(In the above 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 above formula (2), _{R 1} represents the same meaning as _{R 1} in the formula (1).)

(In the above 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, dispersant, urethane resin, water-soluble organic solvent, and nonionic surfactant in the total mass of the ink is 1 to 15% by mass, 0.1 to 15% by mass, and 1 to 20% by mass, respectively. 10 to 45 mass%, 0.01 to 5 mass%, and the remainder is water.   The ink according to claim 1 or 3, wherein the urethane resin is a polycarbonate-based urethane resin.   The ink according to claim 1 or 3, wherein the water-soluble organic solvent further contains an alkylene oxide adduct of polyglycerol.   An ink-jet printing method in which printing is performed by ejecting the ink droplets according to any one of claims 1 to 5 in accordance with a recording signal and attaching the ink droplets to a recording material.   7. The recording material according to claim 6, wherein the recording material is a fiber selected from the group consisting of polyester, cellulose, polyamide, and natural fiber, a blended fiber containing these fibers, or a fabric containing these fibers. Inkjet printing method.   8. An ink jet dyeing method for dyeing a recording material printed by the ink jet textile printing method according to claim 6 or 7 by baking.   The inkjet dyeing | staining method of Claim 8 whose process temperature of the said baking process is 130-250 degreeC, and process time is 10 second-30 minutes.   A dyed product dyed by the ink jet dyeing method according to claim 8 or 9.