JP7340903B2 - Colored dispersions, inkjet printing inks, ink sets, printed hydrophobic fibers, and methods for printing hydrophobic fibers. - Google Patents

Description

The present invention relates to a colored dispersion, an inkjet printing ink, an ink set, printed hydrophobic fibers, and a method for printing hydrophobic fibers.

As information becomes more digitalized, inkjet printing has become widely used as office and home printing machines, but in recent years it has also been increasingly applied to commercial printing, textile printing, etc. As the uses for inkjet printing have expanded, the coloring materials used in ink have also varied depending on the application, from traditional water-soluble dyes such as acid dyes and direct dyes to water-insoluble colorants such as disperse dyes and pigments. Coloring materials have come to be used.

On the other hand, disperse dyes are widely used for industrial dyeing of hydrophobic fibers such as polyester, and are used for dyeing by dispersing water-insoluble dyes in a dye bath or color paste. Under high temperature conditions, the dye permeates and diffuses into the fiber, and is dyed due to hydrogen bonds and intermolecular forces between the fiber dyes. If the dispersibility of the dye, especially the dispersibility at high temperatures, is poor, the dye will aggregate in the high-temperature dye bath, which will easily cause specks on the fiber.

Inkjet printing of polyester fibers using disperse dyes has also been carried out (for example, see Non-Patent Document 1 and Non-Patent Document 2), which is mainly done by applying (printing) dye ink to the fibers and then heat-treating the fibers by steaming or other heat treatment. The direct printing method, in which the dye is dyed, and the thermal transfer printing method, in which dye ink is applied (printed) to an intermediate recording medium (dedicated transfer paper), and then the dye is sublimated and transferred from the intermediate recording medium side to the fiber side using heat. has been made into

Colored dispersions, which are the coloring components of the disperse dye inks used in these prints, are dispersed by dispersing water-insoluble or poorly soluble disperse dyes that have been ground to a size of several tens of nanometers to submicrons using a bead mill in the dispersion process. Disperse it in an aqueous solvent using an agent. A dispersant is required in order to maintain a good dispersion state without causing the disperse dye to precipitate in an aqueous solvent or producing foreign matter derived from the disperse dye. In recent years, there has been a strong demand for improved storage stability of inks using disperse dyes. To this end, improved storage stability and ink-forming resistance of the colored dispersion, which is the colored component, are required. Inking resistance means that when a component other than the colored dispersion used in the ink is added to the colored dispersion, the shock caused by the addition of a component with a polarity different from that of the colored dispersion causes a significant drop in dispersion stability. say to decline.

As dispersants for disperse dyes, anionic dispersants (for example, see Patent Document 1 and Patent Document 2) and ethylene oxide adducts of linear alkyls (for example, Patent Document 3) have been used, but coloring None of the dispersions and ink compositions had satisfactory sedimentation stability, storage stability, and ejection stability of the ink composition from a printer. In addition to these, dispersants such as naphthalenesulfonic acid and ligninsulfonic acid are also used. These dispersants have been used as dispersants by sulfonating coal-derived compounds such as naphthalene, anthracene, and phenanthrene, forming formalin condensates with formaldehyde, and polymerizing them (see Patent Document 1). Currently, ink storage stability, color dispersion liquid storage stability, and ink-forming resistance that are required to achieve the ink life that has been required in recent years cannot be met.

However, it is difficult to control various polarity values with such dispersants whose polymeric constituent unit is only sulfonation, and it is difficult to control disperse dyes with various polarity values under long-term high-temperature storage. It was difficult to maintain sufficient dispersion stability in the case of exposure.

In Patent Document 5, by combining a plurality of dispersants having a desired polarity (retention time) to cover the range of polarity (retention time) of the disperse dye, the dispersion is stabilized when exposed to high temperature storage for a long period of time. Although studies have been made to improve sexual performance, it is still insufficient to improve life, which has been strongly desired in recent years.

Japanese Patent Application Publication No. 9-291235 Japanese Patent Application Publication No. 8-333531 Japanese Patent Application Publication No. 2003-246954 Japanese Patent Application Publication No. 8-291266 Japanese Patent Application Publication No. 2018-154790

Journal of the Imaging Society of Japan Vol. 41 No. 2 No. 68-74 (2002) Senori Keizai Shimbun January 28, 2004 issue, pages 18-21

The object of the present invention is to provide a colored dispersion having excellent initial particle size and particle size over time, an inkjet printing ink with excellent storage stability, an ink set, printed hydrophobic fibers, and a method for printing hydrophobic fibers. It is about providing.

As a result of extensive research, the present inventors have found that a colored dispersion containing a water-insoluble colorant, a dispersant having a specific structure, and water, and containing one or more of the above-mentioned dispersants, solves the above problems. This discovery led to the present invention.

That is, the present invention relates to 1) to 21).
1)
Contains a water-insoluble colorant, a dispersant, and water,
A colored dispersion liquid, wherein the dispersant contains one or more compounds represented by the following formula (1).

In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms. n represents an integer from 1 to 500. M each independently represents hydrogen, a metal ion, or an ammonium ion.
2)
The colored dispersion according to 1), wherein the water-insoluble colorant is a water-insoluble dye.
3)
The colored dispersion according to 2), wherein the water-insoluble dye is a disperse dye.
4)
The colored dispersion according to 3), wherein the disperse dye is at least one type of disperse dye selected from a disperse dye having a coumarin skeleton, a disperse dye having an azo skeleton, and a disperse dye having an anthraquinone skeleton.
5)
The colored dispersion according to 3), wherein the disperse dye is a disperse dye having a coumarin skeleton.
6)
The colored dispersion according to 5), wherein the disperse dye having a coumarin skeleton is a disperse dye represented by the following formula (2).

In formula (2), R ³ represents a substituent. m represents an integer from 0 to 3.
7)
The disperse dye represented by the above formula (2) is C.I. I. The colored dispersion according to 6), which is Disperse Yellow 232.
8)
The colored dispersion according to 3), wherein the disperse dye is a disperse dye having an azo skeleton.
9)
The colored dispersion according to 8), wherein the disperse dye having an azo skeleton is a disperse dye represented by the following formula (3).

In formula (3), R ⁴ represents a substituent. n represents an integer from 0 to 6.
10)
The disperse dye represented by the above formula (3) is C.I. I. The colored dispersion according to 9), which is Disperse Orange 25.
11)
The colored dispersion according to 3), wherein the disperse dye is a disperse dye having an anthraquinone skeleton.
12)
11) The colored dispersion according to 11), wherein the disperse dye having an anthraquinone skeleton is a dye represented by the following formula (4).

In formula (4), R ⁵ represents a substituent. p represents an integer from 0 to 6.
13)
The disperse dye represented by the above formula (4) is C.I. I. The colored dispersion according to 12), which is Disperse Red 60.
14)
The colored dispersion according to any one of 1) to 13), further comprising an anionic dispersant.
15)
14) The colored dispersion according to 14), wherein the anionic dispersant is a sodium naphthalene sulfonate formalin condensate.
16)
15) The colored dispersion according to 15), wherein the sodium naphthalene sulfonate formalin condensate is a formalin condensate of creosote oil sulfonic acid.
17)
The colored dispersion according to any one of 1) to 16), further comprising a phytosterol compound.
18)
An ink for inkjet textile printing, comprising the colored dispersion according to any one of 1) to 17).
19)
18) An ink set comprising the inkjet textile printing ink described in item 18) and at least one ink selected from the group consisting of yellow ink, magenta ink, and cyan ink.
20)
A hydrophobic fiber printed using the inkjet textile printing ink described in 18) or the ink set described in 19).
21)
Step A in which the inkjet textile printing ink described in 18) or the ink set described in 19) is applied to the hydrophobic fiber by an inkjet printer, and in the droplets of the ink composition deposited in step A. A method for printing hydrophobic fibers, comprising a step B of fixing the colorant to the fibers by heat, and a step C of washing the unfixed colorant remaining in the fibers.

According to the present invention, a colored dispersion having an excellent initial particle size and a particle size over time, an inkjet printing ink having excellent storage stability, an ink set, a hydrophobic fiber printed using the ink set, and a hydrophobic A method for printing fibers can be provided.

The present invention will be explained in detail below.

(Colored dispersion)
The colored dispersion of the present invention contains at least a water-insoluble colorant, a dispersant, and water, and the dispersant contains one or more compounds represented by the above formula (1). By including one or more compounds represented by the above formula (1) as a dispersant, the initial dispersibility (initial particle size) and storage stability (particle size over time) of the colored dispersion can be improved.

In the above formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group include straight chain alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, and n-octyl group, branched chain groups such as isopropyl group, sec-butyl group, and tert-butyl group. Examples include cyclic alkyl groups such as alkyl groups, cyclobutyl groups, and cyclohexyl groups, preferably linear alkyl groups having 1 to 5 carbon atoms, and more preferably linear alkyl groups having 1 to 4 carbon atoms. .

In the above formula (1), n represents an integer from 1 to 500, preferably from 1 to 300, more preferably from 1 to 150, particularly preferably from 1 to 100, and from 1 to 75. It is particularly preferable that the number be 1, and it is extremely preferable that the number be 1 to 70. Further, the compounds represented by the above formula (1) may be used alone or in combination of two or more.

In the above formula (1), M each independently represents hydrogen, a metal ion, or an ammonium ion, and each M may be the same or different. For example, when M is hydrogen, it becomes sulfonic acid (-SO ₃ H).

Examples of the metal ions include sodium ions, potassium ions, calcium ions, magnesium ions, etc., and sodium ions are preferred. When M is a sodium ion, it becomes sulfonic acid sodium salt (-SO ₃ Na).

Examples of the ammonium ion include ammonium ion, methylammonium ion, dimethylammonium ion, trimethylammonium ion, tetramethylammonium ion, and tetra-n-butylammonium ion.

As the compound represented by the above formula (1), a commercially available compound or a synthesized compound may be used. Examples of commercially available compounds include Molwet (registered trademark) D-425. Powder, Molwet (registered trademark) D-400 powder, Molwet (registered trademark) D-809 powder (manufactured by Lion Akzo Co., Ltd.), Polity (registered trademark) N-100K (manufactured by Lion Corporation), Supragil (registered trademark) MNS/90, Supragil (registered trademark) RM/210-EI (manufactured by Rhodia Nicca Co., Ltd.), and the like. The compound represented by the above formula (1) can be used alone or in combination.
The above Molwet (registered trademark) D-425 powder is a mixture containing a plurality of compounds represented by the above formula (1), where n is an integer of 1 to 67.

The method for synthesizing the compound represented by the above formula (1) is not particularly limited, but includes, for example, an aromatic compound having a substituent such as a sulfo group, an alkyl group having 1 to 6 carbon atoms, and salts thereof. For example, there is a method including a step of adding formaldehyde to the aromatic compound and polymerizing the aromatic compound with formaldehyde.

^The amount of formaldehyde ^used is not particularly limited. ) can be set at 0.5 to 1.5 mol per 1 mol in total.

The reaction temperature for polymerization using formaldehyde is not particularly limited, but can be, for example, 90 to 100°C. Further, the addition time of formaldehyde is not particularly limited, but can be, for example, 2 to 3 hours. Furthermore, the reaction time is not particularly limited, and can be, for example, about 10 hours.

The method for recovering and purifying the dispersant after the reaction is not particularly limited, and for example, a method of removing unreacted components and solvent under reduced pressure, and other known purification methods can be used.

(Dispersant that can be used in combination)
The dispersant represented by the above formula (1) and a dispersant other than the dispersant represented by the above formula (1) can also be used together. The mass ratio of the total amount of dispersant to the disperse dye (total amount of dispersant/disperse dye) is preferably in the range of 1/10 to 10, more preferably 1/5 to 5, and even more preferably 1/5 to 3. . By being within the above range, the effect of improving the affinity for both the disperse dye and the solvent is appropriately exhibited, and the dispersion stability of the disperse dye tends to be further improved even when exposed to high temperature storage for a long period of time.

Further, the total amount of dispersant in the colored dispersion is preferably 1 to 120% by mass, more preferably 10 to 100% by mass, and even more preferably 20 to 80% by mass, based on the total amount of water-insoluble colorant. %.

The dispersant other than the dispersant represented by the above formula (1) is not particularly limited as long as it is a substance capable of dispersing the water-insoluble colorant and the dye contained in the ink for inkjet textile printing. Examples of such substances include known dispersants, surfactants, resin dispersants, and the like. Further, the dispersant and the surfactant differ only in their names, and may specifically refer to the same substance. Examples of the dispersant include anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, and the like. These dispersants can be used alone or in combination. Among these, at least one type of dispersant selected from an anionic dispersant and a nonionic dispersant is preferable, it is more preferable to include an anionic dispersant, and it is especially preferable to include an anionic dispersant and a nonionic dispersant, respectively. .

Examples of anionic dispersants include formalin condensates of polymeric sulfonic acids, preferably aromatic sulfonic acids, ligninsulfonic acids, formalin condensates of ligninsulfonic acids, salts thereof, or mixtures thereof (hereinafter, unless otherwise specified). Unless otherwise specified, the term "formalin condensate of sulfonic acid" is intended to include "salts thereof, or mixtures thereof.") etc. are preferred. Examples of "these salts" include salts such as sodium salts, potassium salts, and lithium salts. Formalin condensates of aromatic sulfonic acids include, for example, creosote oil sulfonic acid; cresol sulfonic acid; phenolsulfonic acid; β-naphthalene sulfonic acid; β-naphthol sulfonic acid; β-naphthalene sulfonic acid and β-naphthol sulfonic acid. Formalin condensates such as cresolsulfonic acid and 2-naphthol-6-sulfonic acid; ligninsulfonic acid; Among these, formalin condensates of creosote oil sulfonic acid; β-naphthalene sulfonic acid; and lignin sulfonic acid are preferred. These are commercially available under various trade names. As an example, Demol N is a formalin condensate of β-naphthalene sulfonic acid; Demol C is a formalin condensate of creosote oil sulfonic acid; Demol SN-B is a formalin condensate of special aromatic sulfonic acid (both are (manufactured by Kao Corporation); and the like. Examples of the formalin condensate of creosote oil sulfonic acid include the Lavelin W series; examples of the formalin condensate of methylnaphthalene sulfonic acid include the Lavelin AN series (both manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); and the like. Among these, Demol N, Lavelin AN series, and Lavelin W series are preferred, Demol N and Lavelin W are more preferred, and Lavelin W is even more preferred. Examples of the lignin sulfonic acid include Vanillex N, Vanillex RN, Vanillex G, and Pearlex DP (all manufactured by Nippon Paper Industries Co., Ltd.). Among these, Vanillex RN, Vanillex N, and Vanillex G are preferred.

Examples of nonionic dispersants include alkylene oxide adducts of phytosterols, alkylene oxide adducts of cholestanols, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxy Examples include ethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxypropylene block polymer, and substituted derivatives thereof. Among these, alkylene oxide adducts of phytosterols and alkylene oxide adducts of cholestanols are preferred. As the alkylene oxide adduct of phytosterols, C2-C4 alkylene oxide adducts of phytosterols are preferred, and ethylene oxide adducts are more preferred. In the present specification, the term "phytosterols" includes both phytosterols and/or hydrogenated phytosterols. For example, examples of ethylene oxide adducts of phytosterols include ethylene oxide adducts of phytosterols and/or ethylene oxide adducts of hydrogenated phytosterols. As the alkylene oxide adduct of cholestanols, C2-C4 alkylene oxide adducts of cholestanols are preferred, and ethylene oxide adducts are more preferred. In the present specification, the term "cholestanols" includes both cholestanols and/or hydrogenated cholestanols. For example, examples of ethylene oxide adducts of cholestanols include ethylene oxide adducts of cholestanol and/or ethylene oxide adducts of hydrogenated cholestanol. The amount of alkylene oxide (preferably C2-C4 alkylene oxide, more preferably ethylene oxide) added per mole of phytosterols or cholestanols is about 10 to 50 moles, and the HLB is preferably about 13 to 20. Specific examples of these include, for example, NIKKOL BPS-20, NIKKOL BPS-30 (ethylene oxide adduct of phytosterol); NIKKOL BPSH-25 (ethylene oxide adduct of hydrogenated phytosterol); (ethylene oxide adduct of stanol); and the like.

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

Examples of amphoteric dispersants include carboxybetaines, sulfobetaines, aminocarboxylic acid salts, imidazolinium betaines, and the like.

Examples of the resin dispersant include copolymers that can be used as anionic dispersants. Preferred examples of the resin dispersant include a copolymer of a compound containing an aromatic hydrocarbon group and (meth)acrylic acid (ester); a copolymer of a compound containing an aromatic hydrocarbon group and (meth)acrylic acid (ester); , and a copolymer of maleic acid (anhydride). In this specification, "(meth)acrylic acid (ester)" includes acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester, and "(anhydrous)maleic acid" refers to anhydrous They are used to include maleic acid and maleic acid, respectively. As the copolymer of a compound containing an aromatic hydrocarbon group and (meth)acrylic acid (ester), a copolymer having a hydrophilic part and a hydrophobic part in the molecule is preferably mentioned. When copolymerizing a compound containing an aromatic hydrocarbon group and (meth)acrylic acid (ester), a single compound can be used as the latter, or a plurality of compounds can be used in combination. Additionally, when performing copolymerization, maleic acid (anhydride) may be added to form a copolymer of a compound containing an aromatic hydrocarbon group, (meth)acrylic acid (ester), and maleic acid (anhydride). can. In order to strengthen the interaction with the dye, it is preferable to use a compound containing an aromatic hydrocarbon group as the hydrophobic moiety contained in the molecule of the copolymer. The aromatic hydrocarbon group is preferably a phenyl group, a phenylene group, a naphthyl group, or a naphthalene-diyl group, more preferably a phenyl group or a phenylene group, and even more preferably a phenyl group. Specific examples of these copolymers include (α-methyl)styrene-acrylic acid copolymer, (α-methyl)styrene-acrylic acid-acrylic ester copolymer, and (α-methyl)styrene-methacrylic acid. copolymer, (α-methyl)styrene-methacrylic acid-acrylic acid ester copolymer, (α-methyl)styrene-(anhydrous) maleic acid copolymer, acrylic acid ester-(anhydrous) maleic acid copolymer, (α-methyl)styrene-acrylic acid ester-(anhydrous) maleic acid copolymer, acrylic acid ester-allylsulfonic acid ester copolymer, acrylic acid ester-styrene sulfonic acid copolymer, (α-methyl)styrene- Methacryl sulfonic acid copolymer, polyester-acrylic acid copolymer, polyester-acrylic acid-acrylic acid ester copolymer, polyester-methacrylic acid copolymer, polyester-methacrylic acid-acrylic acid copolymer ester; etc. It will be done. Among these, styrene compounds containing an aromatic hydrocarbon group are preferred. Note that (α-methyl)styrene is used herein to include α-methylstyrene and styrene. Specific examples of these copolymers include Joncryl 67, 68, 586, 611, 678, 680, 682, 683, and 690 manufactured by BASF. Among these, Jonkryl 68, 678, 682, 683, and 690 are preferred.

Examples of resin dispersants other than those mentioned above include styrene and its derivatives, vinylnaphthalene and its derivatives, aliphatic alcohol esters of α,β-ethylenically unsaturated carboxylic acids, acrylic acid and its derivatives, maleic acid and its derivatives, itacon, etc. At least two monomers (at least one of which is a hydrophilic or water-soluble monomer) selected from acids and derivatives thereof, fumaric acid and derivatives thereof, vinyl acetate, vinyl alcohol, vinylpyrrolidone, acrylamide, and derivatives thereof, etc. block copolymers, random copolymers, and graft copolymers, and/or salts thereof.

(Water-insoluble colorant)
The water-insoluble colorant used in the present invention is not particularly limited as long as it can be used as a water-insoluble colorant. For example, known disperse dyes, oil-soluble dyes, carbon black, organic pigments, etc. can be used, but water-insoluble dyes are preferably used, and disperse dyes are most preferably used.

Specifically, C. I. Disperse Yellow 3, 4, 5, 7, 8, 9, 13, 23, 24, 30, 33, 34, 39, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 186, 192, 198, 199, 200, 202, 204, 210, 211, 215, 216, 218, 224, 232, 237, C. I. Disperse Orange 1, 1:1, 3, 5, 7, 11, 13, 17, 20, 21, 23, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 60, 61, 66, 71, 73, 76, 78, 80, 86, 89, 90, 91, 93, 96, 97, 118, 119, 127, 130, 139, 142, C. I. Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 55:1, 56, 58, 59, 60, 65, 70, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 158, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 283, 288, 298, 302, 303, 310, 311, 312, 320, 323, 324, 328, 359, 364, C. I. Disperse Violet 1, 4, 8, 11, 17, 23, 26, 27, 28, 29, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77, 97, C. I. Disperse Green9,C. I. Disperse Brown 1, 2, 4, 9, 13, 19, C. I. Disperse Blue 3, 5, 7, 9, 14, 16, 19, 20, 26, 26:1, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 64:1, 71, 72, 72:1, 73, 75, 77, 79, 79:1, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 131, 139, 141, 142, 143, 145, 146, 148, 149, 153, 154, 158, 165, 165:1, 165:2, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 266, 267, 270, 281, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, 341, 353, 354, 358, 359, 360, 364, 365, 366, 368, C. I. Disperse Brack 1, 3, 10, 24, C. I. Solvent Yellow 114, C. I. Solvent Orange 67, C. I. Solvent Red 146, C. I. Solvent Blue 36, 63, 83, 105, 111, C. I. Reactive Yellow 2, 3, 18, 81, 84, 85, 95, 99, 102, C. I. Reactive Orange5, 9, 12, 13, 35, 45, 99, C. I. Reactive Brown 2, 8, 9, 17, 33, C. I. Reactive Red 3, 3:1, 4, 13, 24, 29, 31, 33, 125, 151, 206, 218, 226, C. I. Reactive Violet 1, 24, C. I. Reactive Blue 2, 5, 10, 13, 14, 15, 15:1, 49, 63, 71, 72, 75, 162, 176, C. I. Reactive Green 5, 8, 19, C. I. Reactive Black 1, 8, 23, 39, C. I. Direct Yellow2, 3, 4, 9, 10, 11, 12, 13, 15, 16, 50, 66, 73, 84, 86, 87, 88, 89, 91, 110, 127, 128, 129, 130, 132 , 138, 139, 141, 142, 145, C. I. Direct Orange 20, 25, 35, 38, 39, 41, C. I. Direct Brown 187, 195, 196, 202, 208, 209, 210, 213, C. I. Direct Red 76, 88, 89, 92, 101, 209, 220, 222, 224, 225, 226, 227, 234, 235, 238, 240, 243, 245, 247, C. I. Direct Blue52, 55, 57, 76, 80, 84, 86, 87, 92, 102, 105, 106, 108, 110, 112, 197, 199, 200, 202, 205, 220, 231, 233, 235, 237 , 238, 240, 245, 248, 250, C. I. Direct Green 55, 57, 59, 60, 77, 80, 82, 90, C. I. Direct Black 12, 19, 20, 22, 23, 105, 107, 110, 112, 115, 117, 120, 125, 129, 132, 135, 136, etc., but are not limited to these. do not have.

The above pigments are white or colored powders that are insoluble in water, organic solvents, etc., and include organic pigments and inorganic pigments. In the present invention, the pigment may be an organic pigment or an inorganic pigment, but an organic pigment is preferable. Specifically, C. I. Pigment Yellow 74, 120, 128, 138, 151, 185, 217, C. I. Pigment Orange 13, 16, 34, 43, C. I. Pigment Red 122, 146, 148, C.I. I. Pigment Violet 19, 23, C. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, C. I. Pigment Green 7, 8, etc.
Note that in the present invention, dyes are more preferred.

The above-mentioned coloring material may be a dry coloring material in the form of a powder or lump, or a wet cake or slurry, and may contain a small amount of a dispersant such as a surfactant in order to suppress agglomeration of coloring material particles during or after coloring material synthesis. It may be something. These commercially available coloring materials come in grades for industrial dyeing, resin coloring, ink, toner, inkjet, etc., and they differ in manufacturing method, purity, pigment particle size, etc. In order to suppress agglomeration after pulverization, it is preferable that the colorant has smaller particles, and in view of the influence on dispersion stability and ink ejection accuracy, it is preferable to use a colorant that contains as few impurities as possible. As for dyes, it can be used as a coloring material for black by blending orange dyes and red dyes with blue dyes as the main dye. Further, a small amount of other water-insoluble coloring materials may be included within the range of color tone adjustment.

The above-mentioned water-insoluble colorant may be blended. For example, in preparing black ink, a blue water-insoluble colorant is mainly blended, an orange water-insoluble colorant, and a red water-insoluble colorant are suitably blended to obtain a black color. It can be used as a black water-insoluble colorant. Furthermore, a plurality of water-insoluble colorants may be blended for the purpose of finely adjusting the color tone, such as blue, orange, red, violet, or black, to a desired color tone.

The disperse dye is at least one type of disperse dye selected from disperse dyes having a coumarin skeleton, disperse dyes having an azo skeleton, disperse dyes having an anthraquinone skeleton, disperse dyes having a quinophthalone skeleton, and disperse dyes having a thioindigo skeleton. More preferably, at least one type of disperse dye is selected from disperse dyes having a coumarin skeleton, disperse dyes having an azo skeleton, and disperse dyes having an anthraquinone skeleton.

(Disperse dye with coumarin skeleton)
A preferable form of the disperse dye is a disperse dye having a coumarin skeleton and represented by the above formula (2).

In the above formula (2), R ³ represents a substituent, and m represents an integer of 0 to 3.

In the above formula (2), R ³ is, for example, a hydrogen atom, a cyano group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 6 to 24 carbon atoms. Examples include aromatic hydrocarbon groups, heterocyclic groups, substituted or unsubstituted amino groups, alkoxyl groups, and aryloxy groups. The alkyl group having 1 to 8 carbon atoms may be the same as those described in formula (1) above.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.

Examples of the aromatic hydrocarbon group having 6 to 24 carbon atoms include phenyl group, naphthyl group, biphenyl group, fluorescenyl group, anthracenyl group, and the like. Further, the aromatic hydrocarbon group having 6 to 24 carbon atoms may further have an arbitrary substituent.

Examples of the above-mentioned heterocyclic group include heterocyclic groups such as a thiophenyl group, a furan group, a pyridinyl group, a piperazinyl group, a thiazole group, a thiadiazole group, and an azole group. Moreover, the above-mentioned heterocyclic group may further have an arbitrary substituent.

Examples of the above-mentioned substituted or unsubstituted amino group include amino group, methylamino group, ethylamino group, phenylamino group, dimethylamino group, diethylamino group, diphenylamino group, methylphenylamino group, etc., and it must be a diethylamino group. is preferred. Further, among the above substituted amino groups, the substituted amino group may further have an arbitrary substituent.

Examples of the alkoxyl group include methoxy group, ethoxy group, propoxy group, n-butoxy group, sec-butoxy group, and tert-butoxy group. Further, the alkoxyl group may further have an arbitrary substituent.

Examples of the aryloxy group include a phenoxy group and a naphthoxy group. Moreover, the above-mentioned aryloxy group may further have an arbitrary substituent.

In the above formula (2), m is preferably 1 to 3, more preferably 2 to 3, and particularly preferably 2.

The disperse dye represented by the above formula (2) is C.I. I. Disperse Yellow 232 is highly preferred.

(Disperse dye with an azo skeleton)
A preferable form of the disperse dye is a disperse dye having an azo skeleton and represented by the above formula (3).

In the above formula (3), R ⁴ represents a substituent, and n represents an integer of 0 to 6.

In the above formula (3), R ⁴ may be the same as R ³ described in the above formula (2), and is preferably a nitro group or a diethylamino group which may have a substituent; More preferably, it is a diethylamino group having one cyano group as a substituent.

In the above formula (3), n is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 2.

The disperse dye represented by the above formula (3) is C.I. I. Disperse Orange 25 is highly preferred.

(Disperse dye with anthraquinone skeleton)
A preferable form of the disperse dye is a disperse dye having an anthraquinone skeleton and represented by the above formula (4).

In the above formula (4), R ⁵ represents a substituent, and p represents an integer of 0 to 6.

In the above formula (4), R ⁵ may be the same as R ³ described in the above formula (2), and is preferably an amino group, a hydroxy group, or a phenoxy group.

In the above formula (4), p is preferably 1 to 4, more preferably 2 to 4, and particularly preferably 3.

The disperse dye represented by the above formula (4) is C.I. I. Disperse Red 60 is highly preferred.

As the disperse dye used in the above colored dispersion, C.I. I. Disperse Yellow 54, C. I. Disperse Yellow 232, C. I. Disperse Red 60, C. I. Disperse Red 364, C. I. Disperse Orange 25, C. I. Disperse Orange 60, C. I. Disperse Blue 359, C. I. Disperse Blue 360 is preferred.

The above coloring agents can be used alone or in combination, and can be mixed and adjusted depending on the purpose.

The total content of the dispersant (1) is preferably 1 to 120% by mass, more preferably 10 to 100% by mass, even more preferably 20 to 80% by mass, based on the total amount of the water-insoluble colorant. Mass%. Further, the colored dispersion liquid contains water.

(Other ingredients)
The colored dispersion liquid may further contain additives such as a preservative and antifoaming agent and an antifoaming agent, which will be described later, as other components.

(Ink for inkjet textile printing)
Inkjet textile printing inks containing the above colored dispersion are also included in the present invention. In addition to the above-mentioned colored dispersion, the inkjet textile printing ink may contain an ink preparation agent, if necessary. Examples of ink preparation agents include water-soluble organic solvents, preservatives, antifungal agents, pH adjusters, chelating reagents, rust preventives, ultraviolet absorbers, viscosity adjusters, dye solubilizers, antifading agents, surface tension adjusters, Known additives such as antifoaming agents and water may be used. Among these, the total content of water-soluble organic solvents is usually 0% to 60%, preferably 5% to 40%, more preferably 10% to 35%, even more preferably 10% to the total mass of the ink. % to 20%. The total content of ink preparation agents other than the water-soluble organic solvent is usually about 0 to 10%, preferably about 0.05 to 5%, based on the total mass of the ink.

Examples of water-soluble organic solvents include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; N,N-dimethylformamide, N,N - Amides such as dimethylacetamide; heterocyclics such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimid-2-one Ketones; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-Methyl-1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6- Mono-, oligo-, or polyalkylene glycol or thioglycol having C2-C6 alkylene units such as hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol; glycerin, hexane Polyols (preferably triols) such as -1,2,6-triol and trimethylolpropane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), C1-C4 monoalkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether; γ-butyrolactone; dimethyl sulfoxide and the like.

Examples of water-soluble organic solvents include substances that are solid at room temperature. In other words, substances that are water-soluble even if they are solid at room temperature, whose aqueous solutions contain the same properties as water-soluble organic solvents, and which can be used with the expectation of the same effects are: In this specification, it is referred to as a water-soluble organic solvent. Examples of such substances include solid polyhydric alcohols, sugars, and amino acids.

Examples of the preservative and fungicide include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, and 1-benzisothiazolin-3-one. Examples include amine salt of 3-one, Proxel GXL (S) manufactured by Arch Chemicals, and the like.

Any substance can be used as the pH adjuster as long as it can control the pH of the ink within the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. Examples of the pH adjuster include carbonates of Group 1 elements in the periodic table of elements such as lithium carbonate, sodium carbonate, and potassium carbonate; aminosulfonic acids such as taurine; and the like.

Examples of the chelating reagent include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.

Examples of the rust preventive include acidic sulfites, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and the like.

Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds. Further, compounds such as benzoxazole compounds that absorb ultraviolet rays and emit fluorescence, so-called fluorescent brighteners, etc. can also be used.

Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

Examples of dye-dissolving agents include urea, ε-caprolactam, and ethylene carbonate.

Antifading agents are used for the purpose of improving the storage stability of images. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Examples of the organic type include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of metal complex systems include nickel complexes and zinc complexes.

Examples of surface tension modifiers include surfactants. Examples of the types of surfactants include anionic, cationic, amphoteric, nonionic, silicone-based, and fluorine-based surfactants.

Examples of anionic surfactants include alkyl sulfocarboxylate; α-olefin sulfonate; polyoxyethylene alkyl ether acetate; N-acylamino acid or its salt; N-acylmethyl taurate; alkyl sulfate polyoxyalkyl ether Sulfate; alkyl sulfate polyoxyethylene alkyl ether phosphate; rosin acid soap; castor oil sulfate ester salt; lauryl alcohol sulfate ester salt; alkylphenol type phosphate; alkyl type phosphate ester; alkylaryl sulfonate; diethyl sulfosuccinic acid salts, sulfosuccinic acids such as diethylhexylsulfosuccinate, dioctylsulfosuccinate, and the like. Various types of these surfactants are commercially available. Examples include, for example, manufactured by Lion Corporation under the trade name Ripar 835I, 860K, 870P, NTD, MSC; manufactured by Adeka Corporation under the trade name ADEKA COL EC8600; manufactured by Kao Corporation under the trade name Perex OT-P. Same CS, same TA, same TR; Manufactured by New Japan Chemical Co., Ltd., RIKA MILD ES-100, ES-200, RIKA SURF P-10, RIKA SURF M-30, RIKA M-75, M-300, G- 30, G-600; manufactured by Toho Chemical Industry Co., Ltd., Succinol L-300, L-40, L-400, NL-400; and the like.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, etc. can be mentioned.

Examples of the nonionic surfactant include a formalin condensate of sodium naphthalene sulfonate, and a formalin condensate of creosote oil sulfonic acid is preferable. Examples of nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol Acetylene glycol (alcohol) type products such as Nissin Kagaku Co., Ltd., trade name Surfynol 104, 105, 82, 465, Olfine STG, etc.; Polyglycol ether type (e.g. Tergitol 15-S-7, manufactured by SIGMA-ALDRICH Co., Ltd.) ) etc.

Examples of the silicone surfactant include polyether-modified siloxane, polyether-modified polydimethylsiloxane, and the like. Specific examples of commercially available products include BYK-347 (polyether-modified siloxane); BYK-345 and BYK-348 (polyether-modified polydimethylsiloxane), both manufactured by BYK Chemie.

Examples of fluorine-based surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate compounds, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl ether groups in side chains. Examples include polyoxyalkylene ether polymer compounds. Specific examples of commercially available products include, for example, Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (manufactured by DuPont); PF-151N , PF-154N (manufactured by Omnova), etc.

Examples of antifoaming agents include highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based, and silicone-based compounds.

The above-mentioned inkjet textile printing ink contains water. The water used for preparing the ink is preferably one containing few impurities, such as ion-exchanged water or distilled water. Further, the prepared ink can be subjected to precision filtration using a membrane filter or the like. When using the above ink as an inkjet ink, it is preferable to perform precision filtration in order to prevent nozzle clogging. The pore size of the filter used for precision filtration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

The method for preparing the above-mentioned inkjet textile printing ink is not particularly limited, but includes, for example, a method of preparing a dispersion or solution of a colorant and then adding an ink preparation agent such as a water-soluble organic solvent. The method for preparing the aqueous dispersion of the colorant includes stirring and mixing the components constituting the dispersion using a sand mill (bead mill), roll mill, ball mill, paint shaker, ultrasonic dispersion machine, microfluidizer, etc. The following known methods can be mentioned. Foaming may occur when preparing colorant dispersions. For this reason, an antifoaming agent such as a silicone type or an acetylene alcohol type may be added at the time of preparing the dispersion, if necessary. However, since some antifoaming agents inhibit the dispersion and formation of fine particles of dyes, etc., it is preferable to use an antifoaming agent that does not affect the formation of fine particles or the stability of the dispersion. Preferred antifoaming agents include, for example, Olfine series (SK-14, etc.) manufactured by Nissin Chemical Industry Co., Ltd.; Surfynol series (104, DF-110D, etc.) manufactured by Air Products Japan Co., Ltd.; and the like. .

Examples of the method for preparing the above-mentioned ink for inkjet textile printing include a method of adding and mixing the above-mentioned aqueous dispersion, a water-soluble organic solvent, and, if necessary, an ink preparation agent. The order in which these are mixed is not particularly limited. These ink preparation agents may be added to the extent that they do not impede the effects of the present invention.

The content of the aqueous dispersion contained in the inkjet textile printing ink is usually 2 to 35%, preferably 3 to 30%, more preferably 3 to 30%, based on the total mass of the aqueous ink composition. It is 5-30%. Similarly, the content of the aqueous organic solvent is usually 10 to 50%, preferably 15 to 50%, more preferably 20 to 50%, even more preferably 30 to 50%. Similarly, the total content of ink conditioners is usually 0 to 25%, preferably 0.01 to 20%, based on the total mass of the aqueous ink composition.

The above-mentioned ink for inkjet textile printing preferably has a viscosity of usually about 3 to 20 mPa·s at 25° C. when measured with an E-type viscometer from the viewpoint of high-speed ejection response. Further, the surface tension is usually preferably in the range of 20 to 45 mN/m when measured by the plate method. In practice, it is preferable to adjust the physical property values to appropriate values in consideration of the ejection amount, response speed, ink droplet flight characteristics, etc. of the printer used.

(ink set)
An ink set of the above inkjet textile printing ink and other inks is also included in the present invention. The ink set of the ink for inkjet textile printing is preferably an ink set of ink of a different tone from the ink for inkjet textile printing, for example, the ink set for ink for inkjet textile printing, yellow ink, magenta ink, and cyan ink. and at least one ink selected from the group.

(hydrophobic fiber)
Hydrophobic fibers printed using the above-mentioned inkjet textile printing ink or the above-mentioned ink set are also included in the present invention. Specific examples of the hydrophobic fibers include resins such as polyester, nylon, triacetate, diacetate, and polyamide, and resins containing two or more of these resins. Examples of fibers containing hydrophobic resins include fibers made of the above-mentioned resins, and blended fibers of these fibers with recycled fibers such as rayon, and natural fibers such as cotton, silk, and wool. Contained in fibers containing synthetic resins. Some fibers are known to have an ink-receiving layer (bleeding prevention layer), and such fibers can also be used in the above-described printing method. Fibers having an ink-receiving layer can be prepared by known methods or can be obtained as commercially available products. The material, structure, etc. of the ink receiving layer are not particularly limited, and can be used as appropriate depending on the purpose. Specific examples of the fabric, which is a structure of fibers containing a hydrophobic resin, include satin, tropical, double pique, microfiber, and the like. Examples of films and sheets containing hydrophobic resins include PET films, PET sheets; fabrics coated with hydrophobic resins, glass, metals, ceramics, and the like. Note that "PET" means "polyethylene terephthalate."

(Hydrophobic fiber printing method)
The above-mentioned dyeing methods are methods for dyeing fibers or substances, and are broadly classified into two types. The first method is a fiber dyeing method called direct printing or direct textile printing. This method includes a step A in which droplets of the ink are attached to fibers containing a hydrophobic resin using an inkjet printer to form image information such as letters and designs on the fibers, and a step This method of dyeing fibers includes at least three steps: step B of fixing the dye in the droplets to the fibers by heat, and step C of washing the unfixed dye remaining in the fibers. Step B is generally performed by known steaming or baking. For example, steaming can be carried out using a high-temperature steamer, usually at 170 to 180 degrees Celsius, usually for about 10 minutes; or using a high-pressure steamer, usually at 120 to 130 degrees Celsius, usually for about 20 minutes; by treating the fibers, the dye is dyed onto the fibers. One method is to do so. Baking (thermosol) includes, for example, a method of dyeing the fibers by treating the fibers usually at 190° C. to 210° C., usually for about 60 seconds to 120 seconds. Step C is a step of washing the obtained fibers with warm water and, if necessary, with water. The hot water or water used for cleaning can contain a surfactant. It is also preferable to dry the washed fibers usually at 50 to 120°C for 5 to 30 minutes.

The above-described textile printing method may further include a fiber pretreatment step for the purpose of preventing bleeding and the like. This pretreatment step includes applying an aqueous solution containing at least one or more types of sizing materials and optionally an alkaline substance, a reduction inhibitor, and a hydrotropic agent to the fibers before the ink is attached. Can be mentioned. In the pretreatment step, it is preferable to use an aqueous solution of a pretreatment agent containing at least a sizing agent as the pretreatment liquid, and apply the fibers by coating or impregnating them with the pretreatment liquid.

Examples of the thickening agent include natural gums such as guar and locust bean, starches, sodium alginate, seaweeds such as Funori, plant skins such as pectic acid, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc. Examples include cellulose derivatives, modified starches such as carboxymethyl starch, and synthetic glues such as polyvinyl alcohol and polyacrylic acid esters. Preferred is sodium alginate.

Examples of the alkaline substances include alkali metal salts of inorganic or organic acids; salts of alkaline earth metals; and compounds that liberate alkali when heated; inorganic or organic alkali metal hydroxides and Alkali metal salts are preferred, including sodium compounds and potassium compounds. Specific examples include alkali metal hydroxides such as sodium hydroxide and calcium hydroxide; inorganic compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sodium phosphate. and alkali metal salts of organic compounds such as sodium formate and sodium trichloroacetate. Preferred is sodium hydrogen carbonate.

As the reduction inhibitor, sodium metanitrobenzenesulfonate is preferable. Examples of the hydrotropic agent include ureas such as urea and dimethylurea. Preferably it is urea.

Each of the above-mentioned thickening agent, alkaline substance, anti-reduction agent, and hydrotropic agent may be used as a single compound, or a plurality of compounds may be used in combination. The mixing ratio of each pretreatment agent in the total mass of the pretreatment liquid is, for example, 0.5 to 5% of the sizing agent, 0.5 to 5% of sodium bicarbonate, and 0 to 5% of sodium metanitrobenzenesulfonate. , 1 to 20% urea and the balance water. The pretreatment agent may be applied to the fibers by, for example, a padding method. The aperture ratio of the padding is preferably about 40 to 90%, more preferably about 60 to 80%.

The second method is called sublimation transfer printing, sublimation transfer dyeing, or the like. In this method, the ink droplets are attached to an intermediate recording medium using an inkjet printer to obtain an intermediate recording medium on which image information such as characters and patterns are recorded, and then the ink droplets on the intermediate recording medium are attached to the intermediate recording medium. By bringing the adhesion surface into contact with a substance selected from fibers, films, and sheets containing hydrophobic resins and heating them, the dye in the ink droplets adhering to the intermediate recording medium is sublimated and transferred to the fibers. This is a method of dyeing substances that is dyed using The intermediate recording medium is preferably one in which the dye in the ink droplets adhering to the intermediate recording medium does not aggregate on its surface and does not interfere with the sublimation of the dye during sublimation transfer. An example of such an intermediate recording medium is paper on the surface of which an ink-receiving layer is formed of inorganic fine particles such as silica, and special paper for inkjet recording can be used. As a heating method for transferring a recorded image from an intermediate recording medium to a fiber, a method of dry heat treatment usually at about 190 to 200° C. can be mentioned.

There are no particular restrictions on the above intermediate recording media, and the terminology for paper, paperboard, and pulp [JIS P 0001:1998 (confirmed in 2008, revised on March 20, 1998, published by the Japanese Standards Association)] , page 28 to page 47, "3. Classification f) Paper and paperboard varieties and processed products" (numbers 6001 to 6284. However, number 6235 "Oil-resistant") ”, 6263 “Flute, tier”, 6273 “Pulp molded product”, 6276 “Carbon paper”, 6277 “Multi-copy form paper”, 6278 “Back carbon foam paper”); and cellophane (hereinafter referred to as “paper/ Paperboard types and processed products; and "cellophane" are referred to as "paper, etc."). Among these papers, any paper that can be used for sublimation transfer can be used as an intermediate recording medium. Note that, as described above, when sublimation transfer is performed, heat treatment is usually performed at about 190° C. to 210° C. Therefore, among the above-mentioned intermediate recording media, those that are stable during heat treatment are preferred.

The above ink composition for inkjet textile printing can be used in various fields, but is suitable for aqueous writing ink, aqueous printing ink, information recording ink, textile printing, etc., and is particularly preferably used as an ink for inkjet textile printing.

According to the present invention, the color reproduction range can be expanded compared to conventional inkjet printing without using unlimited types and numbers of dyes as in conventional printing methods using colored pastes and the like.
The dispersion of the present invention does not cause solid aggregation or precipitation even when stored for a long period of time, and has good storage stability. In addition, there are very few changes in physical properties such as viscosity and average particle diameter.
Further, the ink composition of the present invention not only has excellent color development properties but also excellent various fastness properties such as light resistance, abrasion resistance, gas resistance, chlorine resistance, sweat resistance, and washing fastness.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the Examples. In the examples, unless otherwise specified, "part" means part by mass, and "%" means % by mass.
Furthermore, in the text and Table 1 below, Examples 2 to 4 shall be read as Reference Examples 1 to 3.

[Production Example 1 Synthesis of Dispersant 1]
According to the synthesis example described in JP 2018-154790, methylbenzenesulfonic acid and methylbenzene were mixed at an equimolar ratio (1:1) to prepare a mixture with a total of 1 mol. A 30% aqueous formalin solution was added dropwise to the prepared mixture under reflux conditions at 100° C. over 3 hours so that the amount of formalin added was 1 mol. Thereafter, a condensation reaction was carried out for 10 hours, and finally, unreacted components and water were removed under conditions of 0.5 atm and 150°C to obtain Dispersant 1.

[Production Example 2 Synthesis of Dispersant 2]
Dispersant 2 was prepared in the same manner as in Production Example 1, except that methylbenzenesulfonic acid and methylbenzene were mixed at a molar ratio (1:2) and the amount of formalin dropped was changed to 2 moles. Obtained.

[Production Example 3 Synthesis of Dispersant 3]
Dispersant 3 was prepared in the same manner as in Production Example 1, except that methylbenzenesulfonic acid and methylbenzene were mixed at a molar ratio (1:3) and the amount of formalin dropped was changed to 3 moles. Obtained.

[Production Example 4 Synthesis of Dispersant 4]
Methylbenzenesulfonic acid was added dropwise over 3 hours at 100° C. under reflux conditions so that the amount of formalin added was 1 mol per 1 mol. Thereafter, a condensation reaction was carried out for 10 hours, and finally, unreacted components and water were removed under conditions of 0.5 atm and 150° C. to obtain Dispersant 4.

[Examples 1 to 12] Preparation of Dispersions 1 to 12 Glass beads with a diameter of 0.2 mm were added to each component listed in Tables 1 to 2 below, and a dispersion treatment was performed for about 15 hours under water cooling in a sand mill. The resulting liquid was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC) to obtain colored dispersions each having a dye content of 15%. The obtained colored dispersions are referred to as dispersions 1 to 12, respectively.

[Comparative Examples 1 to 8] Preparation of Dispersions 14 to 21 Glass beads with a diameter of 0.2 mm were added to each component listed in Tables 3 to 4 below, and a dispersion treatment was performed for about 15 hours under water cooling in a sand mill. The resulting liquid was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC) to obtain colored dispersions of Preparation Examples 14 to 21, each having a dye content of 15%. The obtained colored dispersions are referred to as dispersions 14 to 21, respectively.

Abbreviations in Tables 1 to 4 below have the following meanings. DR60:C. I. Disperse Red 60
DY54:C. I. Disperse Yellow 54
DOR25:C. I. Disperse Orange 25
DOR60:C. I. Disperse Orange 60
DB359:C. I. Disperse Blue 359
DB360:C. I. Disperse Blue 360
DR364:C. I. Disperse Red 364
DY232:C. I. Disperse Yellow 232
Molwet D425: Molwet D-425 powder (manufactured by Lion Akzo Co., Ltd.)
Labelin W40: Labelin W40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
BPS-30: Nikkor BPS-30 (manufactured by Nikko Chemicals Co., Ltd.)
Surfynol 104: Surfynol 104 (manufactured by Air Products Japan Co., Ltd.)
Proxel GXL (S): Proxel GXL (S) (manufactured by Lonza)

<Evaluation of colored dispersion>
For the dispersions 1 to 12 and 14 to 21 obtained as described above, the initial particle diameter of the dispersion, the particle diameter of the dispersion over time, and the storage stability of the dispersion were evaluated using the evaluation methods described below.

<Initial particle size of dispersion>
Dispersions 1 to 12 and 14 to 21 of Examples and Comparative Examples in Tables 1 to 4 were each diluted 1000 times, and the volume average particle diameter (D50) was measured using Microtrack UPA (manufactured by Nikkiso Co., Ltd.). The value was taken as the initial particle size of the dispersion. The evaluation criteria are as follows. Rank 2 or lower is extremely difficult to put into practical use.
(Evaluation criteria)
Rank 5: The initial particle diameter of the dispersion liquid is less than 100 nm.
Rank 4: The initial particle diameter of the dispersion is 100 nm or more and less than 120 nm.
Rank 3: The initial particle diameter of the dispersion is 120 nm or more and less than 150 nm.
Rank 2: The initial particle size of the dispersion is 150 nm or more and less than 180 nm.
Rank 1: The initial particle size of the dispersion is 180 nm or more.

<Dispersion liquid particle size over time>
100 g of each of dispersions 1 to 12 and 14 to 21 of Examples and Comparative Examples in Tables 1 to 4 were sealed in a glass bottle and left at 60° C. for 14 days. After standing, dispersions 1 to 12 and 14 to 21 were each diluted 1000 times with water, and the volume average particle diameter (D50) was measured using Microtrac UPA (manufactured by Nikkiso Co., Ltd.). The particle size was defined as the liquid particle size over time.
The evaluation criteria are as follows. Rank 2 or lower is extremely difficult to put into practical use.
(Evaluation criteria)
Rank 5: The initial particle diameter of the dispersion liquid is less than 100 nm.
Rank 4: The initial particle diameter of the dispersion is 100 nm or more and less than 120 nm.
Rank 3: The initial particle diameter of the dispersion is 120 nm or more and less than 150 nm.
Rank 2: The initial particle size of the dispersion is 150 nm or more and less than 180 nm.
Rank 1: The initial particle size of the dispersion is 180 nm or more.

<Dispersion storage stability>
Dispersions 1 to 12 and 14 to 21 of Examples and Comparative Examples in Tables 1 to 4 were each diluted 10,000 times, and the absorbance at the maximum absorption wavelength between 400 nm and 780 nm was measured. Next, 100 g of each of Dispersions 1 to 12 and 14 to 21 was sealed in a glass bottle and left at 60° C. for 14 days. After standing, each of the obtained dispersions 1 to 12 and 14 to 21 was diluted 10,000 times, and the absorbance at the maximum absorption wavelength was similarly measured. Taking the absorbance before standing as 100%, the absorbance after standing was calculated, and the value was used to evaluate the storage stability of the dispersion. The evaluation criteria are as follows. Rank 2 or below is extremely difficult to put into practical use.
(Evaluation criteria)
Rank 5: Absorbance after standing is 95% or more.
Rank 4: Absorbance after standing is 90% or more and less than 95%.
Rank 3: Absorbance after standing is 80% or more and less than 90%.
Rank 2: Absorbance after standing is 60% or more and less than 80%.
Rank 1: Absorbance after standing is less than 60%.

From the results in Tables 1 to 4, it is clear that the dispersion of the present invention is a dispersion with excellent particle size stability over time and storage stability.

[Examples 14 to 25] Preparation of Inks 1 to 12 Inks 1 to 12 were obtained by mixing the components listed in Tables 5 to 6 below and stirring for approximately 30 minutes. Each of the obtained inks was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC) to prepare inks 1 to 12 for testing used in inkjet recording, each with a dye content of 5%.

[Comparative Examples 9 to 16] Preparation of Inks 14 to 21 Inks 14 to 21 were obtained by mixing the components listed in Tables 7 to 8 below and stirring for approximately 30 minutes. Each of the obtained inks was filtered through glass fiber filter paper GC-50 (manufactured by ADVANTEC) to prepare inks 14 to 21 for testing used in inkjet recording, each with a dye content of 5%.

The abbreviations in Tables 5 to 8 below have the following meanings: BYK348: Polyether modified polydimethylsiloxane BYK-348 (manufactured by BYK Chemie)
Gly: Glycerin TEGMME: Triethylene glycol monomethyl ether (Tokyo Kasei Kogyo Co., Ltd.)

<Ink evaluation>
Inks 1 to 12 and 14 to 21 obtained as described above were evaluated for ink storage stability using the evaluation method described below.

<Ink storage stability>
Inks 1 to 12 and 14 to 21 of Examples and Comparative Examples in Tables 5 to 8 were each diluted 10,000 times, and the absorbance at the maximum absorption wavelength in the range of 400 nm to 780 nm was measured. Next, 100 g of each of Inks 1 to 12 and 14 to 21 was sealed in a glass bottle and left at 60° C. for 14 days. After standing, each of the obtained inks 1 to 12 and 14 to 21 was diluted 10,000 times, and the absorbance at the maximum absorption wavelength was similarly measured. Taking the absorbance before standing as 100%, the absorbance after standing was calculated, and the ink storage stability was evaluated using that value. The evaluation criteria are as follows. Rank 2 or below is extremely difficult to put into practical use.
(Evaluation criteria)
Rank 5: Absorbance after standing is 95% or more.
Rank 4: Absorbance after standing is 90% or more and less than 95%.
Rank 3: Absorbance after standing is 80% or more and less than 90%.
Rank 2: Absorbance after standing is 60% or more and less than 80%.
Rank 1: Absorbance after standing is less than 60%.

From the results in Tables 5 to 8, it is clear that the ink of the present invention has excellent storage stability.

[Preparation of dyed fabric]
Using Inks 1 to 12 and 14 to 21 of each Example and Comparative Example, a solid pattern was printed on transfer paper, which is an intermediate recording medium, using an inkjet printer PX-105 (manufactured by Seiko Epson Corporation). The portion of the printed transfer paper to which the ink was attached was cut into a size of 35 cm x 40 cm. After overlapping the ink-attached surface of the cut transfer paper with a polyester cloth (Ponzi) of the same size, it was heated at 200°C for 60 seconds using a transfer press TP-600A2 manufactured by Taiyo Seiki Co., Ltd. When the transfer paper was heat-treated and sublimation transfer dyeing was performed on polyester cloth, the desired colors could be obtained.

The ink dispersion composition and aqueous ink composition of the present invention have high storage stability and are particularly useful as aqueous inkjet inks.

Claims (17)

Contains disperse dyes, dispersants, water, phytosterol compounds,
The dispersant contains one or more compounds represented by the following formula (1) and one or more anionic dispersants other than the compound represented by the following formula (1),
The total content of the compound represented by the following formula (1) is 10 to 100% by mass based on the total amount of disperse dye ,
Colored dispersion.

(In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms. n represents an integer of 1 to 500. M each independently represents hydrogen, metal ion, ammonium (Represents an ion.) The colored dispersion according to claim 1 , wherein the disperse dye is at least one type of disperse dye selected from a disperse dye having a coumarin skeleton, a disperse dye having an azo skeleton, and a disperse dye having an anthraquinone skeleton. The colored dispersion according to claim 2, wherein the disperse dye is a disperse dye having a coumarin skeleton. The colored dispersion according to claim 3, wherein the disperse dye having a coumarin skeleton is a disperse dye represented by the following formula (2).

(In formula (2), R ³ represents a substituent. m represents an integer from 0 to 3.) The disperse dye represented by the above formula (2) is C.I. I. The colored dispersion according to claim 4, which is Disperse Yellow 232. The colored dispersion according to claim 1, wherein the disperse dye is a disperse dye having an azo skeleton. The colored dispersion according to claim 6, wherein the disperse dye having an azo skeleton is a disperse dye represented by the following formula (3).

(In formula (3), R ⁴ represents a substituent. n represents an integer from 0 to 6.) The disperse dye represented by the above formula (3) is C.I. I. The colored dispersion according to claim 7, which is DisperseOrange25. The colored dispersion according to claim 1, wherein the disperse dye is a disperse dye having an anthraquinone skeleton. The colored dispersion according to claim 9, wherein the disperse dye having an anthraquinone skeleton is a dye represented by the following formula (4).

(In formula (4), R ⁵ represents a substituent. p represents an integer from 0 to 6.) The disperse dye represented by the above formula (4) is C.I. I. The colored dispersion according to claim 10, which is DisperseRed60. The colored dispersion according to claim 11, wherein the compound represented by formula (1) is a sodium naphthalene sulfonate formalin condensate. The colored dispersion according to claim 12, wherein the sodium naphthalene sulfonate formalin condensate is a formalin condensate of creosote oil sulfonic acid. An inkjet textile printing ink comprising the colored dispersion according to any one of claims 1 to 13. An ink set comprising the inkjet textile printing ink according to claim 14 and at least one ink selected from the group consisting of yellow ink, magenta ink, and cyan ink. A hydrophobic fiber printed using the inkjet textile printing ink according to claim 14 or the ink set according to claim 15. A step A in which the inkjet textile printing ink according to claim 14 or the ink set according to claim 15 is applied to a hydrophobic fiber by an inkjet printer, and a liquid of the ink composition applied in step A. A method for printing hydrophobic fibers, comprising a step B of fixing the colorant in the drops to the fiber by heat, and a step C of washing the unfixed colorant remaining in the fiber.