JP2016190933A - Magenta ink for inkjet printing and fiber printing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a magenta ink composition having an excellent balance between saturation and color development, a fiber printing method using the same, and a fiber printed by the printing method.SOLUTION: A magenta ink composition comprises at least two dyes each having sublimability, where at least one of the dyes has fluorescence and at least one of the dyes has no fluorescence.SELECTED DRAWING: None

Description

The present invention relates to a magenta ink composition used for inkjet printing, an inkjet printing method using the same, and fibers printed by them.

In recent years, a recording method for performing plateless printing by ink jet has been proposed, and ink jet textile printing is also performed on fibers including cloth. Compared with conventional screen printing and the like, ink-jet printing has various advantages such as no plate making; resource saving; energy saving; and easy high-definition expression. Has been.
Hydrophobic fiber cloth such as polyester fiber is generally dyed with a water-insoluble colorant. Therefore, as a water-based ink used for printing of hydrophobic fibers, it is generally necessary to use a dispersed ink in which a water-insoluble colorant is dispersed in water and performance such as dispersion stability is good.

  In inkjet printing using a disperse dye, which is one of water-insoluble colorants, usually three colors of yellow, magenta, and cyan, or four color ink sets with black added to it are used as basic colors. ing. Inkjet textile printing is used for apparel applications such as sports apparel, and its application is expanding. As a result, ink performance for ink jet textile printing requires high stability and lightness, high saturation and lightness; expanded color reproduction range; and safety for living organisms and the environment. It has come to be.

As magenta dyes used for ink jet textile printing, dyes described in the following Patent Documents 1 to 3 are known.
As the magenta dye having fluorescence, C.I. I. Vat Red 41 is C.I. as a magenta disperse dye having no fluorescence. I. Disperse Red 60 is known.

Japanese Patent No. 4818102 Japanese Patent No. 5473114 Special table 2013-515826 gazette

  An object of the present invention is to provide a magenta ink composition having an excellent balance between saturation and color developability, a fiber printing method using the same, and a fiber printed by this printing method.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by an ink composition containing a specific magenta disperse dye as a colorant, and have completed the present invention.

That is, the present invention relates to the following 1) to 15).
1)
Both are magenta ink compositions containing at least two dyes having sublimation properties, wherein at least one dye is a fluorescent dye and at least one dye is a non-fluorescent dye. Magenta ink composition.
2)
Fluorescent dyes are C.I. I. The magenta ink composition as described in 1) above, which is a dye selected from Vat Red.
3)
The magenta ink composition according to 1) or 2) above, wherein the fluorescent dye is a dye having a thioindigo structure in the molecule.
4)
Fluorescent dyes are C.I. I. The magenta ink composition according to any one of 1) to 3), which is Vat Red 41.
5)
A dye having no fluorescence is C.I. I. The magenta ink composition as described in 1) above, which is a dye selected from Disperse Red.
6)
The magenta ink composition as described in 1) or 5) above, wherein the dye having no fluorescence is a dye having an anthraquinone structure in the molecule.
7)
A dye having no fluorescence is C.I. I. The magenta ink composition according to 1), 5) or 6), which is Disperse Red 60.
8)
The magenta ink composition according to any one of 1) to 7), further containing a water-soluble organic solvent.
9)
The magenta ink composition according to any one of 1) to 8), wherein the ink composition has a viscosity of 3 to 20 mPa · s at 25 ° C.
10)
Step A in which droplets of the magenta ink composition according to any one of 1) to 9) are attached to a fiber by an ink jet printer, and a dye in the droplets of the ink composition attached in Step A. A textile printing method comprising: a step B for fixing to a fiber by heat; and a step C for washing an unfixed dye remaining in the fiber.
11)
10. The fiber printing method according to 10), further comprising a fiber pretreatment step of applying an aqueous solution containing at least one paste material to the fibers before the droplets of the magenta ink composition are attached.
12)
After the droplets of the magenta ink composition according to any one of 1) to 9) are attached to an intermediate recording medium by an ink jet printer, the magenta ink composition attachment surface of the intermediate recording medium and fibers A method for textile printing, in which a dye in a magenta ink composition adhering to an intermediate recording medium is sublimated and transferred to a fiber by heating with contact with the medium.
13)
The fiber printing method according to any one of 10) to 12), wherein the fiber is a hydrophobic fiber or a blended fiber containing a hydrophobic fiber.
14)
The fiber printing method according to 13) above, wherein the hydrophobic fiber is a polyester fiber.
15)
A printed fiber obtained by the printing method according to any one of 10) to 14).

According to the present invention, it was possible to provide a magenta ink composition having an excellent balance between saturation and color developability, a fiber printing method using the same, and a fiber printed by this printing method.

  In the present specification, “part” and “%” are described on a mass basis unless otherwise specified, including examples.

The magenta ink composition (hereinafter referred to as “ink composition” unless otherwise specified) is a water-based dispersed ink composition containing water.
Each of the ink compositions contains at least two kinds of dyes having sublimation properties. Of the at least two types of dyes, at least one type is a fluorescent dye, and at least one type is a non-fluorescent dye.

Examples of dyes having sublimation properties include “sensitivity to dyeing fastness test method for dry heat treatment [JIS L 0879: 2005] (confirmed in 2010, revised on January 20, 2005, published by the Japanese Standards Association)”. Examples of the heat treatment test (Method C) include dyes having a contamination (polyester) test result of preferably grade 3-4 or lower; more preferably grade 3 or lower. Among such dyes, C.I. I. Examples of the dye having a number include the following dyes.
Examples of red dyes include C.I. I. Disperse Red (hereinafter referred to as “DiR”) 11, 50, 53, 55, 55: 1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240 C. I. Vat Red (hereinafter referred to as “VR”) 41;
Examples of yellow dyes include C.I. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 82, 86; I. Solvent Yellow 43, 114, 163; and the like.
Examples of orange dyes include C.I. I. Disperse Orange 1, 1: 1, 5, 20, 25, 25: 1, 33, 56, 76; and the like.
Examples of the brown dye include C.I. I. Disperse Brown 2; etc.
Examples of the violet dye include C.I. I. Disperse Violet 8, 17, 23, 27, 28, 29, 36, 57;
Examples of blue dyes include C.I. I. Disperse Blue 19, 26, 26: 1, 35, 55, 56, 58, 64, 64: 1, 72, 72: 1, 81, 81: 1, 91, 95, 108, 131, 141, 145, 359, 360; I. Solvent Blue 3, 63, 83, 105, 111; and the like.
The above-mentioned “CI” means “color index”.

In the present specification, the fluorescent dye means a dye having a maximum fluorescence peak intensity of 1000 or more when measured under the following conditions.
[measuring equipment]
F-7000 spectrofluorometer manufactured by Shimadzu Corporation.
[sample]
An ink composition having a dye content of 5% is prepared, and a solid pattern having a concentration of 100% is applied to transfer paper as an intermediate recording medium, preferably ink jet recording. The surface to which the obtained ink composition is applied is cut into a size of 35 cm × 40 cm, overlapped with a polyester cloth of the same size, preferably a ponge, and then subjected to heat treatment at 200 ° C. for 60 seconds to perform sublimation transfer from the intermediate recording medium to the polyester cloth. Perform printing. The dyed polyester cloth thus obtained is used as a sample, and the maximum intensity of the fluorescence peak is measured with the measuring instrument.
[Ink composition having a dye content of 5%]
As the ink composition having a dye content of 5%, either an aqueous or non-aqueous ink can be used. For example, the dispersed ink composition prepared in the examples of the present specification can be used. Further, a dye solution can be prepared by dissolving the dye in an organic solvent having a dye solubility of 5% or more, and this can be used.
Since the above-mentioned fluorescent peak measurement method uses a polyester cloth subjected to sublimation transfer printing as a sample, specifying a dye content in the ink composition of 5% can obtain a result with a small measurement error. it can.
As the dye having fluorescence, a dye selected from DiR and VR is preferable. Among them, a dye having a thioindigo structure in the molecule is preferable. Such a dye includes VR41.

If the fluorescent property is too strong, it is not preferable because it gives a feeling of glare when visually observed or an impression that the eyes are close. On the other hand, if it is too weak, an impression of lack of vividness is obtained when visually observed, which is also not preferable.
There are individual differences in the impression of hue, and it is difficult to determine it in general. However, as a guideline, when the maximum intensity of the fluorescence peak is usually about 1000 or more and less than 5000, a generally good hue is given.

  The dye having no fluorescence means a dye having sublimation property other than the above-mentioned “dye having fluorescence”. The dye not having fluorescence is preferably a dye selected from DiR. Among them, a dye having an anthraquinone structure in the molecule is more preferable. Such dyes include DiR 11, 53, 55, 55: 1, 59, 60, 70, 75, 93, 146, 190, 190: 1, 207 and the like. Among them, DiR 60 is preferable.

  The ratio of the total mass of the fluorescent dye and the total mass of the non-fluorescent dye contained in the ink composition is not particularly limited. However, when a dye having fluorescence is contained, the fluorescent color is sometimes excessively emphasized, and it may be visually perceived as glaring or as if the eyes are flickering. In this case, for example, when full-color printing is performed using other colors such as magenta, cyan, and black, only the magenta portion is overemphasized, and a sense of incongruity with other hue portions occurs. . In such a case, the ratio of the total mass of the fluorescent dye to the total mass of the non-fluorescent dye is usually 50/50, preferably 60/40, more preferably 75/25. Discomfort between the magenta portion and other hue portions is eliminated.

  For the purpose of finely adjusting the color of the ink composition to a desired color tone, the ink composition may contain other dyes (hereinafter referred to as “toning dyes”) as long as the effects of the present invention are not impaired. Furthermore, it can contain. Such dyes include C.I. I. Disperse and C.I. I. Examples include dyes selected from Solvent. The color of the toning dye is preferably a dye selected from Red, Orange and Violet.

  Among the toning dyes, C.I. I. Disperse Red includes 11, 50, 53, 55, 55: 1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240, and the like.

  Similarly, C.I. I. Disperse Orange is as follows: 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, 61, 66, 71, 73, 76, 78, 80, 86, 89, 90, 91, 93, 96 97, 118, 119, 127, 130, 139, 142, and the like.

  Similarly, C.I. I. Examples of the Disperse Violet include 8, 17, 23, 27, 28, 29, 36, and 57.

  Similarly, C.I. I. Solvent includes C.I. I. Solvent Orange 60, 67, 80; C.I. I. Solvent Red 146;

As the dye, a commercially available dye can be directly used for preparing the ink composition. Moreover, after refine | purifying dye, it can also be used for preparation of an ink composition.
When the ink composition droplets are attached to a fiber or the like by an ink jet printer for printing (in other words, when used for ink jet textile printing), the storage stability of the ink composition and the ejection properties are taken into consideration. It is preferably used after the dye is purified.
Examples of the purification method of the dye include a method using a reverse osmosis membrane; the solid of the dye is added to a water-soluble organic solvent such as acetone, methanol, dimethyl sulfoxide or the like, or these water-soluble organic solvents containing water, and suspension purification or crystallization is performed. And the like.

The ink composition can contain a water-soluble organic solvent for the purpose of preventing clogging at the nozzle.
Specific examples of the water-soluble organic solvent include polyhydric alcohols and pyrrolidones.
Examples of the polyhydric alcohol include C2-C6 polyhydric alcohol having 2 to 3 alcoholic hydroxyl groups; di- or tri-C2-C3 alkylene glycol; or a repeating unit of 4 or more and a molecular weight of about 20,000 or less. And poly C2-C3 alkylene glycol, preferably liquid polyalkylene glycol. Specific examples thereof include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol, and 1,5-pentanediol. Is mentioned.
Examples of pyrrolidones include 2-pyrrolidone and N-methyl-2-pyrrolidone.
In addition, in the present specification, a solid compound is included in the water-soluble organic solvent for convenience, as long as it is a compound having an effect as a wetting agent when dissolved in water. Examples of such compounds include urea, ethylene urea and saccharides.
Considering the storage stability of the ink composition, it is preferable to use a water-soluble organic solvent having a low solubility of the dye contained in the ink composition.
Among the water-soluble organic solvents, it is more preferable to use glycerin together with a water-soluble organic solvent other than glycerin (preferably a polyhydric alcohol other than glycerin).
The total content of the water-soluble organic solvent in the total mass of the ink composition is usually 5 to 40%, preferably 10 to 30%.

The ink composition may contain a dispersant. The dispersant is not particularly limited as long as it can disperse the dye contained in the ink composition. Examples of such substances include known dispersants, surfactants, and resin dispersants.
Further, the dispersant and the surfactant are simply different in name, and may specifically refer to the same substance. Examples of the dispersant include anions, nonions, cations, and amphoteric. Any of these dispersants can be used alone or in combination. Of these, at least one dispersant selected from anionic and nonionic dispersants is preferred.

Examples of the anionic dispersant include a high molecular weight sulfonic acid, preferably a formalin condensate of aromatic sulfonic acid, a lignin sulfonic acid, a formalin condensate of lignin sulfonic acid or a salt thereof, or a mixture thereof (hereinafter, particularly, Unless otherwise stated, when “formalin condensate of sulfonic acid” is described, it means “including these salts or a mixture thereof”) and the like. Examples of these salts include sodium salts, potassium salts, lithium salts and the like.
Formalin condensates of aromatic sulfonic acids include, for example, creosote oil sulfonic acid; cresol sulfonic acid; phenol sulfonic acid; β-naphthalene sulfonic acid; β-naphthol sulfonic acid; β-naphthalene sulfonic acid and β-naphthol sulfonic acid Formalin condensates such as cresol sulfonic acid and 2-naphthol-6-sulfonic acid; lignin sulfonic acid; In these, each formalin condensate of creosote oil sulfonic acid; (beta) -naphthalenesulfonic acid; ligninsulfonic acid; is preferable.
These can be obtained as commercial products of various trade names. As an example, there is demole N as the formalin condensate of β-naphthalene sulfonic acid; demole C as the formalin condensate of creosote oil sulfonic acid; demole SN-B as the formalin condensate of special aromatic sulfonic acid (both Manufactured by Kao Corporation);
Examples of the formalin condensate of creosote oil sulfonic acid include Labelin W series; examples of the formalin condensate of methylnaphthalene sulfonic acid include Labelin AN series (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
Among these, the demole N, the labeline AN series, and the labeline W series are preferable, the demole N and labeline W are more preferable, and the labeline W is more preferable.
Examples of lignin sulfonic acid include Vanillex N, Vanillex RN, Vanillex G, and Pearllex DP (all manufactured by Nippon Paper Industries Co., Ltd.). Among these, Vanillex RN, Vanillex N, and Vanillex G are preferable.

Nonionic dispersants include, for example, alkylene oxide adducts of phytosterols, alkylene oxide adducts of cholestanols, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxy Examples include ethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethyleneoxypropylene block polymer, and substituted derivatives thereof.
Among these, alkylene oxide adducts of phytosterols and alkylene oxide adducts of cholestanols are preferable.
The alkylene oxide adduct of phytosterols is preferably a C2-C4 alkylene oxide adduct of phytosterols, more preferably an ethylene oxide adduct.
In the present specification, the term “phytosterols” includes both phytosterols and / or hydrogenated phytosterols. For example, the ethylene oxide adduct of phytosterols includes an ethylene oxide adduct of phytosterol and / or an ethylene oxide adduct of hydrogenated phytosterol.
The alkylene oxide adduct of cholestanols is preferably a C2-C4 alkylene oxide adduct of cholestanols, more preferably an ethylene oxide adduct.
In this specification, the term “cholestanols” means both cholestanols and / or hydrogenated cholestanols. For example, the ethylene oxide adduct of cholestanols includes an ethylene oxide adduct of cholestanol and / or an ethylene oxide adduct of hydrogenated cholestanol.
The addition amount of alkylene oxide (preferably C2-C4 alkylene oxide, more preferably ethylene oxide) per mole of phytosterols or cholestanols is preferably about 10 to 50 mol and HLB is about 13 to 20.
Specific examples of these include, for example, NIKKOL BPS-20, NIKKOL BPS-30 (phytosterol ethylene oxide adduct); NIKKOL BPSH-25 (hydrogenated phytosterol ethylene oxide adduct); and NIKKOL DHC-30 (core An ethylene oxide adduct of stanol);

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

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

  Examples of amphoteric dispersants include carboxybetaines, sulfobetaines, aminocarboxylates, imidazolinium betaines, and the like.

Examples of the resin dispersant include a copolymer that can be used as an anionic dispersant. As a preferable resin dispersant, a copolymer of a compound containing an aromatic hydrocarbon group and (meth) acrylic acid (ester); a compound containing an aromatic hydrocarbon group, and (meth) acrylic acid (ester) , And (anhydrous) maleic anhydride copolymer; The term “(meth) acrylic acid (ester)” is used herein to mean acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester, and “(anhydrous) maleic acid” is anhydrous. The meanings including maleic acid and maleic acid are used respectively.
Preferred examples of the copolymer of a compound containing an aromatic hydrocarbon group and (meth) acrylic acid (ester) include a copolymer having a hydrophilic part and a hydrophobic part in the molecule.
When a compound containing an aromatic hydrocarbon group and (meth) acrylic acid (ester) are copolymerized, a single compound can be used as the latter, or a plurality of compounds can be used in combination. When copolymerization is performed, maleic anhydride is added to form a compound containing an aromatic hydrocarbon group, (meth) acrylic acid (ester), and (anhydrous) maleic acid copolymer. it can.
For the purpose of strengthening the interaction with the dye, it is preferable to use a compound containing an aromatic hydrocarbon group as the hydrophobic portion of the copolymer in the molecule. 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 acid ester copolymer, (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-styrenesulfonic acid copolymer, (α-methyl) styrene- Methacrylsulfonic acid copolymer, polyester-acrylic acid copolymer, polyester-acrylic acid-acrylic acid ester copolymer, Riesuteru - methacrylic acid copolymer, polyester - methacrylic acid - acrylic acid copolymer ester; and the like. Among these, the compound containing an aromatic hydrocarbon group is preferably styrene.
In the present specification, (α-methyl) styrene is used to mean α-methylstyrene and styrene.
Specific examples of these copolymers include Jonkrill 67, 68, 586, 611, 678, 680, 682, 683, 690 manufactured by BASF. Among these, Jonkrill 68, 678, 682, 683, and 690 are preferable.

  Other resin dispersants include styrene and its derivatives, vinyl naphthalene and its derivatives, aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acids, acrylic acid and its derivatives, maleic acid and its derivatives, itacon At least two monomers selected from acid and derivatives thereof, fumaric acid and derivatives thereof, vinyl acetate, vinyl alcohol, vinyl pyrrolidone, acrylamide, and derivatives thereof (of which at least one is a hydrophilic or water-soluble monomer) Block copolymer, random copolymer and graft copolymer, and / or salts thereof.

  Examples of the surfactant include anionic, nonionic, cationic, and amphoteric surfactants.

  Examples of anionic surfactants include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt, N-acyl glutamate, alkyl ether carboxylate, acylated peptide, alkyl Sulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol sulfate, Secondary higher alcohol sulfates, alkyl ether sulfates, secondary higher alcohol ethoxy sulfates, polyoxyethylene alkyl phenyl ether sulfates, monoglyculates, fatty acid alkylolamide sulfates, alkyl ether phosphates And alkyl phosphate ester salts. Moreover, as a preferable commercial item, Adeka Coal series (EC-8600 etc., made by Adeka Co., Ltd.), Hightenol series (NE-15 etc., made by Daiichi Kogyo Seiyaku Co., Ltd.), Perex series (OT-P etc., Kao) Etc.).

Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether (eg, Emulgen 911), polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, polyoxyethylene poly Oxypropylene alkyl ether (for example, Newpol PE-62), polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, Fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester Sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkyl amine oxides, acetylene glycol, acetylene alcohol, and the like.
Examples of commercially available products include, for example, Olfin series (E1004, E1010, etc.) manufactured by Nissin Chemical Industry Co., Ltd., Surfynol series (420, 440, 465, etc.) manufactured by Air Products Japan Co., Ltd., Nippon Shokubai Co., Ltd. Examples include Softanol series (EP5035, etc.) manufactured by Kao Corporation, and Emulgen series (A-60, etc.) manufactured by Kao Corporation.

  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, and imidazoline derivatives. Can be mentioned.

  The ink composition may further contain an ink preparation agent as necessary. Examples of the ink preparation agent include antiseptic / antifungal agents and pH adjusters.

  Examples of antiseptic / antifungal agents include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, and 1-benzisothiazoline-3 -Amine amine salts and the like.

  Examples of the pH adjuster include alkali hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine and diethylethanolamine.

The method for preparing the ink composition is not particularly limited. For example, a method of adding an ink preparation agent such as a water-soluble organic solvent after preparing an aqueous dispersion of a dye can be mentioned.
Examples of the method for preparing an aqueous dispersion of a dye include a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, and the like. A well-known method is mentioned.
Foaming may occur when preparing a dye dispersion. For this reason, if necessary, an antifoaming agent such as silicone type; acetylene alcohol type, etc. may be added during the preparation of the dispersion. However, since some antifoaming agents inhibit the dispersion and micronization of dyes and the like, it is preferable to use those that do not affect the micronization and the stability of the dispersion. Preferable antifoaming agents include, for example, Olphine series (SK-14 etc.) manufactured by Nissin Chemical Industry Co., Ltd .; Surfynol series (104, DF-110D etc.) manufactured by Air Products Japan Ltd .; .

  When an aqueous dispersion of a dye is used for preparing the ink composition, the total content of the dye in the total mass of the aqueous dispersion is usually 10 to 60%, preferably 20 to 50%, more preferably 20 to 20%. 40%. Similarly, the content of the dispersant is usually 1 to 36%, preferably 5 to 30%, more preferably 5 to 20%, and further preferably 5 to 15%.

The content of the aqueous dispersion in the total mass of the ink composition is usually 2 to 40%, preferably 3 to 38%, more preferably 5 to 35%.
Similarly, the total content of the ink preparation agent is usually 0 to 25%, preferably 0.01 to 20% with respect to the total mass of the aqueous ink composition.

The average particle diameter of the dye contained in the ink composition is generally 50 nm to 150 nm, preferably 60 nm to 150 nm, more preferably 70 nm to 150 nm, and still more preferably 80 nm to 150 nm as D50.
Similarly, D90 is usually 160 nm to 350 nm, preferably 160 nm to 300 nm, more preferably 160 nm to 250 nm, and still more preferably about 160 nm to 200 nm.

  The viscosity when the ink composition is used for ink jet textile printing is preferably about 3 to 20 mPa · s when measured with an E-type viscometer at 25 ° C. By setting it as this viscosity, the discharge responsiveness at high speed becomes favorable. Further, the surface tension is usually preferably in the range of 20 to 45 mN / m when measured by the plate method. In addition, it is preferable to adjust the viscosity and surface tension to appropriate physical property values in consideration of the discharge amount, response speed, ink droplet flight characteristics, and the like of the ink jet printer used.

The textile printing methods are roughly classified into two types.
The first method is a method called direct printing or direct textile printing.
This method includes a step A in which droplets of the ink composition are attached to fibers by an ink jet printer, and image information such as characters and pictures is formed on the fibers.
A step B for fixing the dye in the droplets in the ink composition adhered by the step A to the fiber by heat;
This is a fiber printing method including at least three steps of step C and washing of unfixed dye remaining in the fiber.
Step B is generally performed by known steaming or baking.
For steaming, for example, a high temperature steamer is usually 170 to 180 ° C., usually about 10 minutes; a high pressure steamer is usually 120 to 130 ° C., usually about 20 minutes; The method of doing is mentioned.
Examples of the baking (thermosol) include a method of dyeing a dye on a fiber by treating the fiber usually at 190 ° C. to 210 ° C., usually about 60 seconds to 120 seconds.
Step C is a step of washing the obtained fiber with warm water and, if necessary, 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 textile printing method may further include a fiber pretreatment step for the purpose of preventing bleeding and the like. Examples of the pretreatment step include a step of applying an aqueous solution containing at least one paste material, an alkaline substance, an anti-reduction agent, and a hydrotropic agent to fibers before the ink composition is attached.
As the pretreatment step, an aqueous solution of a pretreatment agent containing a paste, an alkaline substance, a reduction inhibitor and a hydrotropic agent is used as a pretreatment liquid, and the fiber is applied or impregnated in the pretreatment liquid. Is preferred.

  Examples of the paste include natural gums such as guar and locust bean, starches, seaweeds such as sodium alginate and fungi, plant skins such as pectic acid, methyl fibrin, ethyl fibrin, hydroxyethylcellulose, carboxymethylcellulose, etc. Fiber derivatives, processed starches such as carboxymethyl starch, synthetic pastes such as polyvinyl alcohol and polyacrylates. Preferably, sodium alginate is used.

  Examples of the alkaline substance include, for example, an alkali metal salt of an inorganic acid or an organic acid; a salt of an alkaline earth metal; and a compound that liberates alkali when heated, and includes an inorganic or organic alkali metal hydroxide and alkali. Metal salts are preferred, and examples include sodium compounds and potassium compounds. Specific examples include, for example, alkali metal hydroxides such as sodium hydroxide and calcium hydroxide; inorganic compounds such as sodium carbonate, sodium bicarbonate, 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. Preferably, sodium hydrogencarbonate is used.

  As the reduction inhibitor, sodium metanitrobenzenesulfonate is preferable.

  Examples of the hydrotropic agent include ureas such as urea and dimethylurea. Preferably it is urea.

As for the said paste agent, an alkaline substance, a reduction inhibitor, and a hydrotropic agent, all can use a single compound, or can also use a several compound together, respectively.
The mixing ratio of each pretreatment agent in the total mass of the pretreatment liquid is, for example, 0.5 to 5% for a paste, 0.5 to 5% for sodium bicarbonate, and 0 to 5% for sodium metanitrobenzenesulfonate. , Urea is 1 to 20%, and the balance is water.
Examples of the application of the pretreatment agent to the fiber include a padding method. The padding drawing ratio is preferably about 40 to 90%, more preferably about 60 to 80%.

The second method is a method called sublimation transfer printing, sublimation transfer printing, or the like.
In this method, a droplet of the ink composition is attached to an intermediate recording medium by an ink jet printer to obtain an intermediate recording medium on which image information such as characters and pictures is recorded, and then the ink composition of the intermediate recording medium Textile printing method for printing by sublimation-transferring the dye in the ink composition adhered to the intermediate recording medium to the fiber by heating the contact surface of the liquid droplet and the fiber in contact with the fiber It is.
As the intermediate recording medium, a medium in which the dye in the ink composition attached to the intermediate recording medium does not aggregate on the surface and does not interfere with sublimation of the dye when performing sublimation transfer is preferable.
As an example of such an intermediate recording medium, paper having an ink receiving layer formed on the surface with inorganic fine particles such as silica can be used, and dedicated paper for ink jet recording can be used.
As a heating method for transferring a recorded image from an intermediate recording medium to a fiber, a method of performing a dry heat treatment at about 190 to 200 ° C. is usually used.

Although it does not restrict | limit especially as said fiber, A hydrophobic fiber is preferable. Examples of hydrophobic fibers include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended fibers using two or more of these fibers. In addition, in this specification, mixed fibers of these and recycled fibers such as rayon, and natural fibers such as cotton, silk, and wool are also included in the hydrophobic fibers.
Some fibers have an ink receiving layer (bleeding prevention layer), and such fibers can also be used in the above printing method. The fiber having the ink receiving layer can be prepared by a known method, or can be obtained as a commercial product. The material and structure of the ink receiving layer are not particularly limited, and can be appropriately used depending on the purpose.

According to the present invention, the color reproduction range can be expanded as compared with the conventional ink-jet printing, without using an unlimited number and kind of dyes as in the conventional printing method using color paste or the like.
The dispersion of the present invention has good storage stability without causing solid aggregation or precipitation even when stored for a long period of time. In addition, changes in physical properties such as viscosity and average particle diameter are extremely small.
In addition, the ink composition of the present invention is excellent not only in color developability but also in various fastness properties such as light resistance, abrasion resistance, gas resistance, chlorine resistance, sweat resistance, and wash fastness.

  The following examples further illustrate the present invention, but the present invention is not limited to these examples.

[Preparation Examples 1-2]: Preparation of aqueous dispersion.
0.2 mm diameter glass beads were added to each component described in Table 1 below, and dispersion treatment was performed for about 15 hours under water cooling in a sand mill. 100 parts of ion-exchanged water was added to the obtained liquid, and the dye content in the total mass of the liquid was adjusted to 15%. The obtained liquid was filtered with glass fiber filter paper GC-50 (manufactured by ADVANTEC) to obtain an aqueous dispersion of Preparation Examples 1 and 2 each having a dye content of about 15%. Let the obtained dispersion liquid be dispersion liquid 1-2, respectively.

[Examples 1 and 2] and [Comparative Examples 1 and 2]: Preparation of ink compositions.
Each component described in Table 2 below was mixed and stirred for about 30 minutes to obtain ink compositions. The obtained ink compositions were filtered with glass fiber filter paper GC-50 (manufactured by ADVANTEC Co., Ltd.), so that each of the ink compositions of Examples 1-2 used for inkjet printing and Comparative Examples 1-2 for comparison were used. Was prepared.

[Preparation of dyed fabric]
Using the ink composition of Example 1, a solid pattern was printed on transfer paper as an intermediate recording medium with an inkjet printer PX-105 (manufactured by Seiko Epson Corporation). The adhered portion of the ink composition on the printed transfer paper was cut into 35 cm × 40 cm. After the ink adhering surface of the cut transfer paper and a polyester cloth (ponge) of the same size are overlapped, a transfer press machine TP-600A2 manufactured by Taiyo Seiki Co., Ltd. is used and the condition is 200 ° C. × 60 seconds. Then, heat transfer was performed, and sublimation transfer printing from the transfer paper to the polyester cloth was performed. The printed polyester cloth thus obtained is designated as dyed cloth 1.
A dyed fabric 2 was obtained in the same manner as described above except that the ink composition of Example 2 was used instead of the ink composition of Example 1.

[Preparation of comparative dyed fabric]
A printed polyester fabric was obtained in the same manner as described above except that the ink composition of Comparative Examples 1 and 2 was used instead of the ink composition of Example 1. The obtained printed polyester cloth is designated as comparative dyed cloth 1-2.
The obtained dyeing cloth and the comparative dyeing cloth were used as test dyeing cloths, and the following evaluation tests were performed.

[Hue Evaluation 1]
The hue was measured by measuring the test a * value and the b * value using a product name: SpectroEye manufactured by GRETAG-MACBETH, as a colorimeter.
The hues a * and b * of each test dyed cloth obtained as described above were measured with the above colorimeter, and the saturation C * was calculated. The results are shown in Table 3 below. Further, the saturation C * was obtained from the following formula based on the value. Saturation means that a higher numerical value means higher definition and is superior in performance.
C * = [(a *) ² + (b *) ² ] ^1/2 .
[Evaluation criteria]
A: The saturation is 77.0 or more, and it is a very vivid magenta color.
C: A magenta color having a saturation of less than 77.0 and lacking in vividness.

[Hue Evaluation 2]
The hue of the test dyed cloth was visually observed and evaluated according to the following two-stage criteria.
[Evaluation criteria]
A: No glare or sensation of eye contact is obtained.
B: Although there is a slight glare, a feeling that the eyes are close cannot be obtained.
C: A strong sensation of glare and eye flickering.

[Color development evaluation]
Each test dyed fabric was evaluated for color developability. The evaluation of color development was performed by measuring the DM value, which is the reflection density of magenta.
[Evaluation criteria]
A: A magenta having a DM value of 1.4 or more and high color development.
B: The DM value is 1.3 or more and less than 1.4, and it is a medium color developing magenta.
C: A magenta having a DM value of less than 1.3 and low color development.

[Fluorescence evaluation test]
About each test dyeing cloth, the maximum intensity | strength of the fluorescence peak was measured with Shimadzu Corporation F-7000 type | mold spectrofluorimeter. ,

上記結果より、比較染布２は蛍光性が強すぎて色相に問題があり、比較染布１は蛍光性が低く鮮やかさに乏しい。

From the above results, the comparative dyeing cloth 2 is too fluorescent and has a problem in hue, and the comparative dyeing cloth 1 has low fluorescence and poor vividness.

  The ink composition of the present invention can provide a dyed fabric having a very good magenta hue and color developability, and is extremely useful as a magenta ink for ink jet recording, particularly for ink jet textile printing.

Claims (15)

  Both are magenta ink compositions containing at least two dyes having sublimation properties, wherein at least one dye is a fluorescent dye and at least one dye is a non-fluorescent dye. Magenta ink composition.   Fluorescent dyes are C.I. I. The magenta ink composition according to claim 1, which is a dye selected from Vat Red.   The magenta ink composition according to claim 1 or 2, wherein the fluorescent dye is a dye having a thioindigo structure in the molecule.   Fluorescent dyes are C.I. I. The magenta ink composition according to claim 1, which is Vat Red 41.   A dye having no fluorescence is C.I. I. The magenta ink composition according to claim 1, wherein the magenta ink composition is a dye selected from Disperse Red.   The magenta ink composition according to claim 1 or 5, wherein the dye having no fluorescence is a dye having an anthraquinone structure in the molecule.   A dye having no fluorescence is C.I. I. The magenta ink composition according to claim 1, 5 or 6, which is Disperse Red 60.   The magenta ink composition according to any one of claims 1 to 7, further comprising a water-soluble organic solvent.   The magenta ink composition according to any one of claims 1 to 8, wherein the viscosity of the ink composition at 25 ° C is 3 to 20 mPa · s.   A process A in which droplets of the magenta ink composition according to any one of claims 1 to 9 are adhered to a fiber by an ink jet printer, and a dye in the droplets of the ink composition deposited in Step A is heated. A fiber printing method comprising: a step B for fixing to a fiber by the step B; and a step C for washing an unfixed dye remaining in the fiber.   The fiber printing method according to claim 10, further comprising a fiber pretreatment step of applying an aqueous solution containing at least one paste material to the fibers before the droplets of the magenta ink composition are attached.   After the droplets of the magenta ink composition according to any one of claims 1 to 9 are attached to an intermediate recording medium by an ink jet printer, the surface of the intermediate recording medium to which the droplets of the magenta ink composition are attached A textile printing method in which printing is carried out by sublimation transfer of a dye in a droplet of a magenta ink composition adhering to an intermediate recording medium to the fiber by heating it in contact with the fiber.   The textile printing method according to any one of claims 10 to 12, wherein the fiber is a hydrophobic fiber or a blended fiber containing a hydrophobic fiber.   The textile printing method according to claim 13, wherein the hydrophobic fiber is a polyester fiber.   A printed fiber obtained by the printing method according to any one of claims 10 to 14.