JPWO2012060343A1 - Azo dye ink composition and ink set for ink jet printing using the same - Google Patents

Abstract

As a red ink composition suitable for an ink set having a wide color reproduction range for ink jet textile printing, particularly a color range of red to violet to blue to cyan, and a good light fastness, the following general formula (1) An ink composition containing a monoazo dye represented by the formula: water, a dispersant, and a water-soluble organic solvent is provided. Furthermore, an ink set comprising the ink composition, an ink jet printing method using the ink set, and a dyed product obtained by the method are provided. In the formula, R1 and R2 each independently represent a hydrogen atom, a phenyl group which may have a substituent, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aralkyl group. . R3 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R3 are present, they may be the same or different. n shows the integer of 1-5.

Description

  The present invention relates to an ink composition containing a monoazo dye, in particular, an aqueous dispersion for ink jet printing, a disperse dye ink set including the same, and an ink jet printing method for polyester fibers using the same. It has excellent color reproducibility in a wide color reproduction range, particularly in a hue range from red to violet to blue to cyan, and has good light fastness.

  Ink-jet textile printing using an ink-jet printer requires no plate-making process and shortens the process compared with conventional printing methods such as screen printing, roller printing, rotary printing, etc .; There are many merits such as being able to print as it is; being able to produce a wide variety of products even in small quantities; drastically reducing waste of dye color paste; On the other hand, there are problems such as slow printing processing speed and difficulty in reproducing dark colors, which are often used in the range of sample production and small-scale production.

  In recent years, the printing speed of inkjet printers has been greatly improved due to technological advances in computer image processing and printhead manufacturing; digitization of print design has progressed; diversification of print processing and smaller lots Against the backdrop of what has been required in the market; Acid ink for polyamide fibers such as silk and nylon as dye ink for inkjet printing; Reactive dye ink for cellulose fibers such as cotton and rayon; Polyester Disperse dye inks for textiles are sold.

  Ink for ink-jet printing using disperse dyes is required to provide a sufficient density for color development, to have a wide range of color reproduction, and to be able to provide a printed product with high fastness. Various ink sets have been proposed for these requirements. However, the ink set using conventional dyes cannot completely reproduce the hue range obtained by the screen printing method, and uses an azo dye that has a narrow color reproduction range and provides high color density to give a sufficient density. However, the conventional azo dye has a problem that the light fastness is insufficient. An ink set satisfying these points has not yet been provided.

Japanese Patent Publication No. 61-39347 International Publication No. 2005/121263

  There is a need for a disperse dye ink set having excellent color reproducibility in a color reproduction range in ink jet printing, particularly in a hue range of red to violet to blue to cyan, and having good light fastness, and a red ink composition therefor. .

  As a result of intensive research to solve the above-mentioned problems, the present inventors have developed a specific monoazo dye that can increase color reproducibility particularly in the hue range of red, violet, blue, and cyan, and can also obtain high light fastness. The present invention has been completed by finding a red ink composition to be contained and a disperse dye ink set comprising the red ink composition and a cyan ink composition and / or a yellow ink composition.

（式中、Ｒ^１、Ｒ^２は、それぞれ独立に、水素原子、置換基を有していてもよいフェニル基、置換基を有していてもよい炭素数１〜６のアルキル基、又はアラルキル基を示す。Ｒ^３は、水素原子、ハロゲン原子、ニトロ基、シアノ基、アミノ基、又は炭素数１〜４のアルキル基を示し、Ｒ^３が複数存在する場合、それらは同一であっても異なっていてもよい。ｎは１〜５の整数を示す。）That is, the present invention relates to the following 1) to 8).
1) An ink composition containing a monoazo dye represented by the following general formula (1), water, a dispersant, and a water-soluble organic solvent.

(In the formula, R ¹ and R ² are each independently a hydrogen atom, a phenyl group which may have a substituent, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or aralkyl. R ³ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ³ are present, they may be the same (N may be an integer of 1 to 5.)

2) The ink composition according to 1), wherein the monoazo dye is a mixture of a compound represented by the following formula (2) and a compound represented by the following formula (3).

3) The ink composition according to 1) or 2), further comprising an ethylene oxide adduct of phytosterols and / or an ethylene oxide adduct of cholestanols.
4) The above 3) containing 10 to 25% by mass of the above monoazo dye, 3 to 25% by mass of a dispersant, and 0.9 to 11.25% by mass of an ethylene oxide adduct of phytosterols and an ethylene oxide adduct of cholestanols. The ink composition described in 1.

5) An ink set for use in ink jet textile printing, comprising the ink composition according to any one of 1) to 4) as a red ink composition.
6) Further, C.I. I. Cyan ink composition containing Disperse Blue 60 as a colorant and / or C.I. I. The ink set according to 5) above, comprising a yellow ink composition containing Disperse Yellow 114 as a colorant.

7) A method for inkjet printing of hydrophobic fibers, comprising using the ink set described in 5) or 6) above, printing a colorant on hydrophobic fibers by an inkjet method, and performing a steaming or baking treatment.
8) A dyed product obtained by the inkjet printing method described in 7) above.

  The ink composition and ink set of the present invention are excellent in color reproducibility during ink jet textile printing, particularly in the color range of red to violet to blue to cyan, and also have good light fastness. Therefore, according to the printing method using the same, a dyed product having excellent characteristics can be obtained.

  The present invention will be described in detail. The ink composition of the present invention contains a monoazo dye represented by the general formula (1), water, a dispersant, and a water-soluble organic solvent.

R ^{1 to} R ³ in the general formula (1) are each an independent substituent.

R ¹ and R ² each independently represent a hydrogen atom, a phenyl group which may have a substituent, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aralkyl group.

As a substituent of the phenyl group which may have a substituent in R ¹ and R ² , an optionally substituted alkyl group having 1 to 4 carbon atoms, a hydroxy group, and an alkoxy having 1 to 4 carbon atoms Group, amino group, alkylamino group having 1 to 4 carbon atoms, cyano group, phenylamino group, phenyl group and the like. Specific examples of the phenyl group which may have a substituent include phenyl group, methylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, dimethylphenyl group, hydroxyphenyl group, methoxyphenyl. Group, ethoxyphenyl group, aminophenyl group, N, N-dimethylaminophenyl group, N, N-diethylaminophenyl group, N, N-diphenylaminophenyl group, cyanophenyl group, biphenyl group and the like. Here, the substitution position of each substituent is not particularly limited as long as substitution is possible.

Examples of the substituent of the alkyl group having 1 to 6 carbon atoms that may have a substituent in R ¹ and R ² include a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a hydroxy (C1-C4) alkoxy group, A phenoxy group etc. are mentioned. And as a specific example of the C1-C6 alkyl group which may have a substituent, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n -Hexyl group, cyclohexyl group, hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxybutyl group, hydroxyethoxymethyl group, 2-hydroxyethoxy Ethyl group, 3-hydroxyethoxypropyl group, 3-hydroxyethoxybutyl group, 2-hydroxyethoxybutyl group, methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, propyloxy Methyl group, propyloxyethyl group, propyloxypro Group, phenoxymethyl group, phenoxyethyl group, phenoxypropyl group, phenoxymethyl ethoxymethyl group, phenoxy ethoxyethyl, phenoxyethyl ethoxypropyl, and the like.

Examples of the aralkyl group in R ¹ and R ² include a lower alkyl group having 1 to 4 carbon atoms substituted with an aryl group, such as a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Etc.

Of the R ¹ and R ² , a phenyl group, an alkoxyphenyl group having 1 to 4 carbon atoms, and a hydroxy (C1-C4) alkoxy (C1-C4) alkyl group are preferable, and a phenyl group and a hydroxyethoxyethyl group are particularly preferable.

R ³ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, and isobutyl group. It is done.
Examples of the halogen atom for R ³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Of the above R ³ , a chlorine atom, a bromine atom, a nitro group and a cyano group are preferable, and a nitro group and a cyano group are particularly preferable. The substitution position of R ³ is not particularly limited as long as it can be substituted. When a plurality of R ³ are present, they may be the same or different.

The monoazo dye represented by the general formula (1) contained in the ink composition of the present invention can be produced by the method described in Patent Document 1 (Japanese Patent Publication No. 61-39347) or by applying the method. . In addition, a mixture of compounds in which R ¹ and R ² are different substituents can be obtained by mixing two or more types of dyes having a single structure. It can also be obtained by ring reaction.

  As the monoazo dye contained in the ink composition of the present invention, compounds represented by the above formulas (2) and (3) are preferable, and a compound represented by the above formula (2) or the above formula (3) is preferable. A single compound or a mixture of both compounds may be used.

  The dispersant contained in the ink composition of the present invention is not particularly limited, but those usually used for ink jet inks and the like are preferable. For example, high molecular sulfonic acid, preferably aromatic sulfonic acid formalin Examples include condensates and formalin condensates of lignin sulfonic acid. In addition, in the aromatic sulfonic acid etc. in this invention, when it describes as "sulfonic acid", it is used by the meaning containing the salt.

Examples of the aromatic sulfonic acid formalin condensate include creosote oil sulfonic acid formalin condensate, cresol sulfonic acid formalin condensate, phenol sulfonic acid formalin condensate, naphthalene sulfonic acid formalin condensate, β- Examples include a formalin condensate of naphthol sulfonic acid, a formalin condensate of β-naphthalene sulfonic acid and β-naphthol sulfonic acid, a formalin condensate of cresol sulfonic acid and 2-naphthol-6-sulfonic acid, and the like. As described above, any of these condensates may be a salt such as a sodium salt.
Among the above, the dispersant contained in the ink composition of the present invention is particularly preferably a formalin condensate of creosote oil sulfonic acid, a formalin condensate of naphthalene sulfonic acid, a formalin condensate of lignin sulfonic acid, or the like.

  These dispersants can also be obtained as commercial products. Examples of the aromatic sulfonic acid formalin condensate include, for example, Demol TRMN (trade name, manufactured by Kao Corporation), Demol TRMC (trade name, manufactured by Kao Corporation), and Demol TRM which is a special aromatic sulfonic acid formalin condensate. SNB (trade name, manufactured by Kao Corporation) and the like can be mentioned.

The water-soluble organic solvent contained in the ink composition of the present invention is not particularly limited as long as it has a wetting effect for the purpose of preventing clogging at the nozzle, and examples thereof include polyhydric alcohols and pyrrolidones. Can be mentioned. The polyhydric alcohol is, for example, a polyhydric alcohol having 2 to 3 carbon atoms having 2 to 3 alcoholic hydroxyl groups, a di- or trialkylene (2 or 3 carbon atoms) glycol, 4 or more repeating units, and a molecular weight. Examples include polyalkylene (carbon number 2 or 3) glycol of about 20,000 or less, preferably liquid polyalkylene glycol.
Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol, and the like. And monohydric alcohols, 2-pyrrolidone, N-methyl-2-pyrrolidone and the like. In addition, a compound that dissolves in water and serves as a wetting agent is also included in the water-soluble organic solvent in the present invention, and examples thereof include urea, ethylene urea, and saccharides.

Furthermore, in consideration of storage stability, a solvent having a low solubility of the monoazo dye is preferable, and among these, a mixed solvent of glycerin and other solvents, preferably a mixed solvent of glycerin and other liquid polyhydric alcohols.
The content of the water-soluble organic solvent (the sum of those in the case of using a plurality of them) is preferably 5 to 40% by mass, preferably 10 to 30% by mass in the ink composition.

  The ink composition of the present invention may contain an alkylene oxide adduct of phytosterols and / or an alkylene oxide adduct of cholestanols.

  As the alkylene oxide adduct of the phytosterols, an alkylene oxide adduct having 2 to 4 carbon atoms of phytosterols is preferable, and an ethylene oxide (EO) adduct is particularly preferable. The phytosterols include both phytosterols and hydrogenated phytosterols. Examples of ethylene oxide adducts of phytosterols include ethylene oxide adducts of phytosterols and ethylene oxide adducts of hydrogenated phytosterols.

  As the alkylene oxide adduct of the cholestanols, an alkylene oxide adduct having 2 to 4 carbon atoms of cholestanols is preferable, and an ethylene oxide (EO) adduct is particularly preferable.

  The addition amount of alkylene oxide, preferably alkylene oxide having 2 to 4 carbon atoms, more preferably ethylene oxide per mole of phytosterols or cholestanols is preferably about 10 to 50 mol and HLB is about 13 to 20.

  The phytosterol ethylene oxide adduct is, for example, NIKKOLTM BPS-20, NIKKOLRTM BPS-30 (all manufactured by Nikko Chemicals Co., Ltd., EO adduct of phytosterol), NIKKOLRTM BPSH-25 (manufactured by Nikko Chemicals Co., Ltd., hydrogenated phytosterol) EO adduct) and the like can be obtained from the market.

  The ethylene oxide adduct of cholestanols can be obtained from the market as, for example, NIKKOLRTM DHC-30 (manufactured by Nikko Chemicals Co., Ltd., EO adduct of cholestanol).

An example of the method for producing the ink composition of the present invention is described below, but the production method is not limited to this method.
First, if necessary, water-insoluble monoazo dye is finely divided or finely divided, and then mixed with water, a dispersant, and an alkylene oxide adduct of phytosterols and / or an alkylene oxide adduct of cholestanols as appropriate. Then, a slurry in which the dye is dispersed is obtained, and if necessary, the concentration is adjusted by filtration and water dilution to obtain an aqueous dispersion. Usually, the above stirring and mixing is preferably performed while making the water-insoluble monoazo dye fine.
The water-soluble organic solvent may be mixed together at the time of the above mixing, but it is preferable to add the water-soluble organic solvent to an aqueous dispersion not containing them to obtain an ink composition.

  In the above ink composition production method, the concentration of the monoazo dye in the dispersed slurry is usually 15 to 35% by mass, and the concentration of the dispersant is 5 to 35% by mass. The alkylene oxide adduct of phytosterols and / or the alkylene oxide adduct of cholestanols is usually used in an amount of 3 to 45% by mass with respect to the dispersant, and 30 to 150% by mass with respect to the monoazo dye in total with the dispersant. Preferably it is 30-120 mass%, More preferably, it is about 30-100 mass%. The balance is water.

  The concentration of the monoazo dye in the aqueous dispersion after the dispersed slurry, which is the ink composition of the present invention, is diluted with water as necessary, is usually 0.3 to 35% by mass, preferably 1 to 30% by mass, More preferably, it is 3 to 10%, and the concentration of the dispersant is usually 1 to 35% by mass, preferably 2 to 30% by mass, and more preferably 3 to 25% by mass. The concentration of the alkylene oxide adduct of phytosterols and / or the alkylene oxide adduct of cholestanols is usually 0.1 to 15% by mass, and a particularly preferred embodiment is an ethylene oxide adduct and / or cholestanols of phytosterols. This is a case of containing 0.9 to 11.25% by mass of an ethylene oxide adduct. The balance is water and a water-soluble organic solvent.

As a method of mixing the above monoazo dye with other components while making fine particles, a method known per se is used for stirring and mixing using a sand mill (bead mill), roll mill, ball mill, paint shaker, ultrasonic disperser, microfluidizer, etc. Etc. Among these, a sand mill (bead mill) is preferable. In the pulverization of the dye by a sand mill (bead mill), it is particularly preferable to use beads having a small diameter and to perform the treatment under a condition in which the pulverization efficiency is increased by increasing the filling rate of beads.
Furthermore, it is preferable to remove the beads used for dispersion by filtration, centrifugation, or the like after the pulverization treatment.

  Since some dispersants have foaming properties, it is preferable to use grinding conditions that suppress foaming as much as possible in order to increase grinding efficiency. In some cases, silicone-based, acetylene alcohol-based, etc. A very small amount of a foaming agent or the like may be added during grinding. However, some antifoaming agents inhibit dispersion and micronization, and it is preferable to use those that do not affect the stability after micronization or dispersion.

  The particle diameter of the monoazo dye in the ink composition of the present invention thus obtained is preferably about 50 to 150 nm as a volume average median diameter measured by a particle size distribution meter.

  The ink composition of the present invention may contain additives as necessary depending on the purpose of use. The ink additive that is added as necessary may coexist and be mixed together when mixing the above-mentioned monoazo dye and the other components. It is preferable to prepare an ink composition by adding an additive or the like.

  Examples of the additive include antiseptic / antifungal agents, pH adjusters and the like. Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, and 1-benz. And an amine salt of isothiazolin-3-one. 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 total content of these additives is about 0 to 10%, preferably about 0.05 to 5%, based on the entire ink composition. As described above, the ink composition of the present invention can be prepared by dispersing or mixing each component in water by a method known per se such as stirring and mixing using a homogenizer.

  The ink composition of the present invention is usually 2 to 10 mPa · s when the viscosity at 25 ° C. is measured with an E-type viscometer, and the surface tension is measured by a plate method from the viewpoint of ejection responsiveness at high speed. Usually, it is preferably in the range of 20 to 40 mN / m. Specifically, it may be adjusted to an appropriate physical property value in consideration of the discharge amount, response speed, ink droplet flight characteristics, etc. of the printer to be used. It is preferable to adjust the viscosity with the amount of a dispersant or a water-soluble organic solvent, and the surface tension with a silicone-based or acetylene alcohol-based antifoaming agent.

  The present invention also includes an ink set for ink jet textile printing comprising an ink composition containing the above monoazo dye. The ink set is an ink set used for inkjet printing of a fabric polyester made of polyester fiber or the like, and may include a cyan ink composition and / or a yellow ink composition, or a black ink composition. Also good. As the cyan ink composition, C.I. I. Examples thereof include an ink composition containing 0.1 to 20% by mass, preferably 0.5 to 7% by mass of Disperse Blue 60. The yellow ink composition includes C.I. I. Examples thereof include an ink composition containing 0.1 to 20% by mass, preferably 0.5 to 7% by mass of Disperse Yellow 114.

  The cyan ink composition may contain other colorants for the purpose of adjusting the color tone. Examples of the colorant include C.I. I. Disperse Blue 27, 54, 73, 77, 79, 79: 1, 87, 143, 165, 165: 1, 165: 2, 181, 185, 197, 225, 257, 266, 267, 281, 341, 353, Blue dyes such as 354, 358, 364, 365, and 368 are listed. Further, other disperse dyes may be included.

  The red ink composition may contain a colorant other than the dyes of the above formulas (2) and (3) for the purpose of adjusting the color tone. Examples of the colorant include C.I. I. Disperse Red 73, 88, 91, 92, 111, 127, 131, 143, 145, 146, 152, 153, 154, 179, 191, 192, 206, 221, 258, 283, 302, 323, 328, 359, etc. Red dyes. Furthermore, other reactive dyes may be included.

  The yellow ink composition may contain other colorants for the purpose of adjusting the color tone. Examples of the colorant include C.I. I. Examples include yellow dyes such as Disperse Yellow 42, 49, 76, 83, 88, 93, 99, 119, 126, 160, 163, 165, 180, 183, 186, 198, 199, 200, 224, and 237. . Furthermore, other reactive dyes may be included.

  These colorants that may be added for the purpose of adjusting the color tone may be in a powdery or lump dry state, or in a wet cake or slurry state. A dispersion agent such as a surfactant may be added for the purpose of suppressing particle aggregation during or after the synthesis of the colorant. These commercially available colorants include grades for industrial dyeing, resin coloring, ink, toner, inkjet, etc., and the production method, purity, particle size, and the like are different. In order to suppress agglomeration after pulverization, those having smaller particles are preferable.

  In order to reduce the adverse effects on dispersion stability and ink ejection accuracy, the ink composition is preferably prepared using a material having as few impurities as possible. In particular, water that is not subjected to purification operations may contain metal ions such as calcium ions and magnesium ions, and when such water is used during the preparation of the ink composition, the ions and the like are mixed in a trace amount. To do. In the present specification, including these inorganic salts and metal ions, for convenience, they are described as “inorganic impurities”. Inorganic impurities not only significantly reduce the solubility and storage stability of the ink composition, but also cause corrosion and wear of the inkjet printer head. In order to remove these inorganic impurities, it is desirable to remove as much as possible the inorganic impurities contained in the ink composition by using a known method such as an ultrafiltration method, a reverse osmosis method or an ion exchange method. The amount of inorganic impurities contained in the total amount of the ink composition is usually 1% by mass or less, preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.

The inkjet printing method of the present invention is a printing method in which a coloring agent is printed on a hydrophobic fiber, for example, a polyester fiber, and then steamed or baked by a known method to dye the dye in the ink into the hydrophobic fiber. It is. Steaming can be carried out with a high temperature steamer, usually at 170 to 180 ° C., usually for about 10 minutes, and with a high pressure steamer, usually at 120 to 130 ° C., usually for about 20 minutes (wet heat fixation). In baking (thermosol), it can be dyed by a treatment of usually 190 ° C. to 210 ° C., usually about 60 to 120 seconds (dry heat fixation). In any method, after dyeing, it is preferable from the standpoint of fiber fastness to wash away undyed dye on the fiber surface by a method known per se, for example, alkali reduction washing or soaping treatment.
Moreover, the dyeing | staining obtained by the inkjet dyeing | staining method of this invention is also contained in this invention.

Examples of the hydrophobic fibers include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended products using two or more of these fibers. Further, it may be a blended product of these and recycled fibers such as rayon or natural fibers such as cotton, silk and wool.
These hydrophobic fibers are preferably provided with an ink receiving layer (bleeding prevention layer). The method for forming the ink receiving layer is a generally known technique. The ink receiving layer can be provided on the hydrophobic fiber by applying this technique, and the fiber having the ink receiving layer is commercially available. . The ink receiving layer is not particularly limited as long as it has the function.

  According to the present invention, an ink composition for inkjet printing of a monoazo dye having a wide color reproducibility in a hue range of red to violet to blue to cyan and having excellent light fastness and storage stability can be obtained. The composition is also excellent in ejection stability.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. Unless otherwise specified in the examples, “part” means “part by mass” and “%” means “% by mass”.
The viscosity is R-115 type viscometer (E type) manufactured by Toki Sangyo Co., Ltd., the surface tension is CBVP-Z type surface tension meter (plate method) manufactured by Kyowa Interface Science Co., Ltd., and the average particle size is 0.5% of the colorant concentration. It diluted with the ion exchange water to the mass%, and measured the volume average median diameter using the Nikkiso particle size distribution analyzer Nanotrac UPA-EX150. As for the hue, ΔE ^{* and the} like were measured by measuring the color of the dyed cloth using a colorimeter manufactured by GRETAG-MACBETH, trade name: SpectroEye.

[Synthesis Example 1]
2,6-Dichloro-3-cyano-4-methylpyridine (20 parts), isopropanol (40 parts) and aniline (20 parts) were stirred at about 90 to 100 ° C. for 10 hours. Next, the reaction solution was cooled and poured into a mixture of about 150 parts of water, 20 parts of concentrated hydrochloric acid, and 20 parts of ice under stirring. The mixture was further stirred for 1 hour, and the precipitate was subjected to suction filtration and washed with water until neutrality. After drying, 26 parts of a mixture of compounds represented by the following formulas (4) and (5) were obtained.

  24 parts of this mixture were stirred at 120-130 ° C. for 4 hours with 31 parts of 2- (2-aminoethoxy) ethanol. Next, the reaction solution was cooled, 200 parts of water was added to the mixture, and the mixture was acidified with hydrochloric acid to a pH of about 0-1. Here, a small amount of ice was added and cooled so that the liquid temperature did not exceed 30 ° C. Thereby, a reaction solution in which a mixture of coupling components having a structure represented by the following formulas (6) and (7) was dissolved was obtained.

Ice was further added to this reaction liquid, it cooled at 0-10 degreeC, and the diazonium salt solution was added. The diazonium salt solution can be obtained by adding 50 parts of 90% concentrated sulfuric acid to 16 parts of 2-cyano-4-nitroaniline, cooling to 0-5 ° C., and then adding 31 parts of 40% nitrosylsulfuric acid solution little by little. It was. After stirring for 2 hours, excess nitrosylsulfuric acid was quenched by a conventional method.
After the diazonium salt solution was dropped, caustic soda was gradually added so that the pH of the reaction solution was 2 to 3. After completion of the above coupling reaction, the mixture is heated to 70 to 80 ° C., filtered, washed with water, and dried to obtain 43 parts of the mixture of the compounds represented by the above formulas (2) and (3). Obtained.

[Example 1]
(1) Aqueous dispersion Each component having the composition ratio shown in Table 1 is subjected to a dispersion treatment for about 15 hours under water cooling using 0.2 mm diameter glass beads in a sand mill. After the dispersion treatment is completed, 150 parts of ion-exchanged water is added. In addition, each aqueous dispersion having a dye concentration of 15% was prepared. Next, the dispersion was filtered with glass fiber filter paper GC-50 (manufactured by Toyo Filter Paper Co., Ltd.) to remove coarse particles. Each aqueous dispersion obtained had a dye concentration of about 15%, an average particle size of 120 nm, and a viscosity of 5.5 mPa · s.
Labelin WRTM is a formalin condensate powder of creosote oil sulfonic acid manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (15 parts of the condensate powder is mixed with 40% aqueous solution with ion-exchanged water), and NIKKOLRTM BPS-30. Is an EO (30) adduct of phytosterol manufactured by Nikko Chemicals Co., Ltd. 10% Surfynol RTM104PG is a 10-fold dilution of acetylene alcohol-based antifoaming agent manufactured by Air Products with propylene glycol. .

(2) Ink composition A red ink composition was prepared by mixing with the formulation shown in Table 2, and pressure filtered through a 0.8 micron filter (DISMIC 25CS080AN) to obtain an ink composition for printing. The viscosity was 3.5 mPa · s, the average particle size was 120 nm, and the surface tension was 37.9 mN / m.

(3) Textile printing The obtained ink composition was printed on a polyester fiber provided with an ink receiving layer by a commercially available printer (PM-740C manufactured by Seiko Epson Corporation), and steaming was performed at 175 ° C. for 8 minutes with a high temperature steamer. Then, alkali reduction washing was performed, and drying was performed for 30 minutes with a dryer at 80 ° C. to obtain a dyed fabric.
The light fastness of dyed polyester taffeta (manufactured by ATLAS; xenon, test bath temperature 42 ° C., relative humidity 30%, irradiance 1.1 W / m ² , 72 h) has zero color difference (ΔE ^* ) before and after irradiation. .90, and water fastness (JIS L-0846, A) fading color = 4-5 grade, water fastness (JIS L-0846, A) PET (polyethylene terephthalate) contamination = 4-5 grade It was the standard.

[Reference Example 1]
An aqueous dispersion was obtained in the same manner as in Example 1 with the formulation shown in Table 3. The dye concentration of the aqueous dispersion was about 15%, the average particle size was 70 nm, and the viscosity was 4.5 mPa · s.

  A cyan ink composition having the formulation shown in Table 4 was prepared in the same manner as in Example 1 to obtain an ink composition for printing. The viscosity was 3.6 mPa · s, the average particle size was 70 nm, and the surface tension was 36.8 mN / m. The obtained ink composition was dyed in the same manner as in Example 1 to obtain a dyed fabric.

[Reference Example 2]
An aqueous dispersion was obtained in the same manner as in Example 1 with the formulation shown in Table 5. The dye concentration of the aqueous dispersion was about 15%, the average particle size was 100 nm, and the viscosity was 5.0 mPa · s.

  A yellow ink composition having the formulation shown in Table 6 was prepared in the same manner as in Example 1 to obtain an ink composition for textile printing. The viscosity was 3.3 mPa · s, the average particle size was 100 nm, and the surface tension was 36.2 mN / m. The obtained ink composition was dyed in the same manner as in Example 1 to obtain a dyed fabric.

[Example 2]
The red ink composition of Example 1: the cyan ink composition of Reference Example 1 was printed on polyester fibers provided with an ink receiving layer with a commercially available printer (PM-740C manufactured by Seiko Epson Corporation) at a ratio of 3: 1. A dyed fabric was obtained in the same manner as in Example 1.

  For comparison with the present invention, instead of the monoazo dyes of the formulas (2) and (3) used in Example 1, C.I. I. Disperse Red 152 and 154 were used to prepare red inks of comparative examples. Note that C.I. I. Disperse Red 152 is Kayalon Polyester Light Red BS 200 manufactured by Nippon Kayaku Co., Ltd. I. Disperse Red 154 can be obtained as Kayalon Polyester Red BR-S manufactured by Nippon Kayaku Co., Ltd.

[Comparative Example 1]
An aqueous dispersion was obtained in the same manner as in Example 1 with the formulation shown in Table 7. The aqueous dispersion had a dye concentration of 15%, an average particle size of 90 nm, and a viscosity of 4.5 mPa · s.

  A red ink composition having the formulation shown in Table 8 was prepared in the same manner as in Example 1 to obtain an ink composition for textile printing. The viscosity was 4.0 mPa · s, the average particle size was 90 nm, and the surface tension was 38.3 mN / m. The obtained ink composition was dyed in the same manner as in Example 1 to obtain a dyed fabric.

[Comparative Example 2]
An aqueous dispersion was obtained in the same manner as in Example 1 with the formulation shown in Table 9. The dye concentration of the aqueous dispersion was 15%, the average particle size was 100 nm, and the viscosity was 5.0 mPa · s.

  A red ink composition having the formulation shown in Table 10 was prepared in the same manner as in Example 1 to obtain an ink composition for textile printing. The viscosity was 4.0 mPa · s, the average particle size was 90 nm, and the surface tension was 37.6 mN / m. The obtained ink composition was dyed in the same manner as in Example 1 to obtain a dyed fabric.

[Comparative Example 3]
The red ink composition of Comparative Example 1: The cyan ink composition of Reference Example 1 was printed on a polyester fiber provided with an ink receiving layer by a commercially available printer (PM-740C manufactured by Seiko Epson Corporation) at a ratio of 3: 1. A dyed fabric was obtained in the same manner as in Example 1.

[Comparative Example 4]
The red ink composition of Comparative Example 2: The cyan ink composition of Reference Example 1 was printed at a ratio of 3: 1 to a polyester fiber provided with an ink receiving layer by a commercially available printer (PM-740C manufactured by Seiko Epson Corporation). A dyed fabric was obtained in the same manner as in Example 1.

[Evaluation of hue of each dyed fabric]
The hue of each test dyed cloth obtained in Examples 1 and 2, Reference Examples 1 and 2, and Comparative Examples 1, 2, 3, and 4 was evaluated. Hue evaluation was performed by measuring each a dyed cloth using a colorimeter SpectroEye (trade name) manufactured by GRETAG-MACBETH and measuring a ^* and b ^* . It can be said that the smaller the value of b ^*, the wider the color reproduction range and the better. The results are shown in Table 11.

[Evaluation of light fastness of each dyed fabric]
The light fastness of each test dyed cloth obtained in Examples 1 and 2 and Comparative Examples 1, 2, 3 and 4 was evaluated. The light fastness was irradiated for 72 h under the conditions of a test bath temperature of 42 ° C., a relative humidity of 30%, and an irradiance of 1.1 W / m ² using a light resistance tester manufactured by ATLAS. The hue evaluation was performed by measuring each dyed cloth using a colorimeter SpectroEye (trade name) manufactured by GRETAG-MACBETH and measuring Δa ^* , Δb ^* , and ΔE ^* . It can be said that the smaller the value of ΔE ^*, the less fading and the better the fastness. The results are shown in Table 12.

  From the results of Tables 11 and 12, the dyed fabric printed with the ink set for inkjet textile printing of the present invention has a wide color reproduction range in the hue range of red to violet to blue to cyan as compared with each comparative example. It is clear that this is a high-quality dyed cloth with excellent light fastness.

Claims (8)

An ink composition comprising a monoazo dye represented by the following general formula (1), water, a dispersant, and a water-soluble organic solvent.

(In the formula, R ¹ and R ² are each independently a hydrogen atom, a phenyl group which may have a substituent, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or aralkyl. R ³ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ³ are present, they may be the same (N may be an integer of 1 to 5.) The ink composition according to claim 1, wherein the monoazo dye is a mixture of a compound represented by the following formula (2) and a compound represented by the following formula (3).

  The ink composition according to claim 1 or 2, further comprising an ethylene oxide adduct of phytosterols and / or an ethylene oxide adduct of cholestanols.   The monoazo dye is contained in an amount of 3 to 10% by mass, a dispersant is contained in an amount of 3 to 25% by mass, and an ethylene oxide adduct of phytosterols and / or an ethylene oxide adduct of cholestanols is contained in an amount of 0.9 to 11.25% by mass. The ink composition described in 1.   It is an ink set used for inkjet textile printing, Comprising: An ink set provided with the ink composition as described in any one of Claims 1-4 as a red ink composition.   Furthermore, C.I. I. Cyan ink composition containing Disperse Blue 60 as a colorant and / or C.I. I. The ink set according to claim 5, comprising a yellow ink composition containing Disperse Yellow 114 as a colorant.   A method for inkjet printing of hydrophobic fibers, wherein the ink set according to claim 5 or 6 is used, and a colorant is printed on the hydrophobic fibers by an ink jet method, followed by a steaming or baking treatment.   A dyed product obtained by the inkjet printing method according to claim 7.