JPWO2018097061A1 - Ink, ink set, and textile printing method - Google Patents

Abstract

C. I. Reactive Blue 176 and C.I. I. Reactive Red 245 and C.I. I. Reactive Orange 13 and C.I. I. A reactive dye containing at least one of Reactive Orange 99 and an ink containing urea are provided. Also provided are an ink set comprising the ink as a black ink, a textile printing method using the ink or the ink set, and a dyed fiber.

Description

  The present invention relates to an ink and an ink set containing reactive dyes, and a fiber printing method using them.

Compared with textile printing methods such as screen textile printing, roller textile printing, rotary textile printing, etc.
(1) The plate making process is unnecessary and the process can be shortened.
(2) The ability to print the digitized design as it is via a computer;
(3) It is possible to produce a wide variety of products even in small quantities.
(4) Dye color paste waste liquid can be greatly reduced,
There are many merits such as. On the other hand, inkjet printing has problems such as slower printing speed and difficulty in reproducing dark colors compared to conventional plate-making printing, and should be used in the range of sample production and small-scale production. There were many.

  In recent years, with the progress of computer image processing technology and industrial inkjet printhead manufacturing technology, the printing speed of inkjet printers has been greatly improved. In addition to this, the digitization of printing designs, the diversification of printing processes, and the small lots have been demanded in the market, and industrial inkjet printing has been spreading.

  By the way, reactive dyes are used in inks for ink jet printing used for dyeing cellulose fibers such as cotton and rayon. In reactive dyes, reactive groups that react with the fibers present in the dye molecule react with hydroxy groups and the like present in the fibers, and form a covalent bond between the dye and the fibers, thereby fixing to the fibers. . However, in ink jet textile printing, ink droplets are ejected to form an image, so that ink used in conventional textile printing methods such as screen textile printing cannot be directly applied to ink jet textile printing. In order to ensure the ink jet characteristics, it is necessary to adjust not only the physical characteristics such as the surface tension and viscosity of the ink but also the composition of the solvent and the concentration of the color material. Due to such limitations, it is difficult for the conventional inkjet printing to increase the dyeing density of the dyed fabric, and various attempts have been made for these problems.

  For example, Patent Document 1 proposes an ink containing a reactive dye and thiodiglycol as an ink for inkjet printing from which a high-density printed fabric can be obtained. Patent Documents 2 and 3 propose inks containing reactive dyes and 1,2-alkanediol as inks for ink jet printing that can obtain a high-density printed fabric.

Japanese Patent No. 3323549 JP 2004-292523 A JP 2011-195675 A

  An object of the present invention is to provide an ink containing a reactive dye and capable of high-density dyeing, an ink set including the ink, and a textile printing method using the ink.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention described in the following 1) to 27).

1)
C. I. Reactive Blue 176 and C.I. I. Reactive Red 245 and C.I. I. Reactive Orange 13 and C.I. I. A reactive dye containing at least one of Reactive Orange 99 and an ink containing urea.
2)
The reactive dye is C.I. I. The ink according to 1), including Reactive Orange 13.
3)
The reactive dye is C.I. I. The ink according to 1), including Reactive Orange 99.
4)
The reactive dye is C.I. I. Reactive Orange 13 and C.I. I. The ink according to 1), including Reactive Orange 99.
5)
Any one of 1) to 4), which contains a water-soluble organic solvent having a dipole moment value (δP value) containing at least one cyclic amide-based solvent within a range of 9 to 30 MPa ^1/2 and water. The ink according to item.
6)
The ink according to 5), wherein a dipole moment value (δP value) of the water-soluble organic solvent is in a range of 9 to 20 MPa ^1/2 .
7)
The ink according to 5) or 6), wherein the cyclic amide solvent is 2-pyrrolidone.
8)
The ink according to 7), wherein the content of 2-pyrrolidone is 5 to 20% by mass.
9)
The ink according to any one of 1) to 8), wherein the urea content is 5 to 20% by mass.
10)
It contains 2-pyrrolidone, the total content of 2-pyrrolidone and urea is 15 to 30% by mass, and the content ratio of 2-pyrrolidone and urea is 1: 2 to 2: 1 on a mass basis. Yes (except that the total content of 2-pyrrolidone and urea is 15% by mass and the content ratio of 2-pyrrolidone and urea is 2: 1 on a mass basis), 1) to The ink according to any one of 9).
11)
The ink according to any one of 1) to 10), which contains a pH adjuster.
12)
The ink according to 11), wherein the pH adjuster is tris (hydroxymethyl) aminomethane.
13)
C. I. The ink according to any one of 1) to 12), wherein the content of Reactive Blue 176 is 5 to 15% by mass.
14)
C. I. The ink according to 13), wherein the content of Reactive Blue 176 is 8 to 12% by mass.
15)
The ink according to any one of 1) to 14), which comprises at least one of a nonionic surfactant and an anionic surfactant.

16)
An ink set comprising black ink and at least one of magenta ink and cyan ink,
The black ink is the ink according to any one of 1) to 15),
The magenta ink is C.I. I. Containing Reactive Red 245 as reactive dye,
The cyan ink is C.I. I. Reactive Blue 15: 1 and C.I. I. An ink set containing at least one of Reactive Blue 72 as a reactive dye.

17)
1) to 15) an attachment step of causing the ink droplets according to any one of 15) to be ejected by an inkjet printer and attached to the fiber;
A reactive fixing step in which the reactive dye in the ink attached to the fiber in the attaching step is reactively fixed to the fiber by heat; and
A washing step of washing unfixed reactive dye remaining in the fiber;
A textile printing method comprising:
18)
The fiber according to 17), further comprising a pretreatment step of adhering an aqueous solution containing one or more types of glue material, a pretreatment pH adjuster, and a hydrotropic agent to the fiber before the adhesion step. Printing method.
19)
16) an attachment process in which each ink droplet included in the ink set is ejected by an ink jet printer and adhered to the fiber;
A reactive fixing step in which the reactive dye in the ink attached to the fiber in the attaching step is reactively fixed to the fiber by heat; and
A washing step of washing unfixed reactive dye remaining in the fiber;
A textile printing method comprising:
20)
The fiber according to 19), further comprising a pretreatment step of adhering an aqueous solution containing one or more types of glue material, a pretreatment pH adjuster, and a hydrotropic agent to the fibers before the adhesion step. Printing method.
21)
The inkjet printer is a scanning inkjet printer,
The textile printing method according to 19) or 20), wherein, in the attaching step, the black ink and at least one of the magenta ink and the cyan ink are attached to the fiber in an overlapping manner.
22)
21. The textile printing method according to 21), wherein, in the attaching step, the black ink, the magenta ink, and the cyan ink are attached to the fiber in an overlapping manner.
23)
The textile printing method according to 21) or 22), wherein the black ink discharge amount is larger than the other ink discharge amounts.
24)
The textile printing method according to any one of 17) to 23), wherein the fiber is a cellulose fiber or a polyamide fiber.
25)
The fiber printing method according to 24), wherein the fiber is a cellulosic fiber.

26)
Fiber dye | stained using the ink as described in any one of 1) -15), or the ink set as described in 16).
27)
A fiber dyed by the printing method according to any one of 17) to 23).

  ADVANTAGE OF THE INVENTION According to this invention, the reactive dye is contained and the ink which can be dye | stained with high density | concentration, the ink set provided with the ink, and the textile printing method using them can be provided.

<Ink>
The ink according to this embodiment is C.I. I. Reactive Blue 176 and C.I. I. Reactive Red 245 and C.I. I. Reactive Orange 13 and C.I. I. Reactive dye containing at least one of Reactive Orange 99, and urea. According to such an ink, it is possible to dye black with a high dyeing density.

[Reactive dye]
The ink according to this embodiment is C.I. I. As a reactive dye selected from Reactive Blue, C.I. I. Contains Reactive Blue 176. C. I. Reactive Blue 176 is a C.I. I. It is a reactive dye, also called Reactive Black 39, which has excellent color developability and a clear navy color.

  C. I. The content of Reactive Blue 176 is preferably 5 to 15% by mass and more preferably 8 to 12% by mass in the total amount of ink.

  C. I. Reactive Blue 176 is generally known as a Na salt compound, but can be changed to a salt other than Na salt according to the required characteristics of the ink.

C. I. Examples of salts other than the Na salt that Reactive Blue 176 may have include salts with inorganic cations or organic cations. Specific examples of the salt with an inorganic cation include a salt with an alkali metal such as Li and K, a salt with an alkaline earth metal such as Ca and Mg, and an ammonium salt (NH ₄ ⁺ ). Specific examples of the salt with an organic cation include quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetrabutylammonium salt. Among these, a salt with a monovalent cation is preferable, and a Li salt is more preferable. C. I. When Reactive Blue 176 contains a Li salt, the solubility in a solvent is improved, and the effect of improving the dyeing density during printing can be obtained.

  C. I. When Reactive Blue 176 contains Li salt, the molar ratio of Li salt to salt other than Li salt is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20. 30:70 to 70:30, more preferably 40:60 to 60:40, and particularly preferably 40:60 to 50:50. The Li ion concentration in the ink is preferably in the range of 1000 to 2000 mass ppm, more preferably in the range of 1200 to 1700 mass ppm. This Li ion concentration can be measured by a known method.

  When changing the salt as described above, as its preparation method, for example, it is possible to use a known ion exchange method such as preparation by ion exchange using a reverse osmosis membrane purification method or salt exchange crystallization, It is preferable to use a reverse osmosis membrane purification method.

  Further, the ink according to this embodiment is C.I. I. As a reactive dye selected from Reactive Red, C.I. I. Contains Reactive Red 245.

  C. I. The content of Reactive Red 245 is preferably 0.1 to 10% by mass and more preferably 1 to 8% by mass in the total amount of ink.

  Further, the ink according to this embodiment is C.I. I. As reactive dyes selected from Reactive Orange, C.I. I. Reactive Orange 13 and C.I. I. Contains at least one of Reactive Orange 99. The ink according to this embodiment is C.I. I. Reactive Orange 13 and C.I. I. It is preferable to contain both Reactive Orange 99.

  C. I. Reactive Orange 13 and C.I. I. The total content of Reactive Orange 99 is preferably 0.1 to 30% by mass and more preferably 1 to 25% by mass in the total amount of ink.

  The ink according to this embodiment may contain a reactive dye other than those described above as long as the effects of the present invention are not impaired.

  Among other reactive dyes, C.I. I. Examples of those classified as Reactive Blue include C.I. I. Reactive Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 15: 1, 16, 17, 18, 19, 19: 2, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 36: 1, 38, 39, 40, 41, 42, 43, 44, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 10 6, 107, 108, 109, 112, 113, 114, 116, 117, 118, 118: 1, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157,158,159,160,161,162,163,164,165,166,167,168,169,170,171,171: 1,172,173,174,175,177,178,179,180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190 191, 192, 193, 194, 195, 198, 197, 198, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 233, 234, 235, 236, 237, 238, 242, 243, 244, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 80,281,282,283,284, and the like.

  Among other reactive dyes, C.I. I. As what is classified into Reactive Red, for example, C.I. I. Reactive Red 1, 1: 1, 2, 3, 3: 1, 4, 5, 6, 6: 1, 7, 8, 8: 1, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 21: 1, 22, 22: 1, 23, 24, 24: 1, 25, 26, 27, 28, 29, 30, 31, 31: 1, 32, 33, 34, 35, 35: 1, 35: 2, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 45: 1, 46, 47, 48, 49, 50, 51, 51: 1, 52, 53, 54, 55, 56, 58, 59, 59: 1, 60, 60: 1, 61, 61: 1, 62, 63, 63: 1, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 73: 1, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 106: 1, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 123, 124, 125, 126, 128, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 17 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199 , 200, 201, 202, 203, 204, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225 226,227,228,229,230,231,232,233,234,235,236,237,238,238: 1,239,241,242,243,246,247,248,249,250,251 252, 253, 254, 255, 257, 258, 259, 260, 2 1,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280,281,282,283,284,285, 286, 287, 288 and the like.

  Among other reactive dyes, C.I. I. As what is classified into Reactive Orange, for example, C.I. I. Reactive Orange 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 15: 1, 16, 16: 1, 16: 2, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 28: 1, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 66, 67, 68, 69, 70, 71, 72, 72: 1, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 100, 101, 102, 10 3, 104, 105, 106, 107, 108, 109, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144 and the like.

  These other reactive dyes may be used alone or in combination of two or more. However, the content of other reactive dyes is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total amount of ink.

[urea]
The ink according to the present embodiment contains urea. The content of urea is preferably 5 to 20% by mass and more preferably 10 to 20% by mass in the total amount of ink. By setting the urea content to 5% by mass or more, the dyeing density is further increased and the drying resistance of the ink tends to be further improved. Further, when the urea content is 20% by mass or less, the high-temperature storage stability of the ink tends to be improved.

[water]
The ink according to the present embodiment is a water-based ink and contains water. The water used for preparing the ink is preferably one that has been subjected to a purification operation such as ion exchange water or distilled water. In particular, water that is not subjected to purification operations contains metal ions such as Ca ions and Mg ions. Therefore, when such water is used for ink preparation, the ions and the like are mixed in a minute amount. In this specification, such metal ions and inorganic salts are referred to as “inorganic impurities” for convenience. These inorganic impurities are preferably reduced in order to deteriorate the solubility in ink and the storage stability.

[Water-soluble organic solvent]
The ink according to this embodiment may contain a water-soluble organic solvent in addition to water. Examples of the water-soluble organic solvent 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; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyrimido-2 Heterocyclic ketones such as -one; ketones or keto alcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2- Til-1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexylene Mono-, oligo-, or polyalkylene glycols or thioglycols having C2-C6 alkylene units such as glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol; trimethylolpropane; Polyol (preferably triol) such as glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl C1-C4 monoalkyl ethers of polyhydric alcohols such as ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; γ-butyrolactone; dimethyl sulfoxide; Can be mentioned.

In particular, the ink according to this embodiment has a dipole moment value (δP value) of 9 to 30 MPa ^1/2 including at least one kind of cyclic amide solvent from the viewpoint of improving ejection stability and low-temperature storage stability. It is preferable to contain a water-soluble organic solvent within the range (preferably within the range of 9 to 20 MPa ^1/2 ). The dipole moment value (δP value) is a polarization term of a Hansen solubility parameter, and can be estimated using computer software (Hansen Solubility Parameters in Practice (HSPIP)).

  Examples of the cyclic amide solvent include a solvent in which a carboxy group and an amino group are dehydrated and condensed to form a 3- to 7-membered ring structure. Specific examples include α-lactam (21.7), β-lactam ( 17.9), ε-caprolactam (13.8), 2-pyrrolidone (12), N-methyl-2-pyrrolidone (12.3), N-ethyl-2-pyrrolidone (12), etc. The numerical value in each indicates the δP value). A cyclic amide solvent may be used individually by 1 type, and may use 2 or more types together.

  The ink according to this embodiment preferably contains 2-pyrrolidone among the cyclic amide solvents. The content of 2-pyrrolidone is preferably 5 to 20% by mass and more preferably 8 to 12% by mass in the total amount of ink.

  In addition, when the ink which concerns on this embodiment contains 2-pyrrolidone, the total content rate of 2-pyrrolidone and urea is 15-30 mass%, and the content ratio of 2-pyrrolidone and urea is mass. 1: 2 to 2: 1 on the basis (however, the total content of 2-pyrrolidone and urea is 15% by mass, and the content ratio of 2-pyrrolidone and urea is 2: 2 on the mass basis). 1 is preferred).

Examples of water-soluble organic solvents having a dipole moment value (δP value) in the range of 9 to 30 MPa ^1/2 other than cyclic amide solvents include, for example, ethylene glycol (11), propylene glycol (10.4). ), Glycerin (11.3), trade names manufactured by Idemitsu Kosan Co., Ltd. Ecamide B-100 (9) and Ecamide M-100 (10.4), 1,4-butanediol (11), ethylene urea (17 .6), 2-methyl-1,3-propanediol (9.2), cinnamide (27.6), etc. (all numerical values in parentheses indicate δP values). One type of water-soluble organic solvent other than the cyclic amide solvent may be used alone, or two or more types may be used in combination.

  The ink according to this embodiment preferably contains at least one of ethylene glycol and propylene glycol, and more preferably contains both ethylene glycol and propylene glycol, among water-soluble organic solvents other than cyclic amide solvents. . The total content of ethylene glycol and propylene glycol is preferably 1 to 50% by mass and more preferably 5 to 40% by mass in the total amount of ink.

[Other ingredients]
The ink according to this embodiment includes, as other components, a pH adjuster, an antiseptic / antifungal agent, a chelating reagent, a rust preventive agent, an ultraviolet absorber, a viscosity adjusting agent, an antifading agent, a surface tension adjusting agent, an antifoaming agent, and the like. The ink preparation agent may be contained. Each ink preparation agent may be used individually by 1 type, and may use 2 or more types together.

(PH adjuster)
Examples of the pH adjuster include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; triethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine, tris (hydroxymethyl) aminomethane and the like. Tertiary amines, preferably mono-, di- or tri-C1-C4 alkylamines optionally substituted with a hydroxy group; and the like. Of these, tris (hydroxymethyl) aminomethane is preferred.

  When the ink according to this embodiment contains a pH adjuster, the content is usually 0.01 to 3% by mass, preferably 0.02 to 2.5% by mass, based on the total amount of the ink. More preferably, it is 0.05-2 mass%.

(Antiseptic and antifungal agent)
Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts. Examples of the organic halogen compound include sodium pentachlorophenol. Examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide. Examples of the isothiazoline-based compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Can be mentioned. Other antiseptic / antifungal agents include sodium acetate, sodium sorbate, sodium benzoate, trade names Proxel ^RTM GXL (S) and Proxel ^RTM XL-2 (S) manufactured by Arch Chemical Co., Ltd. The superscript RTM means a registered trademark.

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

(anti-rust)
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

(UV absorber)
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds. In addition, a compound that absorbs ultraviolet rays such as a benzoxazole-based compound and emits fluorescence, a so-called fluorescent whitening agent, and the like can also be used.

(Viscosity modifier)
Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents. Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamine, polyimine, poly C2-C3 alkylene glycol having a molecular weight of about 20000 or less, preferably liquid polyalkylene glycol. For example, polyoxypropylene diglyceryl ethers such as trade names SC-P400, SC-P750, SC-P1000, SC-P1200, SC-P1600 manufactured by Sakamoto Pharmaceutical Co., Ltd .; SC-E450, SC-E750, SC- Polyoxyethylene diglyceryl ethers such as E1000, SC-E1500, and SC-E2000; and the like, and SC-P1000 is preferably used.

(Anti-fading agent)
The anti-fading agent is used for the purpose of improving image storage stability. As the antifading agent, various organic and metal complex antifading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. . Examples of the metal complex anti-fading agent include nickel complexes and zinc complexes.

(Surface tension regulator)
Surfactant is mentioned as a surface tension regulator. Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Among the surfactants, at least one of a nonionic surfactant and an anionic surfactant is preferable.

  Examples of the anionic surfactant include alkyl sulfocarboxylates; α-olefin sulfonates; polyoxyethylene alkyl ether acetates; N-acyl amino acids or salts thereof; N-acyl methyl taurates; Alkyl ether sulfate; alkyl sulfate polyoxyethylene alkyl ether phosphate; rosin acid soap; castor oil sulfate ester; lauryl alcohol sulfate ester; alkylphenol phosphate ester; alkyl phosphate ester; alkyl aryl sulfonate salt; Examples thereof include sulfosuccinates such as oxalate, diethylhexylsilsulfate, and dioctylsulfosuccinate. Sulfosuccinic acid is preferable, and examples of commercially available products thereof include Lion Corp., trade name Ripar 835I, 860K, 870P, NTD, MSC; Adeka Co., Ltd., trade name Adeka Coal EC8600. Manufactured by Kao Co., Ltd., trade names Perex OT-P, CS, TA, and TR; manufactured by Shin Nippon Rika Co., Ltd., Rica Mild ES-100, ES-200, Rika Surf P-10, and M- 30, the same M-75, the same M-300, the same G-30, the same G-600; manufactured by Toho Chemical Industry Co., Ltd., Sakukunol L-300, the same L-40, the same L-400, the same NL-400; Etc.

  When the ink according to the present embodiment contains an anionic surfactant, the content is usually 0.05 to 2% by mass, preferably 0.05 to 1.5% by mass with respect to the total amount of the ink. %, More preferably 0.05 to 1% by mass, and still more preferably 0.1 to 0.5% by mass.

(Nonionic surfactant)
Examples of nonionic surfactants include ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether. Polyesters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate Acetylene alcohol system such as 3,5-dimethyl-1-hexyn-3-ol; 2,4,7,9-tetramethyl-5-decyne-4 7-diol, 3,6-dimethyl-4-octyne-3,6-diol, manufactured by Air Products, trade names Surfinol 104, 104PG50, 82, 420, 440, 465, 485; Acetylene glycol type such as STG; Among these, acetylene glycol type or acetylene alcohol type is preferable, and acetylene glycol type is more preferable.

  When the ink according to this embodiment contains a nonionic surfactant, the content is usually 0.05 to 2% by mass, preferably 0.05 to 1.5% by mass, based on the total amount of the ink. %, More preferably 0.05 to 1% by mass, and still more preferably 0.1 to 0.5% by mass.

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

(Amphoteric surfactant)
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 and the like.

(Defoamer)
Examples of the antifoaming agent include highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based and silicone-based compounds.

[Ink properties]
The viscosity at 20 ° C. of the ink according to the present embodiment is, for example, preferably 4 to 30 mPa · s, and more preferably 5 to 20 mPa · s.
In addition, when used in a printer equipped with an industrial inkjet head, the static surface tension at 25 ° C. of the ink according to the present embodiment is 20 from the viewpoint of improving high-speed continuous ejection under a low temperature environment. It is preferably ˜45 mN / m, and more preferably 25 to 40 mN / m.

[Ink preparation method]
In the ink according to the present embodiment, the order in which the components are added is not particularly limited, and the ink may be prepared by mixing until substantially becoming a solution by stirring. As described above, it is preferable to use water having a small amount of inorganic impurities such as distilled water and ion-exchanged water as the water used in preparing the ink.

  The ink is preferably subjected to microfiltration using a membrane filter or the like, and a filtrate from which impurities are removed is preferably used. The pore size of the filter when performing microfiltration is usually 0.1 to 1.0 μm, preferably 0.1 to 0.8 μm. The content of inorganic impurities is usually 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, based on the total amount of ink. A lower limit can be made below the detection limit of a detection apparatus, ie, 0 mass%. And after removing an inorganic impurity, it can adjust to a desired dye density | concentration by dilution or concentration, and can obtain an ink.

<Ink set>
The ink set according to the present embodiment includes black ink and at least one of magenta ink and cyan ink. The ink set according to the present embodiment preferably includes both magenta ink and cyan ink.

  Since the ink according to the present embodiment described above is used as the black ink, detailed description thereof is omitted.

  Magenta ink is a C.I. I. Reactive Red 245 is included as a reactive dye. C. I. The content of Reactive Red 245 is preferably 1 to 30% by mass, and more preferably 5 to 25% by mass in the total amount of magenta ink.

  Magenta ink is a C.I. I. Reactive Red 3, 3: 1, 4, 13, 24, 29, 31, 33, 125, 151, 206, 218, 226, etc. I. It may contain other reactive dyes classified as Reactive Red. However, the content of other reactive dyes is preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total amount of magenta ink.

  The cyan ink is C.I. I. Reactive Blue 15: 1 and C.I. I. At least one of Reactive Blue 72 is contained as a reactive dye. C. I. Reactive Blue 15: 1 and C.I. I. The total content of Reactive Blue 72 is preferably 1 to 30% by mass and more preferably 5 to 25% by mass in the total amount of cyan ink.

  The cyan ink is C.I. I. Reactive Blue 2, 5, 10, 13, 14, 15, 49, 63, 71, 75, 162, 176, etc. I. Other reactive dyes classified as Reactive Blue may be contained. However, the content of other reactive dyes is preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total amount of cyan ink.

  Magenta ink and cyan ink are water-based inks and contain water. Further, the magenta ink and the cyan ink may contain a water-soluble organic solvent and other ink preparation agents, similarly to the ink according to the present embodiment described above.

<Fiber printing method and dyed fiber>
The fiber printing method according to this embodiment is a method of printing on fibers (preferably cellulosic fibers or polyamide fibers) using the ink according to this embodiment described above or the ink set according to this embodiment. . More specifically, it is preferable to print on a fabric mainly composed of cellulosic fibers or polyamide fibers. Examples of the cellulosic fibers include natural fibers such as cotton and hemp, regenerated cellulose fibers such as rayon, and blended fibers containing these.

Examples of the textile printing method include a method of sequentially performing the following three steps.
(Adhesion process)
Ink droplets are ejected by an ink jet printer and adhered to the fiber.
(Reaction fixing process)
The reactive dye in the ink attached to the fiber in the attaching step is reactively fixed to the fiber by heat.
(Washing process)
Unreacted reactive dye remaining in the fiber is washed.

  There is no restriction | limiting in particular about the ink nozzle of an inkjet printer, According to the objective, it can select suitably. Also, the printing method of the ink jet printer is not particularly limited, and an arbitrary printing method such as a scanning method or a single pass method can be selected.

  As the attaching step, there is a method in which a container filled with the ink according to the present embodiment described above is loaded in a predetermined position of the ink jet printer, and the ink droplets are ejected in accordance with a recording signal to adhere to the fiber. Can be mentioned. When using the ink set according to the present embodiment described above, a container filled with each ink is loaded in a predetermined position of the ink jet printer, and each ink droplet is ejected in accordance with a recording signal to adhere to the fiber. Just do it.

  Examples of the reaction fixing step include a method in which the fiber to which the ink is attached is allowed to stand at room temperature to 150 ° C. for 0.5 to 30 minutes and preliminarily dried and then subjected to a steaming treatment. The conditions for the steaming treatment include a condition in which the fibers to which the ink is attached are allowed to stand for 5 to 40 minutes in an environment with a humidity of 80 to 100% and a temperature of 95 to 105 ° C.

  As a washing | cleaning process, the method of wash | cleaning the fiber which performed the steaming process with water is mentioned. The water used for washing | cleaning may contain surfactant. The dyed fiber can be obtained by drying the fiber after washing the unfixed dye at 50 to 120 ° C. for 5 to 30 minutes.

  The textile printing method according to the present embodiment may include a pretreatment step for the fiber as a step before the attaching step. Examples of the pretreatment step include a step of attaching an aqueous solution containing one or more types of paste material, a pretreatment pH adjuster, and a hydrotropic agent to the fiber as a pretreatment solution. Although this pretreatment step is not essential, there is a case where the effect of preventing the bleeding of the dye can be obtained at the time of printing. Therefore, a printing method in which four steps including the pretreatment step are sequentially performed is preferable.

  The pH adjusting agent contained in the pretreatment liquid has the same purpose of use as the pH adjusting agent contained in the ink, but preferred specific examples thereof are different. For this reason, in this specification, the pH adjuster contained in the ink is simply described as “pH adjuster”, and the pH adjuster contained in the pretreatment liquid is described as “pH adjuster for pretreatment”. Distinguish between the two.

  As paste, natural gums such as guar and locust bean, starches, seaweed such as sodium alginate, funari, plant skins such as pectic acid, methyl fibrin, ethyl fibrin, hydroxyethylcellulose, carboxymethylcellulose, etc. Examples thereof include fiber derivatives, processed starches such as carboxymethyl starch, processed natural gums such as shiratsu gum and roast bean gum, and synthetic glues such as polyvinyl alcohol and polyacrylate. Among these, sodium alginate is preferable as the paste used for the pretreatment of the cellulosic fibers. Moreover, as a paste used for pre-processing of a polyamide fiber, natural gums such as guar and locust bean, and processed natural gums such as silat gum and roast bean gum are preferable.

  As the pH adjuster, a pH adjuster suitable for the fiber is selected. The pH adjuster used for the pretreatment of the cellulosic fiber is preferably one that exhibits alkalinity when made into an aqueous solution. For example, an alkali metal salt of an inorganic acid or an organic acid; an alkaline earth metal salt; Compounds that liberate alkali; and the like. In particular, alkali metal hydroxides and alkali metal salts of inorganic acids or organic acids are preferred. Specific examples include sodium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium phosphate and the like, and sodium bicarbonate is preferred. On the other hand, as the pH adjuster used for the pretreatment of the polyamide-based fiber, one that exhibits acidity when made into an aqueous solution is preferable. Specific examples include acidic ammonium salts such as ammonium sulfate, ammonium tartrate, and ammonium acetate, with ammonium sulfate being preferred.

  Examples of the hydrotropic agent include urea such as urea, dimethylurea, thiourea, monomethylthiourea, and dimethylthiourea, and urea is preferable.

  Each of the above-mentioned sizing agent, pH adjusting agent for pretreatment, and hydrotropic agent may be used alone or in combination of two or more.

  It is difficult to determine the contents of the above-mentioned glue, pretreatment pH adjuster, and hydrotropic agent depending on, for example, the blend ratio of each of the cellulose fibers and polyamide fibers, but as a guideline. Is 0.5 to 5% by mass of the paste, 0.5 to 5% by mass of the pH adjusting agent for pretreatment, and 1 to 20% by mass of the hydrotropic agent with respect to the total amount of the pretreatment liquid, The balance is water.

  Examples of the method for attaching the pretreatment liquid to the fiber include a padding method. The drawing ratio of padding is preferably about 40 to 90%, more preferably about 60 to 80%.

  In recent years, there has been a demand for high-quality ink-jet printed products that have not only high density but also high-definition and suppressed graininess peculiar to ink-jet, and it is possible to discharge micro droplets of several pL to 10 pL. Inkjet printers equipped with various inkjet heads have been developed. However, when such an ink jet printer is used, the amount of ink per droplet per dyed fabric is small, and it becomes difficult to achieve a high density by printing once. It is necessary to print the same part repeatedly, and the production speed is significantly reduced. This is remarkable in the black color where high density is strongly required.

  Therefore, when printing on a fiber using the ink set according to the above-described embodiment, the black ink and at least one (preferably both) of magenta ink and cyan ink are overlapped and adhered to the fiber. Also good. For example, a black ink and at least one of magenta ink and cyan ink may be overlapped and adhered to the fiber using a scanning ink jet printer. In this way, by overlapping the black ink and at least one of the magenta ink and the cyan ink and attaching them to the fiber, it is possible to obtain a clear black ink-jet printed matter having a high dyeing density without repeated printing. it can.

  When the black ink and at least one of the magenta ink and the cyan ink are overlapped and adhered to the fiber, the discharge amount of the black ink is preferably larger than the discharge amounts of the other inks.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples. In Examples, “part”, “%”, and “ppm” are based on mass unless otherwise specified.

<Example 1>
[Preparation of ink]
C. adjusted to a concentration of about 1 to 10%. I. A solution of Reactive Blue 176 (Na salt) was added to a lithium hydroxide solution by a reverse osmosis membrane purification method and then evaporated to dryness to adjust the Li ion concentration to about 15000 ppm. I. A dry powder of Reactive Blue 176 was obtained. Then, each component (unit: part) described in Table 1 below was mixed and stirred for about 1 hour until the solid content was dissolved in a state where the liquid temperature was maintained at 40 ° C., and then a 0.45 μm membrane filter (cellulose) A test ink was prepared by filtering through an acetate filter paper (manufactured by Advantech).

The abbreviations in Table 1 have the following meanings.
RB176 ... C. I. Reactive Blue 176
RO13 ... C. I. Reactive Orange 13
RO99 ... C. I. Reactive Orange 99
RR245 ... C. I. Reactive Red 245
2PD ... 2-pyrrolidone EG ... ethylene glycol PG ... propylene glycol SC-P1000 ... polyoxypropylene diglyceryl ether SF440 ... surfinol 440 (acetylene glycol surfactant)
GXL ... Proxel ^RTM GXL
THMAM ... Tris (hydroxymethyl) aminomethane

[Viscosity evaluation]
The viscosity of the ink of Example 1 at 20 ° C. was measured using an E-type viscometer. The results are shown in Table 2 below. The unit of this viscosity is mP · s.

[Evaluation of solubility during ink preparation]
The solubility of RB176 at the time of ink preparation was evaluated. After mixing each component described in Table 1 above and stirring for about 1 hour until the solid content was dissolved in a state where the liquid temperature was maintained at 40 ° C., the ink was obtained and left at room temperature. evaluated. The results are shown in Table 2 below.
(Evaluation criteria)
A: No precipitate is observed even after standing for 7 days or more.
B: Precipitates are not observed in less than 7 days, but precipitates are observed when left for 7 days or longer.
C: Slight deposits are observed when left for 3 days or more and less than 7 days.
D: A clear precipitate is observed in less than 3 days.

[Low temperature storage stability evaluation]
The low temperature storage stability of the ink of Example 1 was evaluated. The low-temperature storage stability was evaluated by the following criteria after storage at −5 ° C. for 3 days and then standing at room temperature for several hours. The results are shown in Table 2 below.
(Evaluation criteria)
A: Precipitation of dye and gelation of ink are not confirmed.
B: There is slight sedimentation of the dye, but no gelation of the ink is confirmed.
C: Precipitation of the dye is considerable or gelation of the ink is confirmed.

[Inkjet printing]
A pretreatment liquid containing sodium alginate, urea, and sodium bicarbonate was attached to the cotton cloth by the pad method, and then dried to obtain a pretreated cotton cloth. The pretreated cotton fabric was cut into A4 size.

  The container filled with the ink of Example 1 was loaded into an industrial inkjet head evaluation apparatus (expandable coating apparatus EV2500; manufactured by Ricoh Co., Ltd.), and the pretreated cotton cloth was 200 mm × 250 mm in an environment of 25 ° C. A solid pattern was printed. The obtained cotton fabric was dried at 60 to 80 ° C. and then subjected to a steaming treatment at 100 to 103 ° C. for 10 minutes. The obtained cotton fabric was washed successively with water, boiling water at 95 to 100 ° C. (10 minutes), and water, and then dried to obtain a printed fabric for evaluation. Using the dyed cloth as a test sample, the following evaluation test was performed. When color measurement was necessary in the evaluation test, a colorimeter manufactured by GRETAG-MACBETH (trade name: SpectroEye) was used.

[Dye density test]
After measuring the reflection density of the dyed cloth with the above colorimeter to obtain the Dk value, the dyeing density was evaluated according to the following criteria. A higher Dk value means a higher dyeing density, so the quality is superior. The results are shown in Table 3 below.
(Evaluation criteria)
A: Dk value is 1.6 or more B: Dk value is 1.4 or more and less than 1.6 C: Dk value is less than 1.4

[Discharge stability test]
The container filled with the ink of Example 1 was left in the above-described evaluation apparatus for 2 days with the apparatus stopped, then purged once, and a 200 mm × 250 mm solid pattern on the pretreated cotton cloth. Was printed. The ejection stability was evaluated according to the following criteria. The results are shown in Table 3 below.
(Evaluation criteria)
A: It can be printed well to the end.
B: Although printing can be performed satisfactorily to the end, slight scattering and streak missing are confirmed in the printed image.
C: Scatter and streaks in the printed image are severe.

  As shown in Table 2, the ink of Example 1 had high dye solubility at the time of ink preparation and excellent low-temperature stability. As shown in Table 3, the ink of Example 1 was capable of high-density dyeing and was excellent in ejection stability.

<Examples 2 to 9, Comparative Example 1>
[Preparation of ink]
C. adjusted to a concentration of about 1 to 10%. I. A solution of Reactive Blue 176 (Na salt) was added to a lithium hydroxide solution by a reverse osmosis membrane purification method and then evaporated to dryness to adjust the Li ion concentration to about 15000 ppm. I. A dry powder of Reactive Blue 176 was obtained. Then, each component (unit: part) described in Tables 4 and 5 below was mixed and stirred for about 1 hour until the solid content was dissolved in a state where the liquid temperature was maintained at 40 ° C., and then a 0.45 μm membrane filter. A test ink was prepared by filtering with a cellulose acetate filter paper (manufactured by Advantech). In Table 5, “-” indicates that the component is not contained.

[Viscosity evaluation]
The viscosity at 20 ° C. of each ink of Examples 2 to 9 and Comparative Example 1 was measured using an E-type viscometer. The results are shown in Tables 6 and 7 below. The unit of this viscosity is mP · s.

[Drying resistance evaluation]
The inks of Examples 2 to 9 and Comparative Example 1 were put in a petri dish and held at 60 ° C. for 4 hours, and the drying resistance was evaluated according to the following criteria. The results are shown in Tables 6 and 7 below.
(Evaluation criteria)
S: No precipitate is observed.
A: A slight precipitate is observed.
B: Obvious precipitates are observed.

[Inkjet printing]
Containers filled with the inks of Examples 2 to 9 and Comparative Example 1 were loaded into an industrial inkjet head evaluation apparatus (expandable coating apparatus EV2500; manufactured by Ricoh Co., Ltd.), and cotton cloth (sirket under an environment of 25 ° C. Cotton broad, no mercerized cotton knit, or mercerized cotton knit) was printed with a solid pattern of 200 mm × 250 mm. Each cotton fabric obtained was dried at 60 to 80 ° C. and then subjected to a steaming treatment at 100 to 103 ° C. for 10 minutes. Each cotton fabric obtained was washed successively with water, boiling water at 95 to 100 ° C. (10 minutes), and water, and then dried to obtain a printed fabric for evaluation. Each dyed cloth was used as a test sample, and the following evaluation test was performed. When color measurement was necessary in the evaluation test, a colorimeter manufactured by GRETAG-MACBETH (trade name: SpectroEye) was used.

[Dye density test]
The reflectance R _λ at 380 to 730 nm of each dyed cloth was measured, and the K / S value was calculated by the Kubelka-Munk equation: K / S = (1−R _λ ) ² / 2R _λ . Then, a ΣK / S value that is the sum of the K / S values at each wavelength was calculated, and the staining density was evaluated according to the following criteria. A higher ΣK / S value means a higher dyeing density, so that the quality is excellent. The results are shown in Tables 6 and 7 below.
(Evaluation criteria for mercerized cotton broad)
A: ΣK / S value is 220 or more B: ΣK / S value is 200 or more and less than 220 C: ΣK / S value is 190 or more and less than 200 D: ΣK / S value is less than 190 (evaluation criteria for mercerized cotton knit)
A: ΣK / S value is 320 or more B: ΣK / S value is 300 or more and less than 320 C: ΣK / S value is 290 or more and less than 300 D: ΣK / S value is less than 290 (evaluation criteria for mercerized cotton knit)
A: ΣK / S value is 280 or more B: ΣK / S value is 250 or more and less than 280 C: ΣK / S value is 220 or more and less than 250 D: ΣK / S value is less than 220

  As shown in Tables 6 and 7, the inks of Examples 2 to 9 showed printing resistance equal to or higher than that of the ink of Comparative Example 1, and the dyeing density was higher than that of the ink of Comparative Example 1. I was able to get things.

<Examples 10 to 19>
[Preparation of ink]
Each component (unit: part) described in Table 8 below was mixed and stirred for about 1 hour until the solid content was dissolved while maintaining the liquid temperature at 40 ° C. Then, a 0.45 μm membrane filter (cellulose acetate type) Each ink for a test was prepared by filtering with a filter paper (made by Advantech). In Table 8, “-” indicates that the component is not contained.

The abbreviations in Table 8 have the following meanings.
RB176 ... C. I. Reactive Blue 176
RO13 ... C. I. Reactive Orange 13
RO99 ... C. I. Reactive Orange 99
RR245 ... C. I. Reactive Red 245
RB15: 1 ... C. I. Reactive Blue 15: 1
RB72 ... C. I. Reactive Blue 72
RY2 ... C. I. Reactive Yellow 2
RY95 ... C. I. Reactive Yellow 95
EG ... ethylene glycol PG ... propylene glycol SF440 ... surfinol 440 (acetylene glycol surfactant)
GXL ... Proxel ^RTM GXL
THMAM ... Tris (hydroxymethyl) aminomethane

[Inkjet printing]
A pretreatment liquid containing sodium alginate, urea, and sodium hydrogen carbonate was attached to the cotton cloth by the pad method, and then the cotton cloth was dried to obtain a pretreated cotton cloth. The pretreated cotton fabric was cut into A4 size.

  A container filled with each ink prepared in [Preparation of ink] is loaded into an industrial inkjet head evaluation device (expandable coating device EV2500; manufactured by Ricoh Co., Ltd.), and after pretreatment in a 25 ° C. environment. A solid pattern of 200 mm × 250 mm was printed on a cotton cloth under the conditions shown in Table 9 below. The printing condition of the solid pattern with black ink is regarded as 100% ink ejection amount, and in the case of magenta ink, cyan ink 1, cyan ink 2, and yellow ink, 0 to 100% based on the ink ejection amount of black ink Printing was performed with any numerical value. The obtained cotton fabric was dried at 60 to 80 ° C. and then subjected to a steaming treatment at 100 to 103 ° C. for 10 minutes. The obtained cotton fabric was washed successively with water, boiling water at 95 to 100 ° C. (10 minutes), and water, and then dried to obtain a printed fabric for evaluation.

[Dye density test]
The reflection density of each dyed fabric obtained as described above was measured with a colorimeter (trade name: SpectroEye) manufactured by GRETAG-MACBETH to obtain a Dk value. A higher Dk value means a higher dyeing density, and therefore better quality. The results are shown in Table 9 below.
In Table 9, symbol K indicates black ink, M indicates magenta ink, C1 indicates cyan ink 1, and Y indicates yellow ink. The numbers described in parentheses after each ink symbol are numerical values of the ink ejection amount when the ink ejection amount of 100% black is 100, 60 means 60%, and 90 means 90%. To do.

  As shown in Table 9, the dyed fabrics of Examples 10 to 13 obtained by overprinting the black ink and the magenta ink or the cyan ink 1 were obtained by the same single printing without repeatedly printing the same portion. As compared with the dyed fabric of Example 14, the Dk value was high. In addition, the dyed fabrics of Examples 10 and 11 both showed higher Dk values than the dyed fabric of Example 15 obtained by overprinting the black ink and the yellow ink. Further, the dyed fabrics of Examples 12 and 13 obtained by overprinting the black ink, the magenta ink, and the cyan ink 1 are Examples 16 and 17 obtained by overprinting the black ink, the magenta ink, and the yellow ink. Compared with the dyed cloth of Example 18 and 19, in which the black ink, the cyan ink 1 and the yellow ink were overprinted, both showed high Dk values. These results indicate that a high Dk value can be obtained by hitting black ink and at least one of magenta ink and cyan ink.

<Examples 20 to 28>
[Preparation of color paste]
In the same manner as in Examples 10 to 19, black ink, cyan ink 1 and cyan ink 2 were prepared. And each component (unit: part) of following Table 10 was mixed, and the color paste for a test was prepared. In Table 10, “-” indicates that the component is not contained.

[Screen printing]
Using each color paste prepared in the above [Preparation of color paste], screen printing was performed on a cotton fabric (a mercerized cotton broad, no mercerized cotton knit, or a mercerized cotton knit) in an environment of 25 ° C. The obtained cotton fabric was dried at 60 to 80 ° C. and then subjected to a steaming treatment at 100 to 103 ° C. for 10 minutes. The obtained cotton fabric was washed successively with water, boiling water at 95 to 100 ° C. (10 minutes), and water, and then dried to obtain a printed fabric for evaluation.

[Dye density test]
The reflection density of each dyed fabric obtained as described above was measured with a colorimeter (trade name: SpectroEye) manufactured by GRETAG-MACBETH to obtain a Dk value. A higher Dk value means a higher dyeing density, and therefore better quality. The results are shown in Table 11 below.

  As shown in Table 11, the dyed fabrics of Examples 20 to 25 printed using color paste 1 in which black ink and cyan ink 1 are mixed or color paste 2 in which black ink and cyan ink 2 are mixed are cyan. Compared with the dyed fabrics of Examples 26 to 28 printed using the color paste 3 not mixed with ink, a high Dk value was exhibited. These results show that a high Dk value can be obtained by depositing the black ink and the cyan ink on the fiber.

Claims (27)

  C. I. Reactive Blue 176 and C.I. I. Reactive Red 245 and C.I. I. Reactive Orange 13 and C.I. I. A reactive dye containing at least one of Reactive Orange 99 and an ink containing urea.   The reactive dye is C.I. I. The ink of claim 1, comprising Reactive Orange 13.   The reactive dye is C.I. I. The ink of claim 1, comprising Reactive Orange 99.   The reactive dye is C.I. I. Reactive Orange 13 and C.I. I. The ink of claim 1, comprising Reactive Orange 99. 5. The water-soluble organic solvent having a dipole moment value (δP value) containing at least one cyclic amide-based solvent within a range of 9 to 30 MPa ^1/2 and water. The ink according to item. The ink according to claim 5, wherein a dipole moment value (δP value) of the water-soluble organic solvent is in a range of 9 to 20 MPa ^1/2 .   The ink according to claim 5 or 6, wherein the cyclic amide solvent is 2-pyrrolidone.   The ink according to claim 7, wherein the content of 2-pyrrolidone is 5 to 20% by mass.   The ink according to any one of claims 1 to 8, wherein the urea content is 5 to 20% by mass.   It contains 2-pyrrolidone, the total content of 2-pyrrolidone and urea is 15 to 30% by mass, and the content ratio of 2-pyrrolidone and urea is 1: 2 to 2: 1 on a mass basis. 1 (excluding those in which the total content of 2-pyrrolidone and urea is 15% by mass and the content ratio of 2-pyrrolidone and urea is 2: 1 on a mass basis). The ink as described in any one of -9.   The ink according to any one of claims 1 to 10, comprising a pH adjuster.   The ink according to claim 11, wherein the pH adjuster is tris (hydroxymethyl) aminomethane.   C. I. The ink according to any one of claims 1 to 12, wherein the content of Reactive Blue 176 is 5 to 15% by mass.   C. I. The ink according to claim 13, wherein the content of Reactive Blue 176 is 8 to 12% by mass.   The ink according to claim 1, comprising at least one of a nonionic surfactant and an anionic surfactant. An ink set comprising black ink and at least one of magenta ink and cyan ink,
The black ink is the ink according to any one of claims 1 to 15,
The magenta ink is C.I. I. Containing Reactive Red 245 as reactive dye,
The cyan ink is C.I. I. Reactive Blue 15: 1 and C.I. I. An ink set containing at least one of Reactive Blue 72 as a reactive dye. An attachment step of causing the ink droplets according to any one of claims 1 to 15 to be ejected by an ink jet printer and attached to a fiber;
A reactive fixing step in which the reactive dye in the ink attached to the fiber in the attaching step is reactively fixed to the fiber by heat; and
A washing step of washing unfixed reactive dye remaining in the fiber;
A textile printing method comprising:   The fiber according to claim 17, further comprising a pretreatment step of adhering an aqueous solution containing one or more types of paste material, a pretreatment pH adjuster, and a hydrotropic agent to the fiber before the attachment step. Textile printing method. An attachment step of causing each ink droplet of the ink set according to claim 16 to be ejected by an inkjet printer and attached to the fiber;
A reactive fixing step in which the reactive dye in the ink attached to the fiber in the attaching step is reactively fixed to the fiber by heat; and
A washing step of washing unfixed reactive dye remaining in the fiber;
A textile printing method comprising:   The fiber according to claim 19, further comprising a pretreatment step of adhering an aqueous solution containing one or more types of paste material, a pretreatment pH adjuster, and a hydrotropic agent to the fiber before the attachment step. Textile printing method. The inkjet printer is a scanning inkjet printer,
The textile printing method according to claim 19 or 20, wherein, in the attaching step, the black ink and at least one of the magenta ink and the cyan ink are attached to the fiber in an overlapping manner.   The textile printing method according to claim 21, wherein, in the attaching step, the black ink, the magenta ink, and the cyan ink are attached to the fiber in an overlapping manner.   The textile printing method according to claim 21 or 22, wherein a discharge amount of the black ink is larger than discharge amounts of other inks.   The fiber printing method according to any one of claims 17 to 23, wherein the fiber is a cellulose fiber or a polyamide fiber.   The textile printing method according to claim 24, wherein the fiber is a cellulosic fiber.   Fiber dye | stained using the ink as described in any one of Claims 1-15, or the ink set as described in Claim 16.   A fiber dyed by the printing method according to any one of claims 17 to 23.