JP7192250B2 - Ink for inkjet textile printing and ink set for inkjet textile printing - Google Patents

Description

The present invention relates to an ink for inkjet textile printing and an ink set for inkjet textile printing.

The inkjet recording method is a method of recording by ejecting droplets of ink from fine nozzles and depositing them on a recording medium. This method is characterized in that high-resolution, high-quality images can be recorded at high speed with a relatively inexpensive device. In the inkjet recording method, there are a great many factors to consider, including the properties of the ink to be used, the stability in recording, and the quality of the resulting image. .

In addition, dyeing (textile printing) of fabrics and the like is also performed using an inkjet recording method. Conventionally, screen textile printing, roller textile printing, etc. have been used as textile printing methods for fabrics (woven fabrics and non-woven fabrics). is advantageous, so various studies have been made.

Inks for inkjet textile printing have also been studied. For example, the colors to be developed, productivity, compatibility with the printing target, etc. have been studied, and formulations that improve each characteristic have been proposed. ing. For example, Patent Document 1 discloses an ink composition containing a reactive dye, a compound having a structure in which ethylene oxide and/or propylene oxide is addition-polymerized to diglycerin, a nonionic surfactant, an anionic surfactant, and water. Disclosed, the composition has excellent continuous ejection stability at a high driving frequency regardless of temperature changes in both room temperature and low temperature environments in a printer equipped with an industrial inkjet head, and is compatible with cellulosic fibers and There is a description that polyamide fibers can be dyed satisfactorily.

WO2001/013503

On the other hand, inkjet inks are also required to have properties such as suppression of foaming and rapid defoaming when foam is generated (antifoaming property). In order to impart such properties to the inkjet ink, the incorporation of a compound having a surface active action may be considered. Compounds having surface activity are used to adjust various properties of ink such as hydrophilicity, hydrophobicity, antifoaming, and wettability, and selection of the type of surface active compound and study of blending are carried out. .

In addition, the inkjet ink must be able to fill the flow path of the ejection head of the inkjet device without air bubbles (filling property), and must be able to quickly discharge air bubbles that occur in the ejection head (air bubble ejection property). It is also required to ensure ejection stability by For example, in the technique described in Patent Document 1, an attempt is made to improve continuous discharge stability by blending a compound having a specific structure, a nonionic surfactant, an anionic surfactant, or the like.

However, when searching for the type and combination of surfactants to improve certain properties, even if the necessary performance can be achieved under certain conditions, the performance will be insufficient under different conditions. often. Moreover, these performances are correlated with each other, and a lot of research is required to obtain an inkjet ink that has good overall characteristics under various conditions, and it is usually difficult to carry out with a simple design guideline.

For example, even if the ejection stability can be improved by the technique of Patent Document 1, there is concern about the generation of air bubbles and the deterioration of antifoaming properties because a large amount of anionic surfactant is blended. Furthermore, ink for inkjet textile printing should be designed considering the penetrating power into the fabric and the wetting and spreading property in the lateral direction when it is attached to the fabric. And more detailed examination is desired for blending.

Furthermore, ink for inkjet textile printing is required to have characteristics such as ejection stability from the ejection head and high image quality of the image dyed on the fabric, in addition to dyeing the fabric satisfactorily. The inventors, while studying ink for inkjet textile printing, found that when a water-soluble dye is used, although the color developability and the like are relatively good, the ejection stability tends to decrease. It was found that the tendency is related to the ease of discharging air bubbles in the ink channel and the fillability of the ink channel. Furthermore, it has been found that ink for inkjet textile printing using a water-soluble dye tends to spread more in the lateral direction of the fabric, and the image tends to blur.

One of the objects of some embodiments of the present invention is an ink for inkjet textile printing containing a water-soluble dye, which has good filling properties in the ink flow path, excellent air bubble discharging properties, and excellent ejection stability. to provide ink. Another object of some aspects of the present invention is to provide a printed article containing the ink for inkjet printing, which has good filling properties in the ink flow path, excellent air bubble discharge properties and ejection stability, and suppressed bleeding. To provide an ink set for inkjet textile printing capable of forming

The present invention has been made to solve at least part of the above problems, and can be implemented as the following aspects or application examples.

One aspect of the ink for inkjet textile printing according to the present invention is
a water-soluble dye that is one or more selected from acid dyes, reactive dyes and direct dyes;
A nonionic surfactant of 0.05% by mass or more and 3.0% by mass or less with respect to the total amount,
An anionic surfactant of 1 mass ppm or more and 100 mass ppm or less with respect to the total amount,
including.

By containing an anionic surfactant at a specific concentration, such an ink for inkjet textile printing can perform textile printing with good filling properties of the ink flow path, excellent air bubble expelling properties, and excellent ejection stability. In addition, the concentration relationship between the nonionic surfactant and the anionic surfactant is appropriate, so that foaming is suppressed and the permeability to the printing target is good. Furthermore, the use of water-soluble dyes enables sufficient textile printing.

In the ink for inkjet textile printing according to the present invention,
The water-soluble dye may be one or more selected from RBk39, RY95, RBk5, ABk172, AY79, DB87, AR138 and AV97.

Such an inkjet textile printing ink can dye the fabric more deeply.

In the ink for inkjet textile printing according to the present invention,
The anionic surfactant may be an aromatic sulfonic acid compound having an alkyl group or a salt thereof.

According to such an ink for inkjet textile printing, the penetration in the depth direction of the fabric is better, and along with this, it is easy to suppress the penetration in the lateral direction of the fabric, so bleeding can be further suppressed. can.

In the ink for inkjet textile printing according to the present invention,
The aromatic sulfonic acid compound having an alkyl group or a salt thereof may be one or more selected from dodecyldiphenyletherdisulfonic acid and salts thereof and dodecylbenzenesulfonic acid and salts thereof.

According to such an ink for inkjet textile printing, the penetration in the depth direction of the fabric is better, and along with this, it is easy to suppress the penetration in the lateral direction of the fabric, so bleeding can be further suppressed. can.

In the ink for inkjet textile printing according to the present invention,
The nonionic surfactant may be an acetylene glycol surfactant.

According to such an inkjet textile printing ink, the balance between the action of the anionic surfactant and the action of the nonionic surfactant is better, the filling property of the ink channel is even better, and the penetration into the printing object is improved. The properties are even better.

One aspect of the ink set for inkjet textile printing according to the present invention is
An ink set for inkjet textile printing comprising two or more kinds of inks, wherein one or more of the inks is the above ink for inkjet textile printing.

According to such an ink set for inkjet textile printing, since it contains the ink for inkjet textile printing described above, it is possible to carry out textile printing with at least good fillability of the ink flow path with the ink and excellent air bubble discharging performance and ejection stability. can. In addition, by using the ink, the permeability to the printing target is improved, and bleeding of the image on the printed matter can be suppressed.

RBk39, RY95, RBk5, ABk172, AY79, DB87, AR138 and AV97 are C.I. I. Reactive Black 39, C.I. I. Reactive Yellow 95, C.I. I. Reactive Black 5, C.I. I. Acid Black 172, C.I. I. Acid Yellow 79, C.I. I. Direct Blue 87, C.I. I. Acid Red 138 and C.I. I. It refers to Acid Violet 97.

Several embodiments of the present invention are described below. The embodiments described below describe examples of the present invention. The present invention is by no means limited to the following embodiments, and includes various modifications implemented within the scope of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.

1. Ink for Inkjet Textile Printing The ink for inkjet textile printing of the present embodiment (hereinafter also referred to as “inkjet textile ink” or simply “ink”) is used by attaching it to fabric by an inkjet method. First, the ink for inkjet textile printing will be described.

The ink for inkjet textile printing of the present embodiment contains a water-soluble dye that is one or more types selected from acid dyes, reactive dyes and direct dyes, a nonionic surfactant, and an anionic surfactant.

1.1. Water-Soluble Dye The inkjet textile ink of the present embodiment contains one or more water-soluble dyes selected from acid dyes, reactive dyes, and direct dyes. Further, the water-soluble dye used in the present embodiment is a dye capable of dyeing fabric (fiber), but the dyeing mechanism is not particularly limited. Furthermore, these may be used individually by 1 type, and may use 2 or more types together.

Specific examples of acid dyes include:
C. I. Acid Red 1, 6, 8, 9, 13, 14, 18, 19, 24, 26, 27, 28, 32, 35, 37, 42, 51, 52, 57, 62, 75, 77, 80, 82, 83, 85, 87, 88, 89, 92, 94, 95, 97, 106, 111, 114, 115, 117, 118, 119, 127, 128, 129, 130, 131, 133, 134, 138, 143, 145, 149, 151, 154, 155, 158, 168, 180, 183, 184, 186, 194, 198, 199, 209, 211, 215, 216, 217, 219, 249, 252, 254, 256, 257, 260, 261, 262, 263, 265, 266, 274, 276, 282, 283, 289, 299, 301, 303, 305, 315, 318, 320, 321, 322, 336, 337, 361, 396, 397 ;
C. I. Acid Violet 5, 7, 11, 15, 31, 34, 35, 41, 43, 47, 48, 49, 51, 54, 66, 68, 75, 78, 90, 97, 103, 106, 126, etc.;
C. I. Acid Yellow 1, 3, 7, 11, 17, 19, 23, 25, 29, 36, 38, 39, 40, 42, 44, 49, 50, 59, 61, 64, 70, 72, 75, 76, 78, 79, 98, 99, 110, 111, 112, 114, 116, 118, 119, 127, 128, 131, 135, 141, 142, 143, 151, 159, 161, 162, 163, 164, 165, 169, 174, 184, 190, 195, 196, 197, 199, 207, 218, 219, 222, 227, 246, etc.;
C. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 49, 54, 59, 60, 62, 72, 74, 76, 78, 80, 82, 83, 87, 90, 92, 93, 100, 102, 103, 104, 106, 112, 113, 114, 117, 120, 126, 127, 127: 1, 128, 129, 130, 131, 133, 138, 140, 142, 143, 151, 154, 156, 158, 161, 166, 167, 168, 170, 171, 175, 181, 182, 183, 184, 185, 187, 192, 193, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, 232, 239, 247, 249, 258, 260, 264, 271, 277, 277: 1, 278, 279, 280, 284, 288, 290, 296, 298, 300, 317, 324, 326, 333, 335, 338, 342, 350, etc.;
C. I. Acid Black 1, 2, 7, 24, 26, 29, 31, 44, 48, 50, 51, 52, 52: 1, 58, 60, 62, 63, 64, 67, 72, 76, 77, 94, 107, 108, 109, 110, 112, 115, 118, 119, 121, 122, 131, 132, 139, 140, 155, 156, 157, 158, 159, 172, 191, 194, 234, etc.;
C. I. Acid Orange 1, 7, 8, 10, 19, 20, 24, 28, 33, 41, 43, 45, 51, 56, 63, 64, 65, 67, 74, 80, 82, 85, 86, 87, 88, 94, 95, 122, 123, 124, etc.;
C. I. Acid Green 3, 7, 9, 12, 16, 19, 20, 25, 27, 28, 35, 36, 40, 41, 43, 44, 48, 56, 57, 60, 61, 65, 73, 75, 76, 78, 79, etc.;
C. I. Acid Brown 2, 4, 13, 14, 19, 20, 27, 28, 30, 31, 39, 44, 45, 46, 48, 53, 100, 101, 103, 104, 106, 160, 161, 165, 188, 224, 225, 226, 231, 232, 236, 247, 256, 257, 266, 268, 276, 277, 282, 289, 294, 295, 296, 297, 298, 299, 300, 301, 302, etc. is mentioned.

Specific examples of direct dyes include:
C. I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, etc.;
C. I. Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, etc.;
C. I. Direct Yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 132, 142, 144, 161, 163, etc.;
C. I. Direct Blue 1, 10, 15, 22, 25, 41, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 120, 151, 156, 158, 159, 160, 153, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 226, 229, 236, 237, 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 291 etc.;
C. I. Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125, 132, 146, 154, 166, 168, 173, 195, 199 and the like.

Specific examples of reactive dyes include:
C. I. Reactive Yellow 1, 2, 3, 5, 11, 13, 14, 15, 17, 18, 20, 21, 22, 23, 24, 25, 26, 27, 29, 35, 37, 40, 41, 42, 47, 51, 55, 65, 67, 81, 95, 116, 142, 161 etc.;
C. I. Reactive Red 1, 3, 3:1, 4, 13, 14, 17, 19, 21, 22, 23, 24, 24: 1, 25, 26, 29, 31, 32, 35, 37, 40, 41, 43, 44, 45, 46, 49, 55, 60, 66, 74, 79, 96, 97, 108, 141, 180, 218, 226, 245, etc.;
C. I. Reactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, etc.;
C. I. Reactive Blue 1, 2, 3, 5, 7, 8, 10, 13, 14, 15, 17, 18, 19, 21, 23, 25, 26, 27, 28, 29, 32, 35, 38, 41, 49, 63, 72, 75, 80, 95, 190, etc.;
C. I. Reactive Black 1, 3, 4, 5, 7, 8, 11, 12, 14, 17, 21, 23, 26, 31, 32, 34, 39 and the like.

The content of the water-soluble dye in the total amount of the ink for inkjet textile printing is about 0.1% by mass or more and 30% by mass or less, preferably 0.5% by mass or more and 25% by mass or less, more preferably 1% by mass or more. It is 20 mass % or less, more preferably 3 mass % or more and 20 mass % or less.

In the inkjet textile printing ink of the present embodiment, the water-soluble dye is at least one selected from acid dyes, reactive dyes and direct dyes, so that the textile can be dyed darkly with the inkjet textile printing ink.

Furthermore, in the ink for inkjet textile printing of the present embodiment, the water-soluble dyes are RBk39 (C.I. Reactive Black 39), RY95 (C.I. Reactive Yellow 95), RBk5 (C.I. Reactive Black 5), ABk172 (C.I. Acid Black 172), AY79 (C.I. Acid Yellow 79), DB87 (C.I. Direct Blue 87), AR138 (C.I. Acid Red 138) and AV97 (C.I. Acid Violet 97) is more preferable.

Further, by selecting such a dye in the ink for inkjet textile printing of the present embodiment, it is possible to obtain even more excellent results of dyeing (printing) the fabric with the ink for inkjet textile printing.

1.2. Nonionic Surfactant The inkjet textile printing ink of the present embodiment contains a nonionic surfactant. Examples of nonionic surfactants include acetylene glycol surfactants, silicone surfactants, and fluorine surfactants.

The acetylene glycol surfactant is not particularly limited, but for example, Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE- F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (all trade names, manufactured by Air Products and Chemicals, Inc.), Olphine B, Y, P, A, STG, SPC , E1004, E1010, PD-001, PD-002W, PD-003, PD-004, PD-005, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), Acetylenol E00, E00P, E40, E100 (all trade names, river (manufactured by Ken Fine Chemical Co., Ltd.).

The silicone-based surfactant is not particularly limited, but preferably includes a polysiloxane-based compound. Examples of the polysiloxane-based compound include, but are not particularly limited to, polyether-modified organosiloxane. Examples of commercial products of the polyether-modified organosiloxane include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (trade names of BYK-Chemie Japan). ), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22 -4515, KF-6011, KF-6012, KF-6015, and KF-6017 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer, and a specific example thereof is BYK-340 (manufactured by BYK-Chemie Japan).

Further, as nonionic surfactants, polyethylene glycol esters, polyethylene glycol ethers, polyethylene glycol amines, polyethylene glycol amides, polyhydric alcohol fatty acid (partial) esters, and the like may be used. Examples of such nonionic surfactants include polypropylene glycol ethylene oxide adducts, polyoxyethylene nonylphenyl ethers, polyoxyethylene octylphenyl ethers, polyoxyethylene dodecylphenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene Fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, aliphatic alkanolamides, glycerin esters, sorbitan esters and the like. Commercially available products of such nonionic surfactants include, for example, manufactured by NOF Corporation: trade name Dispanol TOC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: trade names Aqualon HS-10, Aqualon KH-05, Nippon Emulsifier Co., Ltd. : Trade name Newcole 2308LY and the like.

The above nonionic surfactants can be used singly or in combination. The content of the nonionic surfactant is 0.05 mass % or more and 3 mass % or less in total of the nonionic surfactant with respect to the entire ink for inkjet textile printing. The total content of nonionic surfactants is preferably 0.05% by mass or more and 2.5% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less, and particularly preferably 0.2% by mass or more. It is 1.5% by mass or less.

Among the above, the nonionic surfactant contained in the ink for inkjet textile printing of the present embodiment is more preferably an acetylene glycol surfactant. The acetylene glycol-based surfactant improves the balance between the action of the anionic surfactant described later and the action of the acetylene glycol-based surfactant (nonionic surfactant) (anionic surfactant and Because of this, for example, it is possible to further improve the filling property of the ink flow path, and further improve the permeability to the fabric to be printed.

Since the ink for inkjet textile printing contains a nonionic surfactant, it has good stability when the ink is ejected from the recording head. Also, the use of an appropriate amount of nonionic surfactant can improve the penetration into the fabric, e.g. be.

1.3. Anionic Surfactant The inkjet textile printing ink of the present embodiment contains an anionic surfactant. The anionic surfactant is not particularly limited. and a compound having a functional group.

More specifically, the anionic surfactants include alkylbenzenesulfonic acids such as sodium dodecylbenzenesulfonate or salts thereof; dialkylsulfosuccinic acids such as sodium diethylhexylsulfosuccinate and sodium diisotridecylsulfosuccinate or salts thereof; (Polyoxyethylene 2-ethylhexyl ether) sodium sulfosuccinate, di(polyoxyethylene isotridecyl ether) dipolyoxyethylene alkyl ether sulfosuccinic acid such as sodium sulfosuccinate or salts thereof; polyoxyethylene lauryl ether sodium sulfate, polyoxy Polyoxyalkylene alkyl ether sulfuric acid such as sodium ethylene myristyl ether sulfate or salts thereof; Polyoxyethylene alkyl ether sulfate ester salts such as sodium polyoxyethylene alkyl ether sulfate and ammonium polyoxyethylene alkyl ether sulfate; Sodium polyoxyethylene alkylphenyl ether sulfate , Polyoxyethylene alkylphenyl ether sulfate salts such as polyoxyethylene alkylphenyl ether ammonium sulfate; Polyoxyethylene polycyclic phenyl ether sulfate salts such as sodium polyoxyethylene polycyclic phenyl ether sulfate and polyoxyethylene polycyclic phenyl ether ammonium sulfate ; polyoxyethylene-polyoxypropylene glycol ether sulfuric acid or salts thereof; sodium lauryl sulfate, higher alcohol sodium sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate or other alkyl sulfuric acids or salts thereof; potassium oleate, sodium oleate, semi-cured Fatty acids such as sodium tallow fatty acid or salts thereof; diammonium dodecyldiphenyletherdisulfonate, sodium dodecyldiphenyletherdisulfonate, calcium dodecyldiphenyletherdisulfonate, alkyldiphenyletherdisulfonic acid such as sodium alkyldiphenyletherdisulfonate or salts thereof; aromatic sulfonic acid and formaldehyde salts of condensates with; salts of condensates of aromatic sulfonic acids and formaldehyde such as naphthalenesulfonic acid formalin condensate; N-acylsarcosinates such as sodium lauroyl sarcosinate, sodium N-myristoyl-N-methyltaurate , Coconut Fatty Acid Methyl Taurid Sodium class fatty acid amidosulfonic acid or salts thereof; and N-acylglutamic acid or salts thereof such as disodium N-stearoylglutamate and monosodium N-stearoylglutamate;

Commercially available anionic surfactants may be used, for example, manufactured by Taiko Yushi Kagaku Kogyo Co., Ltd.: trade names Typol NLT-42, Typol NLL-27, Typol NOS-35, Typol NOES-340, Kao Company: trade names Neoperex G-65, Pelex SS-H, Emal TD, Daiichi Kogyo Seiyaku Co.: trade names Aqualon HS-10, Aqualon KH-05, Sanyo Chemical Co., Ltd.: Eleminol MON-2, etc. mentioned.

The above anionic surfactants can be used singly or in combination. The content of the anionic surfactant is 1 mass ppm or more and 100 mass ppm or less in total with respect to the entire ink for inkjet textile printing. That is, the total content of the anionic surfactant is 0.0001% by mass or more and 0.01% by mass or less with respect to the entire inkjet textile printing ink. Mass ppm represents a unit obtained by dividing the total mass of the contained anionic surfactants by the mass of the entire ink for inkjet textile printing. The total content of the anionic surfactant is preferably 3 ppm by mass or more and 80 ppm by mass or less, more preferably 5 ppm by mass or more and 50 mass ppm or less, and particularly preferably 10 mass ppm or more and 50 mass ppm or less.

Among the above examples, the anionic surfactant contained in the ink for inkjet textile printing of the present embodiment is more preferably an aromatic sulfonic acid compound having an alkyl group or a salt thereof. By selecting such an anionic surfactant, for example, it is possible to further improve the filling property of the ink flow path and the air bubble discharging property. In addition, by selecting such an anionic surfactant, it is possible to improve the permeability of the ink for inkjet textile printing in the depth direction of the fabric to be printed, and in addition to this, Since it is easy to suppress directional permeation, for example, blurring of an image can be further suppressed.

As another aspect of the selection of the anionic surfactant, the anionic surfactant contained in the ink for inkjet textile printing, among the above-exemplified aromatic sulfonic acid compounds having an alkyl group or a salt thereof, is dodecyl diphenyl ether disulfone It is more preferably one or more selected from acids and salts thereof, and dodecylbenzenesulfonic acid and salts thereof. By selecting such an anionic surfactant, for example, it is possible to further improve the filling property of the ink flow path and the air bubble discharging property. In addition, by selecting such an anionic surfactant, it is possible to improve the permeability of the ink for inkjet textile printing in the depth direction of the fabric to be printed, and in addition to this, Since it is easy to suppress directional permeation, for example, blurring of an image can be further suppressed.

1.4. Other Ingredients 1.4.1. Water The ink for inkjet textile printing according to the present embodiment may contain water. Examples of water include pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, and distilled water, and water in which ionic impurities are reduced, such as ultrapure water. In addition, the use of water sterilized by ultraviolet irradiation, addition of hydrogen peroxide, or the like can suppress the generation of bacteria and fungi when the ink for inkjet printing is stored for a long period of time.

The content of water is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably 50% by mass or more, relative to the total amount of the ink for inkjet textile printing. Note that the water in the ink for inkjet textile printing includes, for example, the water when the raw material contains water and the water to be added. When the water content is 30% by mass or more, the ink for inkjet textile printing can have a relatively low viscosity. The upper limit of the water content is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, relative to the total amount of the ink for inkjet textile printing.

1.4.2. Organic Solvent, etc. The inkjet textile printing ink of the present embodiment may contain an organic solvent such as a nitrogen-containing compound, an alkyl polyol, or a glycol ether.

<Nitrogen-containing compound>
Examples of nitrogen-containing compounds include ε-caprolactam [136°C], N-methyl-2-pyrrolidone [204°C], N-ethyl-2-pyrrolidone [212°C], N-vinyl-2-pyrrolidone [193°C]. , 2-pyrrolidone[245.degree. Numbers in parentheses represent normal boiling points. These nitrogen-containing compounds may be used singly or in combination of two or more. Such a nitrogen-containing compound can be expected to have the effect of easily dissolving the dye described above and suppressing the solidification and drying of the ink for inkjet textile printing.

When the nitrogen-containing compound is used, the total content is 1% by mass or more and 30% by mass or less, preferably 2% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, relative to the total mass of the ink. % or less, more preferably 4 mass % or more and 10 mass % or less.

<Alkyl polyol>
Specific examples of alkyl polyols include 1,2-propanediol [188°C], 1,2-butanediol [194°C], 1,2-pentanediol [210°C], 1,2-hexanediol [224°C ], 1,2-heptanediol [227°C], 1,3-propanediol (propylene glycol) [210°C], 1,3-butanediol [230°C], 1,4-butanediol [230°C], 1,5-pentanediol [242°C], 1,6-hexanediol [250°C], 2-ethyl-2-methyl-1,3-propanediol [226°C], 2-methyl-2-propyl-1 ,3-propanediol [230°C], 2-methyl-1,3-propanediol [214°C], 2,2-dimethyl-1,3-propanediol [210°C], 3-methyl-1,3- butanediol [203°C], 2-ethyl-1,3-hexanediol [244°C], 3-methyl-1,5-pentanediol [250°C], 2-methylpentane-2,4-diol [197°C] ], diethylene glycol [245° C.], dipropylene glycol [232° C.], triethylene glycol [287° C.], glycerin [290° C.], and the like. In addition, the numerical value in a parenthesis represents a normal boiling point. These alkyl polyols may be used singly or in combination of two or more.

If the content of the alkyl polyol is 5% by mass or more relative to the total mass of the inkjet textile printing ink, the effect can be exhibited, but it is preferably 5% by mass or more and 30% by mass or less. , 8% by mass or more and 27% by mass or less, and more preferably 10% by mass or more and 25% by mass or less.

<Glycol ether>
Glycol ethers are preferably monoalkyl ethers of glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and polyoxyethylene polyoxypropylene glycol. More preferably, methyltriglycol (triethylene glycol monomethyl ether), butyltriglycol (triethylene glycol monobutyl ether), butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether, etc. are mentioned, and diethylene glycol is a typical example. Monobutyl ether [230°C] may be mentioned. Numbers in parentheses represent normal boiling points.

Glycol ethers may be used in combination of multiple types. In the case of using glycol ether, the blending amount is 0.2% by mass or more and 30% by mass in total with respect to the total amount of the inkjet textile printing ink from the viewpoint of adjusting the viscosity of the inkjet textile printing ink and preventing clogging due to the moisturizing effect. Below, it is preferably 0.4% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and still more preferably 2% by mass or more and 10% by mass or less.

<Other organic solvents>
Furthermore, examples of organic solvents that can be used in the ink for inkjet textile printing of the present embodiment include lactones such as γ-butyrolactone, betaine compounds, and the like. When these organic solvents are used, the wettability and permeation rate can be controlled, and thus the color developability of the image can be improved.

1.4.3. Surfactant The inkjet textile printing ink according to the present embodiment may contain a cationic surfactant, an amphoteric surfactant, etc., in addition to the nonionic surfactant and anionic surfactant described above. Such a surfactant may be used for the purpose of reducing the surface tension of the ink for inkjet textile printing and adjusting and improving the wettability with the fabric (penetrability into the fabric), and the effect of the surfactant described above may be used. It may be used supplementarily as long as it does not interfere.

1.4.4. pH Adjusting Agent A pH adjusting agent can be added to the inkjet textile printing ink of the present embodiment for the purpose of adjusting the pH. Examples of pH adjusters include, but are not particularly limited to, acids, bases, weak acids, and appropriate combinations of weak bases. Examples of acids and bases used in such combinations include inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate and dihydrogen phosphate. sodium, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, ammonia and the like, and organic bases such as triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, trishydroxymethylaminomethane ( THAM) and the like, and examples of organic acids include adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES), 4-(2-hydroxy ethyl)-1-piperazineethanesulfonic acid (HEPES), morpholinoethanesulfonic acid (MES), carbamoylmethyliminobisacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N- Goods such as (2-acetamido)-2-aminoethanesulfonic acid (ACES), colamin hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamidoglycine, tricine, glycinamide, bicine, etc. Buffers, phosphate buffers, citrate buffers, Tris buffers and the like may be used. Furthermore, among these, as part or all of the pH adjuster, tertiary amines such as triethanolamine and triisopropanolamine, and carboxyl group-containing organic acids such as adipic acid, citric acid, succinic acid, and lactic acid, It is preferable because the pH buffering effect can be obtained more stably.

When a pH adjuster is used in the ink for inkjet textile printing of the present embodiment, it is added as appropriate while monitoring the pH. % by mass or less, preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.2% by mass or more and 1% by mass or less.

1.4.5. Ureas In addition, ureas may be used as moisturizing agents for inkjet textile printing inks, or as dyeing assistants for improving the dyeing properties of dyes. Specific examples of ureas include urea, ethyleneurea, tetramethylurea, thiourea, 1,3-dimethyl-2-imidazolidinone and the like. When urea is contained, its content can be 1% by mass or more and 10% by mass or less with respect to the total mass of the ink.

1.4.6. Saccharide A suitable amount of saccharide may be used for the purpose of suppressing solidification and drying of the ink for inkjet textile printing. Specific examples of sugars include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.

1.4.7. Chelating Agent A suitable amount of chelating agent may be used for the purpose of removing unnecessary ions in the ink for inkjet textile printing. Chelating agents include, for example, ethylenediaminetetraacetic acid and salts thereof (ethylenediaminetetraacetic acid dihydrogen disodium salt, ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, metaphosphate, etc.). be done.

1.4.8. Preservatives and Antifungal Agents Antiseptic agents and antifungal agents may be appropriately used in the ink for inkjet textile printing. Examples of antiseptics and antifungal agents include sodium benzoate, pentachlorophenol sodium, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one (Zeneca Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL.2, Proxel TN, Proxel LV), 4-chloro-3-methylphenol (Bayer's Preventol CMK, etc.) and the like.

1.4.9. Others As components other than the above, additives that can be commonly used in inkjet inks, such as rust inhibitors, antioxidants, ultraviolet absorbers, oxygen absorbers, and dissolution aids, may be contained. The ink for inkjet textile printing of the present embodiment may contain a dye other than the above-described acid dye, reactive dye, or direct dye as long as it is a water-soluble dye.

1.5. Production and Physical Properties of Inkjet Textile Ink The inkjet textile ink according to the present embodiment is obtained by mixing the components described above in an arbitrary order and removing impurities by filtration or the like as necessary. As a method for mixing each component, a method of sequentially adding the materials to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirring and mixing them is preferably used.

The ink for inkjet textile printing according to the present embodiment preferably has a surface tension of 20 mN/m or more and 40 mN/m or less at 20° C. from the viewpoint of the balance between textile printing quality and reliability as an inkjet ink. It is more preferably m or more and 35 mN/m or less. From the same viewpoint, the viscosity of the ink at 20° C. is preferably 1.5 mPa·s or more and 10 mPa·s or less, more preferably 2 mPa·s or more and 8 mPa·s or less. One method for setting the surface tension and viscosity within the above ranges is to appropriately adjust the types of the above-mentioned organic solvents and surfactants, and the amounts of these and water added.

1.6. Textile printing target The ink for inkjet textile printing of the present embodiment can be used, for example, on various fabrics as a textile printing target. The material constituting the fabric is not particularly limited, and examples include natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable materials such as polylactic acid. fibers, etc., and they may be blended fibers. As the fabric, the above fibers may be in any form such as woven fabric, knitted fabric, or non-woven fabric. Among these, it is more preferable that the fabric to be printed in the present embodiment is a fabric containing polyamide fibers. By using such a fabric, it is possible to obtain more excellent dyeability of ink for inkjet textile printing. Moreover, if necessary, a pretreatment composition containing at least one of an alkaline agent and a hydrotropic agent may be applied to the fabric. This may further improve the dyeability of the dye.

1.7. Effects, etc. The ink for inkjet textile printing of the present embodiment contains an anionic surfactant at a specific concentration, so that the ink flow path and cartridge filling properties of an inkjet device are good, and the air bubble discharging property and ejection stability are excellent. printing can be performed. In addition, the concentration relationship between the nonionic surfactant and the anionic surfactant is appropriate, so that foaming is suppressed and the permeability to the printing target is good. Furthermore, the use of the water-soluble dye allows the fabric to be printed satisfactorily.

While the inventors are conducting various studies of ink for inkjet textile printing, when a water-soluble dye is used, in the fabric to be printed, when the ink for inkjet textile printing adheres, the lateral direction of the fabric rather than the depth direction It has been found that the spread to the edge tends to be predominant, and image blurring is likely to occur. One reason for this phenomenon is thought to be that the ink is more likely to move along the direction in which the fibers that make up the fabric extend. Although the exact cause is unknown, it is speculated that it is affected by the type and amount of impurities contained in the dye. found to be caused by

As a result of various investigations based on such knowledge, it was found that using a nonionic surfactant and an anionic surfactant, and blending the nonionic surfactant at a specific concentration, and adding the anionic surfactant In particular, the present inventors have found that the ink for ink-jet textile printing of the present embodiment is obtained by finding that the filling property and the discharge of air bubbles are improved by blending at a low concentration. The concentration of the anionic surfactant in the ink for inkjet textile printing of the present embodiment is much lower than that used in general inks, but the unexpected effect is demonstrated by the examples described later.

2. Ink Set for Inkjet Textile Printing The ink for inkjet textile printing of the present embodiment described above constitutes an ink set in which an arbitrary number of compositions and an arbitrary number of colors are combined with an inkjet textile ink containing a dye of any other color. be able to.

For example, the ink set for inkjet textile printing of the present embodiment can be an ink set for inkjet textile printing containing at least cyan ink, magenta ink, yellow ink and black ink. Further, for example, the ink set for inkjet textile printing of the present embodiment may further include at least one of blue ink, orange ink, red ink, and brown ink. At least one of the inks included in these inkjet textile printing ink sets is the inkjet textile printing ink of the present embodiment described above.

The cyan ink, magenta ink, yellow ink, black ink, blue ink, orange ink, red ink, brown ink, and the like, which constitute the ink set, are the same as the inks for inkjet textile printing described above. Components such as surfactants can be blended independently.

According to such an ink set for inkjet textile printing, since it contains the ink for inkjet textile printing described above, it is possible to perform textile printing with at least the above-described ink having good fillability in the ink flow path and excellent air bubble discharging performance and ejection stability. can be done. In addition, by using at least the ink described above, the permeability to the printing target is improved, and bleeding of the image on the printed matter can be suppressed. That is, the ink set for inkjet textile printing of the present embodiment contains the above ink for inkjet textile printing, and as a result of increasing the permeability of the ink in the depth direction of the textile object, spreading in the lateral direction is suppressed. Therefore, bleeding (bleeding) between the above ink for inkjet textile printing and other inks adhered to the printing object adjacent to the ink is suppressed, so that the image of the printed matter can be suppressed from bleeding.

3. EXAMPLES AND COMPARATIVE EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

3.1. Examples and comparative examples of inkjet textile printing ink 3.1.1. Preparation of ink for inkjet printing Each component was placed in a container so as to have the composition shown in Table 1, mixed and stirred with a magnetic stirrer for 2 hours, and then filtered through a membrane filter with a pore size of 5 μm. was obtained. Units of numerical values in Table 1 are shown in each column.

In the table, both Surfynol 465 and 104 are from Air Products and Chemicals.
, Inc. are nonionic surfactants, which are 2,4,7,9-tetramethyl-5-decyne-4,7-diol-di(polyoxyethylene) ether and 2,4,7, respectively. It refers to 9-tetramethyl-5-decyne-4,7-diol. In addition, each anionic surfactant used was commercially available as a reagent.

3.1.2. Evaluation method of ink for inkjet textile printing <Evaluation of fillability>
Ink was discharged from the head of Monna Lisa 180 T16 (manufactured by Robustelli), and each of the inkjet textile printing inks of Examples and Comparative Examples was introduced into the flow path for supplying ink to the head. After that, the cleaning operation of the device was performed to check the number of cleaning operations until the ink entered the head and was ejected normally from all the nozzles. Then, the fillability of each ink jet textile printing ink for the head was evaluated according to the following criteria, and the results are shown in Table 1. In the following criteria, A, B or C is the allowable range.
A: Successfully ejected within 3 times B: Successfully ejected 4-5 times C: Successfully ejected 6-7 times D: 8-9 times required for normal ejection There was E: No normal discharge even 10 times or more

<Evaluation of Air Bubble Dischargeability>
The head of Monna Lisa 180 T16 (manufactured by Robustelli) is filled with ink, and the cleaning operation of the device is performed. did. Then, in this state, the suction cap for cleaning was opened, and the air was caused to flow backward from the nozzle into the head and the flow path. After that, the flow path for supplying ink to the head was opened, and the cleaning operation of the device was carried out, and the number of cleaning operations until the backflow of air was discharged and the ink was ejected normally from all the nozzles was examined. . Then, the air bubble discharging property of each example of the ink for inkjet textile printing to the head was evaluated according to the following criteria, and the results are shown in Table 1. In addition, A, B, or C is the allowable range in the standard.
A: Successfully ejected within 3 times B: Successfully ejected 4-5 times C: Successfully ejected 6-7 times D: 8-9 times required for normal ejection there were.
E: No normal discharge even 10 times or more

<Evaluation of ejection stability>
Monna Lisa 180 T16 (manufactured by Robustelli) was filled with the ink for inkjet textile printing of each example, and 720×540 d.p.m. p. i. , continuous printing was performed on roll media in the 3-pass mode, and it was examined whether or not printing could be performed normally without omissions, bends, or the like. The length of the media when coming off, bending, etc. occurred was evaluated according to the following criteria, and the results are shown in Table 1. In addition, A, B, or C is the allowable range in the standard.
A: 1000 m or more could be printed normally B: 500 m or more and less than 1000 m could be normally printed C: 200 m or more and less than 500 m could be normally printed D: Dropouts and bending occurred at less than 200 m

3.2. Examples and Comparative Examples of Ink Set for Inkjet Textile Printing 3.2.1. Inkjet Textile Printing Ink Set The inkjet textile printing inks of the above Examples and Comparative Examples were combined as shown in Table 2 to obtain the inkjet textile printing ink sets of Examples and Comparative Examples. That is, the ink sets of Examples and Comparative Examples are ink sets composed of two colors of X-color ink and Y-color ink.

3.2.2. Evaluation method of ink set for inkjet textile printing <Ink set examples: S1, S2, and CS1>
A cotton cloth with a basis weight of 130 g / m2 is soaked in the following pretreatment agent, squeezed with a mangle at a pick-up rate of 20%, and then placed in an oven with a temperature inside the tank of 60 ° C. for 10 minutes to dry. It was created.
<Pretreatment agent>
Sodium alginate 1.0% by mass
Guar gum 1.0% by mass
Ammonium sulfate 4.0% by mass
Urea 10.0% by mass
remaining water

Next, an inkjet printing machine "Monna-Lisa 180 T16" (manufactured by Robustelli) was filled with two colors (X color and Y color) of each ink set example in the yellow column and the cyan column, respectively, and the above evaluation was performed. 540×720d. p. i. , the following pattern was printed in 3-pass mode.
Pattern A: A thin line with a width of 0.5 mm is drawn in X color and surrounded by a solid Y color.
Pattern B: A fine line with a width of 0.5 mm is drawn in Y color and surrounded by solid X color.

After printing, steam treatment was performed at 102° C. for 12 minutes using a steamer (manufactured by Matisse: steamer DHe type), and then washed with water to remove undyed dye. Furthermore, it was washed with an aqueous solution containing 0.2% by mass of Laccol STA (manufactured by Meisei Chemical Co., Ltd., surfactant) at 95° C. for 10 minutes and dried in an oven at 60° C. to obtain a printed sample.

<Ink set example: S3, S4, S5, S6, and CS2, CS3>
A silk fabric having a basis weight of 60 g/m 2 was pretreated in the same manner as described above to prepare a fabric 2 for evaluation. After that, in the same manner as described above, printing was performed on the evaluation fabric 2 with a combination of each ink set example.

After printing, steam treatment was performed at 100° C. for 30 minutes using a DHe steamer, and washed with water to remove undyed dye. Further, it was washed with an aqueous solution containing 0.2% by mass of Laccol STA at 55° C. for 30 minutes and dried in an oven at 60° C. to obtain a printed sample.

Table 2 shows the results of evaluating each printed sample obtained according to the following criteria. In addition, A, B or C is the allowable range in the following criteria.
A: The outline of the fine line is clearly visible, and no bleeding is seen. B: The fine line looks slightly thick, but no bleeding is seen. C: The fine line looks slightly thin, but the line is recognizable and no bleeding is seen. D: Fine lines look thick E: Fine lines look thick, bleeding is also seen F: Fine lines are eroded solid and look thin, or lines cannot be recognized

3.3. Looking at the evaluation results Table 1, a water-soluble dye, a total of 0.05% by mass or more and 3.0% by mass or less of a nonionic surfactant with respect to the total amount, and a total of 1 ppm by mass or more and 100 It was found that the ink for inkjet textile printing of each of Examples (A-1 to A-11) containing an anionic surfactant of mass ppm or less was excellent in filling property, bubble discharging property, and ejection stability.

On the other hand, in Comparative Example B-1, which does not contain an anionic surfactant, the filling property and air bubble discharging property were insufficient. Further, in Comparative Example B-2, which does not contain a nonionic surfactant, the filling property and air bubble discharging property were acceptable, but the ejection stability was poor.

Further, in Comparative Example B-3, which contained only 0.1 ppm by mass of an anionic surfactant, the filling property and bubble discharging property were insufficient. Conversely, Comparative Example B-5 containing 200 ppm by mass of an anionic surfactant also exhibited insufficient filling properties and air bubble discharging properties. From these results, it was found that the filling property and air bubble discharging property are poor when the anionic surfactant is too little or too much. This suggests that the amount of anionic surfactant has a very strong effect on the surface tension and wettability of the ink. It has been found that in some cases there is a very small and very narrow range of suitable dosages.

Furthermore, Comparative Example B-4 containing only 0.01% by mass of nonionic surfactant and Comparative Example B-6 containing 5% by mass of nonionic surfactant both had insufficient ejection stability. . Although it may depend on the compatibility with the anionic surfactant and the amount ratio, it is considered that there is a suitable addition amount of the nonionic surfactant for ejection stability.

The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same function, method, and result, or configurations that have the same purpose and effect). Moreover, the present invention includes configurations in which non-essential portions of the configurations described in the embodiments are replaced. In addition, the present invention includes a configuration that achieves the same effects or achieves the same purpose as the configurations described in the embodiments. In addition, the present invention includes configurations obtained by adding known techniques to the configurations described in the embodiments.

Claims (4)

a water-soluble dye that is one or more selected from acid dyes, reactive dyes and direct dyes;
A nonionic surfactant of 0.05% by mass or more and 3.0% by mass or less with respect to the total amount,
An anionic surfactant of 1 mass ppm or more and 100 mass ppm or less with respect to the total amount,
including
The nonionic surfactant is an acetylene glycol surfactant,
An ink for inkjet textile printing, wherein the anionic surfactant is an aromatic sulfonic acid compound having an alkyl group or a salt thereof . In claim 1,
An ink for inkjet textile printing, wherein the water-soluble dye is one or more selected from RBk39, RY95, RBk5, ABk172, AY79, DB87, AR138 and AV97. In claim 1 or claim 2 ,
The ink for inkjet textile printing, wherein the aromatic sulfonic acid compound having an alkyl group or a salt thereof is one or more selected from dodecyldiphenyletherdisulfonic acid and salts thereof and dodecylbenzenesulfonic acid and salts thereof. An ink set for inkjet textile printing comprising two or more inks, wherein one or more of the inks is the ink for inkjet textile printing according to any one of claims 1 to 3 . .