JP2015183344A - Printing ink set and printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing ink set that has excellent long-term storage stability, and keeps excellent color developability even after long-term storage.SOLUTION: A printing ink set according to the present invention is for performing printing on a fiber with a reactive dye, the printing ink set comprising a first ink comprising a reactive dye and a second ink comprising an alkali agent, and the second ink not comprising urea or urea derivatives.

Description

  The present invention relates to an ink set for textile printing and a textile printing method using the ink set.

  Conventional textile printing has been performed using a printing method using a plate or a screen printing method. In recent years, a printing technique using an ink jet method has been attracting attention because it does not require a plate and can cope with a small variety of products.

  Examples of dye types used for printing include direct dyes, reactive dyes, acid dyes, and disperse dyes. In general, the type of dye having good compatibility varies depending on the type of fiber. For example, reactive dyes are suitable for printing fibers such as cotton, silk, wool, hemp, rayon, polynosic, cupra and lyocell.

  For example, Patent Documents 1 to 3 disclose ink sets used when printing using such reactive dyes. These ink sets are made of various materials such as pretreatment ink and dyeing auxiliary ink in addition to dye ink.

JP 2004-143621 A Japanese Patent No. 5060235 Japanese Patent No. 4710337

  However, in the ink set disclosed in the above-mentioned patent document, an alkali agent for fixing a reactive dye, a urea or a urea derivative for increasing steaming efficiency, etc. , Also referred to as “urea and the like”). If an alkali agent and urea coexist, urea and the like are decomposed by the alkali agent due to high temperature storage during long-term storage and transportation, and the long-term storage stability of pretreatment ink and dyeing auxiliary ink is impaired. there were. If urea or the like is decomposed, the introduction of moisture into the fiber is lowered, and the color developability may be lowered. In addition, carbon dioxide and ammonia are generated by the decomposition of urea, so that the surrounding environment may be deteriorated. In particular, in the inkjet method, ejection stability may be impaired due to generation of bubbles.

  Some aspects of the present invention provide an ink set for textile printing that has excellent long-term storage stability and good color developability even after long-term storage by solving at least a part of the above problems. Is.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the ink set for textile printing according to the present invention is:
A printing ink set for printing on a fiber with a reactive dye,
A first ink containing a reactive dye and a second ink containing an alkaline agent,
The second ink contains neither urea nor a urea derivative.

  According to the textile printing ink set of Application Example 1, the second ink containing an alkali agent is configured to contain neither urea nor a urea derivative, thereby suppressing the reaction between the alkali agent and urea or the like. Therefore, the long-term storage stability of the second ink is improved. Moreover, according to such an ink set, the color developability can be improved even after long-term storage.

[Application Example 2]
In the ink set for textile printing of Application Example 1,
The first ink may contain at least one selected from the group consisting of urea and urea derivatives.

  According to the textile printing ink set of Application Example 2, by adding urea or the like to the first ink, moisture introduction into the fiber can be improved during the steam treatment, and the reactive dye follows the moisture. As a result, uniform and high color printing is possible.

[Application Example 3]
In the printing ink set of Application Example 1 or Application Example 2,
Furthermore, it can have the 3rd ink containing at least 1 sort (s) selected from the group which consists of urea and a urea derivative.

  According to the textile printing ink set of the application example 3, by having the third ink containing urea or the like, it is possible to add or reduce the amount of urea or urea derivative added to the first ink. Thereby, the balance of the viscosity of each ink can be kept favorable, and for example, an ink set suitable for an ink jet system is obtained.

[Application Example 4]
In the textile printing ink set of Application Example 3,
The third ink may further contain at least one polymer compound selected from the group consisting of sodium alginate, carboxymethylcellulose, and hydroxyethylcellulose.

  According to the ink set for textile printing of Application Example 4, the reactive dye easily adheres to the fiber by the paste, so that textile printing with reduced bleeding can be realized.

[Application Example 5]
In the printing ink set of any one of Application Examples 1 to 4,
The alkaline agent is at least selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, and sodium triphosphate. It can be one kind.

  According to the ink set for textile printing of Application Example 5, the reactive dye can be reliably fixed on the cloth, and high-color textile printing is possible.

[Application Example 6]
In the printing ink set of any one of Application Examples 1 to 5,
The second ink may further contain an anti-reduction agent.

  According to the printing ink set of Application Example 6, it is possible to suppress the bond between the fiber and the reactive dye from being cut by a reducing action, and to prevent printing unevenness and reproducibility of printing density and hue. And high color developability can be obtained.

[Application Example 7]
In the printing ink set of any one of Application Examples 1 to 6,
The first ink may further contain a humectant, a penetrating agent, and a surfactant.

  According to the textile printing ink set of Application Example 7, since the ink viscosity and surface tension can be adjusted to appropriate values, an ink set suitable for inkjet textile printing can be obtained.

[Application Example 8]
One aspect of the textile printing method according to the present invention is:
The fiber is dyed using the printing ink set of any one of Application Examples 1 to 7.

  According to the printing method of Application Example 8, since the printing ink set of any one of the above examples is used, even when the printing ink set after long-term storage is used, it is possible to realize printing with excellent color development. Can do.

[Application Example 9]
In the printing method of application example 8,
The fibers may include at least one of cellulosic fibers and polyamide fibers.

  According to the printing method of Application Example 9, since the cellulose fiber and the polyamide fiber have good compatibility with the reactive dye, it is possible to realize printing that is further excellent in color development and fastness.

  Hereinafter, preferred embodiments of the present invention will be described. The embodiment described below describes an example of the present invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention.

  Hereinafter, the ink set for textile printing and the textile printing method will be broadly described in this order. In this specification, “inkjet printing” refers to recording ink on a fiber (the surface thereof) which is one type of recording medium using an inkjet method, and is one type of inkjet recording. “Printing” refers to a method in which a reactive dye is printed on a fiber (the surface) which is one type of recording medium, and dyed onto the fiber by a process such as heat treatment.

1. Textile ink set The textile ink set according to the present embodiment is a textile ink set for textile printing with a reactive dye, and includes a first ink containing a reactive dye, an alkali A second ink containing an agent, wherein the second ink contains neither urea nor a urea derivative. The textile printing ink set according to the present embodiment may have a third ink containing at least one selected from the group consisting of urea and urea derivatives. Hereinafter, the first ink, the second ink, and the third ink will be described in this order.

1.1. First ink 1.1.1. Reactive dye The first ink contains a reactive dye as a colorant. Specific examples of the reactive dye are not particularly limited and include those exemplified below.

  C. I. Reactive Black 5, 8, 13, 14, 31, 34, 39; C.I. I. Reactive Yellow 2, 3, 7, 15, 17, 18, 22, 23, 24, 25, 27, 37, 39, 42, 57, 69, 76, 81, 84, 85, 86, 87, 92, 95, 102 , 105, 111, 125, 135, 136, 137, 142, 143, 145, 151, 160, 161, 165, 167, 168, 175, 176; I. Reactive Orange 1, 4, 5, 7, 11, 12, 13, 15, 16, 20, 30, 35, 56, 64, 67, 69, 70, 72, 74, 82, 84, 86, 87, 91, 92 93, 95, 107; C.I. I. Reactive Red2, 3, 3: 1, 5, 8, 11, 21, 22, 23, 24, 28, 29, 31, 33, 35, 43, 45, 49, 55, 56, 58, 65, 66, 78 83, 84, 106, 111, 112, 113, 114, 116, 120, 123, 124, 128, 130, 136, 141, 147, 158, 159, 171, 174, 180, 183, 184, 187, 190 193, 194, 195, 198, 218, 220, 222, 223, 226, 228, 235; I. Reactive Violet 1, 2, 4, 5, 6, 22, 23, 33, 36, 38; C.I. I. Reactive Blue 2, 3, 4, 7, 13, 14, 15, 19, 21, 25, 27, 28, 29, 38, 39, 41, 49, 50, 52, 63, 69, 71, 72, 77, 79 89, 104, 109, 112, 113, 114, 116, 119, 120, 122, 137, 140, 143, 147, 160, 161, 162, 163, 168, 171, 176, 182, 184, 191, 194 195, 198, 203, 204, 207, 209, 211, 214, 220, 221, 222, 231, 235, 236; I. Reactive Green 8, 12, 15, 19, 21; C.I. I. Reactive Brown 2, 7, 9, 10, 11, 17, 18, 19, 21, 23, 31, 37, 43, 46 and the like. These reactive dyes may be used alone or in combination of two or more.

  The content of the reactive dye in the first ink is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass.

1.1.2. Urea and urea derivatives The first ink preferably contains urea and urea derivatives. By containing urea or the like in the first ink, moisture introduction into the fiber can be improved during the steam treatment, and the reactive dye follows the moisture, so that uniform and high color printing is possible. Become.

  Examples of the urea derivative include alkylureas such as dimethylurea, thiourea, monomethylthiourea, and dimethylthiourea.

  The content of urea or the like in the first ink is preferably 10 to 20% by mass, and more preferably 10 to 15% by mass when the third ink containing urea or the like is not used. On the other hand, the content of urea or the like in the first ink can be made additive-free or smaller when a third ink containing urea or the like is used. That is, the content of urea or the like in the first ink can be appropriately adjusted while balancing with the content of urea or the like contained in the third ink.

In any of the above embodiments, from the viewpoint of increasing the efficiency of dyeing of reactive dyes to fibers, the amount of urea and the like is preferably 1 to ⁸ g per 1 m ^{2 of} fibers, and preferably 1 to ⁴ g. Is more preferable.

1.1.3. Water The first ink preferably contains water as a liquid medium. As the water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. In addition, the use of water sterilized by ultraviolet irradiation or hydrogen peroxide is preferable because generation of mold and bacteria can be prevented when the textile printing ink set according to the present embodiment is stored for a long period of time.

1.1.4. Other Additives Additives such as a humectant, a penetrating agent, a surfactant, and an antiseptic can be added to the first ink as necessary. With these additives, the viscosity and surface tension of the ink can be adjusted to appropriate values, so that an ink set suitable for ink jet textile printing can be obtained.

<Humectant>
Examples of the humectant include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2- Polyhydric alcohols such as pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-octanediol, glycerin, hexanetriol, thiodiglycol; 2-pyrrolidone, N -Heterocyclic compounds such as methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone; sulfoxides such as dimethyl sulfoxide. These humectants may be used alone or in combination of two or more.

  The content of the humectant in the first ink is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.

<Penetration agent>
Examples of penetrants include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monopropyl ether, Examples include glycol ethers such as dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether. These penetrants may be used alone or in combination of two or more.

  The content of the penetrant in the first ink is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass.

<Surfactant>
Examples of the surfactant include a silicon-based surfactant, an acetylene glycol-based surfactant, an anionic surfactant, and a fluorine-based surfactant.

As the silicon-based surfactant, a polysiloxane compound or the like is preferably used, and examples thereof include polyether-modified organosiloxane. More specifically, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (above trade names, manufactured by Big Chemie Japan Co., Ltd.), KF-351A, KF- 352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-2
2-4515, KF-6011, KF-6012, KF-6015, KF-6017 (above trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  Examples of acetylene glycol surfactants include Surfinol 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 (all trade names, manufactured by Air Products and Chemicals Inc.), Olphin B, Y, P, A, STG, SPC, E1004, E1010, PD- 001, PD-002W, PD-003, PD-004, 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, Kawaken Fine Chemical Co., Ltd.).

  Although it does not specifically limit as an anionic surfactant, For example, Perex SS-H, SS-L, Latem WX, E-150, Neoperex GS, G-15, G-25, G-35 (all goods above) Name, manufactured by Kao Corporation).

  As a fluorine-type surfactant, what was synthesize | combined suitably may be used and a commercial item may be used. Examples of the commercially available products include S-144, S-145 (manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, Fluorard-FC4430 (manufactured by Sumitomo 3M Co., Ltd.); FSO, FSO-100, FSN, FSN- 100, FS-300 (manufactured by Dupont); FT-250, 251 (manufactured by Neos Corporation), and the like. Among these, FSO, FSO-100, FSN, FSN-100, and FS-300 manufactured by Dupont are preferable because they can provide good print quality and storage stability.

  The content of the surfactant in the first ink is preferably 0.1 to 1.5% by mass, more preferably 0.1 to 1.0% by mass.

<Preservative>
Preferred specific examples of the preservative include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzoisothiazolin-3-one (Zeneca Corp. Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL2, Proxel TN, Proxel LV), 4-chloro-3-methylphenol (Bayer's Preventol CMK, etc.) and the like.

1.2. Second ink 1.2.1. Alkaline agent The second ink contains an alkali agent for reacting the reactive dye with the fiber.

  Examples of the alkali agent include sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, and sodium triphosphate. These alkaline agents may be used alone or in combination of two or more.

  The content of the alkali agent in the second ink is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, from the viewpoint of sufficiently attaching the alkali agent to the fibers.

It is preferable that the adhesion amount of the alkaline agent is 0.5 to 5 g per 1 m ^{2 of} fiber, and 1 to ³ g
More preferably. When the adhesion amount of the alkaline agent is smaller than 0.5 g / m ^2, there is a possibility that the reactive dye cannot be sufficiently fixed to the fabric. Moreover, if the adhesion amount of the alkaline agent is larger than 5 g / m ² , the fabric may turn yellow. In addition, when an alkaline agent is applied with an ink jet head, the head may be damaged.

1.2.2. Urea and urea derivatives The second ink contains neither urea nor urea derivatives. It has been found by the present inventors that when an alkali agent coexists with urea or the like, urea or the like is decomposed by the alkali agent by long-term storage, and long-term storage stability is impaired. Note that “long term” in this specification means a period of about 6 months at room temperature (25 ° C.). If urea or the like is decomposed, the introduction of moisture into the fiber is lowered, which causes a decrease in color developability. In addition, carbon dioxide and ammonia are generated by the decomposition of urea, so that the surrounding environment may be deteriorated. In particular, in the ink jet method, ejection stability may be impaired due to generation of bubbles. Therefore, in the textile printing ink set according to the present embodiment, the second ink containing the alkali agent is configured to contain neither urea nor a urea derivative, thereby solving the above problem. .

1.2.3. Anti-reduction agent The second ink preferably contains an anti-reduction agent. By adding an anti-reducing agent to the second ink, it is possible to suppress the bond between the fiber and the reactive dye from being cut by the reducing action, and to prevent printing unevenness and the printing density and hue. Reproducibility is improved and high color development can be obtained. As such a reduction inhibitor, nitrobenzene sulfonate is preferably used, and an alkali metal salt of metanitrobenzene sulfonic acid, particularly a sodium salt is preferably used.

  The content of the anti-reduction agent in the second ink is preferably 0.1 to 5.0% by mass.

1.2.4. Water The second ink preferably contains water as a liquid medium. As the water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. In addition, the use of water sterilized by ultraviolet irradiation or hydrogen peroxide is preferable because generation of mold and bacteria can be prevented when the textile printing ink set according to the present embodiment is stored for a long period of time.

1.2.5. Other Additives To the second ink, additives such as a moisturizing agent, a penetrating agent, a surfactant, and a preservative described in the first ink can be added as necessary. The type and content of each additive are the same as those of the first ink. With these additives, the viscosity and surface tension of the ink can be adjusted to appropriate values, so that an ink set suitable for ink jet textile printing can be obtained.

1.3. Third Ink The textile printing ink set according to the present embodiment may have a third ink containing at least one selected from the group consisting of urea and urea derivatives. By having the third ink containing urea or the like in the textile printing ink set according to the present embodiment, the urea or the like added to the first ink can be added without or a smaller amount. Thereby, the balance of the viscosity of each ink can be kept favorable, and for example, an ink set suitable for an ink jet system is obtained.

1.3.1. Urea and urea derivatives The third ink contains at least one selected from the group consisting of urea and urea derivatives described in the first ink.

  The content of urea or the like in the third ink can be adjusted as appropriate while balancing with the content of urea or the like in the first ink. For example, when the content of urea or the like in the first ink is 0% by mass, the content of urea or the like in the third ink is preferably 10 to 20% by mass, more preferably 10 to 15% by mass. It is.

From the viewpoint that the adhesion amount of urea or the like is 1 to ⁸ g per 1 m ^{2 of} fiber, the total of the content of urea or the like in the first ink and the content of urea or the like in the third ink is 10 to 20 mass. It is preferable to adjust so that it may become%.

1.3.2. Adhesive agent It is preferable that the third ink contains an adhesive agent. By adding a paste to the third ink, a reactive dye can be effectively attached to the fiber, so that printing with reduced bleeding can be realized.

  Examples of the paste include natural gums such as guar gum and locust bean gum, starches, seaweeds such as sodium alginate and fungi, plant skins such as pectic acid, cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, Processed starches such as roasted starch, alpha starch, carboxymethyl starch, carboxyethyl starch, hydroxyethyl starch, processed natural gums such as shiratsu gum and roast bean gum, algin derivatives, or polyvinyl alcohol, polyacrylates, etc. Synthetic glue, emulsion and the like can be mentioned. Among these, from the viewpoint of effectively realizing printing with reduced bleeding, at least one polymer compound selected from the group consisting of sodium alginate, carboxymethylcellulose, and hydroxyethylcellulose is preferable.

  The content of the paste in the third ink is preferably 0.05 to 5.0% by mass, more preferably 0.1 to 2.0% by mass.

1.3.3. Water The third ink preferably contains water as a liquid medium. As the water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. In addition, the use of water sterilized by ultraviolet irradiation or hydrogen peroxide is preferable because generation of mold and bacteria can be prevented when the textile printing ink set according to the present embodiment is stored for a long period of time.

1.3.4. Other Additives To the third ink, additives such as a moisturizing agent, a penetrating agent, a surfactant, and a preservative described in the first ink can be added as necessary. The type and content of each additive are the same as those of the first ink. With these additives, the viscosity and surface tension of the ink can be adjusted to appropriate values, so that an ink set suitable for ink jet textile printing can be obtained.

2. Printing Method The printing method according to the present embodiment is characterized in that fibers are dyed using the above-described printing ink set. According to the printing method according to the present embodiment, since any one of the above-described printing ink sets is used, it is possible to achieve printing with excellent color development even when using an ink set after long-term storage. it can.

  In the printing method according to the present embodiment, it is preferable that the fiber to be printed includes at least one of a cellulose fiber and a polyamide fiber. Cellulosic fibers and polyamide fibers have good compatibility with reactive dyes, so that it is possible to realize printing with excellent color development and fastness.

  Examples of cellulosic fibers include cotton, hemp, rayon, polynosic, cupra, and lyocell. Examples of polyamide fibers include silk, wool, and nylon.

  Hereinafter, the textile printing method according to the present embodiment will be specifically described. The main steps of the textile printing method according to the present embodiment include the following pretreatment and printing steps, fixing steps, and washing steps.

(1) Pretreatment and printing process: a process of applying the first ink, the second ink, and, if necessary, the third ink to a place where the fiber needs to be dyed. The second ink and the third ink are used to perform pretreatment on a portion that needs to be dyed. The first ink is used for dyeing fibers and forming an image. The pretreatment and the printing process are preferably performed by an ink jet method in order to apply ink to a necessary portion.

  As an ink jet method, a piezo head type ink jet method in which ink droplets are formed and ejected by a change in the mechanical volume of the piezoelectric element; thermal energy is applied to the ink, and ink droplets are formed and ejected using the resulting volume expansion. Any of a bubble jet (registered trademark) ink jet method may be used. However, the piezo head is excellent in durability and can be said to be particularly preferable in a field where stable ejection is required for a long time such as textile printing. Therefore, the piezo head type ink jet method is preferable. As a recording method for the ink jet printer, either a serial head method or a line head method can be used.

  In the present embodiment, the pretreatment with the second ink (and the third ink as necessary) and the printing with the first ink are simultaneously performed. That is, in order to perform printing in a predetermined area, when the recording operation from the start of scanning on the predetermined area with the inkjet head to the end of scanning is performed once, in the present embodiment, this one time is performed. In this recording operation, the first ink is applied immediately after applying the second ink (and the third ink if necessary) by the head. As described above, by simultaneously performing the preprocessing and the printing in one recording operation, it is possible to prevent the position where the preprocessing ink and the printing ink are applied from being shifted.

  Preprocessing and printing may be performed in separate recording operations. That is, in the first recording operation, the pretreatment is performed on the predetermined area with the second ink (and the third ink if necessary), and then the second recording operation is performed with the first ink. The printing may be performed on the predetermined area. Further, the second ink, the third ink, and the first ink may be applied by separate recording operations. In this case, since the first ink can be applied after the second ink (and the third ink if necessary) is dried, it is possible to prevent bleeding of the first ink. Become.

After the pretreatment and the printing process, the fiber on which the image is formed may be preliminarily dried by leaving it at a temperature of room temperature to 150 ° C. for 0.5 to 30 minutes. This preliminary drying improves the color density and
Bleeding can be effectively prevented.

(2) Fixing step: A step of reacting the reactive dye with the fiber by steam treatment to fix the reactive dye to the fiber. The conditions for the steam treatment can be appropriately determined in consideration of the fiber type and the like. For example, the humidity is 50 to 100% (preferably the humidity is 80 to 100%) and the temperature is 90 to 120 ° C. (preferably 95 to 105). C.) for 3 to 60 minutes (preferably 5 to 40 minutes).

(3) Washing step: This is a step of removing reactive dyes that were not fixed by washing the fibers (that did not contribute to the reaction). When the reactive dye that has not been fixed remains on the fiber, the color developability may deteriorate and the fastness may decrease. In addition, the alkaline agent, urea, etc. attached to the fibers can be removed by the washing step. In the washing step, washing with warm water containing a surfactant is preferable.

3. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.

3.1. Production of ink set for textile printing The materials and compositions shown in Tables 1 to 3 were sufficiently mixed and stirred, and then filtered through a membrane filter having a pore size of 5.0 μm to obtain the first shown in Table 1. Ink (1A, 1B, 1C), the second ink (2A, 2B, 2C, 2D) shown in Table 2, and the third ink (3A, 3B, 3C) shown in Table 3 were prepared.

In addition, the brand names in Tables 1 to 3 are as follows.
・ Orphine E1010 (manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant)
Proxel XL2 (manufactured by Zeneca, 1,2-dibenzisothiazolin-3-one)
・ Perex SS-H (manufactured by Kao Corporation, sodium alkyldiphenyl ether disulfonate)

  Next, as shown in Table 4, the ink sets for textile printing of Examples 1 to 4 and Comparative Examples 1 and 2 were combined by combining the first ink, the second ink, and the third ink obtained above. Configured.

3.2. Printing method 3.2.1. Pretreatment step and printing step An ink jet printer PX-G930 (manufactured by Seiko Epson Corporation) was filled with the first ink, the second ink, and the third ink prepared as described above. Thereafter, the first ink, the second ink, and the third ink were applied to the fibers (100% cotton). The image resolution was 1440 × 720 dpi.

3.2.2. Fixing process The dyed product obtained through the pretreatment process and the printing process is subjected to a steam treatment under the following conditions using an HT steamer (HT3-550, manufactured by Sakurai Dyeing Machine Co., Ltd.), and a reactive dye is used as a fiber. Fixed to.
・ Steam temperature: 102 ℃
・ Humidity: 100% RH
・ Processing time: 10 minutes

3.2.3. Washing process The dyed product obtained through the fixing process was washed with water and gradually added with warm water. Then, it was immersed in 85 degreeC warm water containing an anionic surfactant, and stirred for 15 minutes. Furthermore, it was washed manually while putting tap water in the cleaning solution. Finally, the washed cloth was ironed to obtain a printed product.

3.3. Evaluation method 3.3.1. Evaluation of color development The OD value of each printed matter of Examples 1 to 4 and Comparative Examples 1 and 2 was measured using a densitometer (Spectroino: manufactured by Gretag). The evaluation criteria for color developability are as follows.
◎: OD value 1.5 or more ○: OD value 1.3 or more and less than 1.5 Δ: OD value 1.1 or more and less than 1.3 ×: OD value less than 1.1

3.3.2. Evaluation of coloring property after storage Each ink set for textile printing of Examples 1 to 4 and Comparative Examples 1 and 2 was stored in a thermostat set at 60 ° C for 5 days. Using the ink set for textile printing after storage, a printed matter was obtained in the same manner as in the textile printing method described above, and the color development evaluation was carried out. The evaluation criteria for color developability are the same as described above.

3.3.3. Bleeding Evaluation Regarding the printed matter obtained by the above-described printing method, the printed matter obtained in Example 1 was used as a reference, and it was visually determined whether or not bleeding was observed.
○: Bleeding is not observed as compared with the printed matter of Example 1.
X: Bleeding is recognized more than the printed matter of Example 1.

3.4. Evaluation results Table 4 shows the combinations of the ink sets for textile printing and the results of the evaluation tests.

  As is apparent from the results of Examples 1 to 4 in Table 4, the storage stability of the ink set for textile printing can be obtained by adopting a configuration in which the second ink containing an alkaline agent does not contain either urea or a urea derivative. It became clear that the color development of the printed matter obtained using the ink set for printing after storage at 60 ° C. for 5 days was also good.

  On the other hand, the textile printing ink set of Comparative Example 1 uses the second ink in which an alkali agent and urea coexist, and therefore urea and the like are decomposed by the alkali agent in the second ink after being stored at 60 ° C. for 5 days. As a result, it was found that the color developability of the obtained printed matter was also poor.

  In the printing ink set of Comparative Example 2, since the second ink does not contain an alkali agent, the reactivity between the reactive dye and the fiber is poor, and the colorability of the obtained printed matter may be poor. found.

  In addition, since the results of bleeding in Examples 2 to 4 were better than the results of bleeding in Example 1, it was found that the use of ink containing a paste can effectively suppress bleeding.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (9)

A printing ink set for printing on a fiber with a reactive dye,
A first ink containing a reactive dye and a second ink containing an alkaline agent,
The ink set for textile printing, wherein the second ink contains neither urea nor a urea derivative.   The ink set for textile printing according to claim 1, wherein the first ink contains at least one selected from the group consisting of urea and a urea derivative.   The ink set for textile printing according to claim 1 or 2, further comprising a third ink containing at least one selected from the group consisting of urea and urea derivatives.   The ink set for textile printing according to claim 3, wherein the third ink further contains at least one polymer compound selected from the group consisting of sodium alginate, carboxymethylcellulose, and hydroxyethylcellulose.   The alkaline agent is at least selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, and sodium triphosphate. The ink set for textile printing according to any one of claims 1 to 4, which is one kind.   The textile printing ink set according to any one of claims 1 to 5, wherein the second ink further contains a reduction inhibitor.   The textile printing ink set according to any one of claims 1 to 6, wherein the first ink further contains a humectant, a penetrating agent, and a surfactant.   A textile printing method comprising dyeing fibers using the textile printing ink set according to any one of claims 1 to 7.   The textile printing method according to claim 8, wherein the fibers include at least one of cellulosic fibers and polyamide fibers.