JP4710337B2 - Fixing accelerating composition for inkjet printing, inkjet printing set, and inkjet printing method - Google Patents

Description

  The present invention relates to a fixing accelerating composition for inkjet printing, an inkjet printing set, and an inkjet printing method. According to the present invention, yellowing in a non-image area can be effectively prevented.

In ink jet textile printing in which the ink jet recording method is applied to textile printing, ink droplets are ejected onto various kinds of pretreated fabrics, and ink is attached and colored to form an image. This is because among various blending components of ink compositions used in conventional textile printing methods, there are blending components that are relatively difficult to adjust to low viscosity suitable for inkjet recording methods, such as glue. On the one hand, high-viscosity components such as glue are preliminarily carried on the entire fabric by padding treatment, and on the other hand, the ink composition containing reactive dye is adjusted to low viscosity for ink jet recording. The pretreatment fabric is discharged from the printer head.
Therefore, for example, as shown in FIG. 1, in the case of forming an E-shaped image region 1 and a non-image region 2 which is the other ground portion on the fabric 10, a conventional printing method using a printing screen is used. Since the printing ink is applied to the fabric 10 through the printing screen, the printing ink supplied to the portion of the image area 1 reaches the cloth 10 through the printing screen, whereas the portion of the non-image area 2 The printing ink supplied to is blocked by the printing screen and does not reach the fabric 10. That is, the printing ink does not adhere to the non-image area 2 at all, and the printing ink adheres only to the image area 1.

  On the other hand, when the E-shaped image region 1 and the non-image region 2 which is the other ground portion are formed on the fabric 10 by the inkjet textile printing method as shown in FIG. Is pre-prepared with a pre-treatment liquid, and a pre-treatment fabric is prepared in advance, and then ink is ejected from the ink jet recording printer head to only the image area 1 portion. As a result, the image area 1 is dye-fixed (colored) only, and an E-shaped image area 1 is formed. Ink is not attached to the non-image area 2 and no image is formed, but the compounding components contained in the pretreatment liquid remain.

  By the way, since inkjet printing is generally suitable for small-lot production of various varieties, the pretreated fabric is stored for a long period of time in a wound state until the inkjet printing is performed. . During this long-term storage, the pretreated fabric may turn yellow overall. This yellowing appears mainly in silk fabrics and wool fabrics. This is considered to be caused by gradually modifying the silk fabric or the wool fabric to cause color development because the pretreatment liquid contains an alkali agent. Such yellowing is observed in the entire fabric before ink-jet printing, but is often concealed in the image area after ink-jet printing because it is colored by reactive dyes. It doesn't matter. However, the yellowing of the non-image area remains without being concealed.

  Further, in ink jet textile printing, after imprinting ink on a pretreated fabric, a fixing process similar to the conventional textile printing method is performed. This fixing process is performed, for example, by a steaming process for about 8 minutes in an environment with a temperature of about 102 ° C. and a humidity of 98% or more. Also in this fixing process, for example, yellowing occurs in a non-image area in a silk fabric or a wool fabric. The reason for this is also considered that the pretreatment liquid contains an alkali agent. This yellowing seems to have actually occurred in the entire fabric, but in the image area, it is often concealed by coloring by the reactive dye, and is not a practical problem in many cases. However, the yellowing of the non-image area is not concealed.

Such yellowing does not occur in conventional printing, and is a problem inherent to inkjet printing. Moreover, in inkjet printing, it occurs not only when the pretreated fabric is stored for a long period of time, but also occurs when the ink printing is performed immediately after the preparation of the pretreated fabric, due to the fixing process. However, this kind of yellowing phenomenon has not been taken up at all, and therefore no solution has been proposed.
Accordingly, an object of the present invention is to eliminate the yellowing inherent in ink jet printing.

The above problems are solved by the present invention.
A pretreatment agent for ink jet textile printing comprising a fixing accelerating composition that can be ejected from a printer head for ink jet recording, and a non-alkali pretreatment liquid,
The fixing accelerating composition includes an alkali agent, a humectant, and water,
The humectant Ri Oh polyhydric alcohol having a boiling point of not lower than 0.99 ° C. at normal pressure,
The non-alkaline pretreatment liquid includes a paste and water,
The sizing agent can be solved by a pretreatment agent for ink jet printing, which contains at least one selected from sodium alginate and carboxymethylcellulose fiber .
In a preferred embodiment of the pretreatment agent according to the present invention, the fixing accelerating composition and / or the non-alkaline pretreatment liquid further contains a hydrotropic agent,
The hydrotropic agent is at least one selected from the group consisting of urea, dimethylurea, thiourea, monomethylthiourea, and dimethylthiourea.

The present invention also relates to an ink jet printing set comprising a combination of the fixing accelerating composition and the non-alkali pretreatment liquid and an ink composition for ink jet printing .
In another preferred embodiment of the ink jet textile printing set according to the present invention, the ink composition for ink jet textile printing contains a reactive dye whose fixability is improved by steaming with an alkali agent.

In the present invention, the entire fabric is treated with a non-alkaline pretreatment liquid, and then the above-mentioned fixing accelerating composition and ink-jet printing ink composition are applied to the image area from the ink-jet recording printer head in the following (1). Alternatively, the present invention also relates to an ink-jet printing method characterized by discharging in the order described in (2) .
(1) First, the fixing accelerating composition is printed, and then the ink-jet printing ink composition is printed.
(2) In a preferred embodiment of the ink-jet printing method according to the present invention , in which the ink composition for ink-jet printing is first printed and subsequently the fixing accelerating composition is printed, the ink composition is applied to a fabric made of animal fibers. To do.

  In conventional inkjet printing, the entire printing paste component is divided into two components, a pretreatment agent and ink, and the entire fabric (image region and non-image region) is padded with the pretreatment agent, and the ink is removed from the printer head. In the present invention, the conventional pretreatment agent is further divided into a fixing accelerating composition and a non-alkaline pretreatment liquid, whereas the alkali agent contained in the conventional pretreatment agent is discharged in the image area. Is added only to the fixing accelerating composition, and on the other hand, a non-alkaline pretreatment liquid containing a paste and excluding an alkaline agent is prepared. Then, pretreatment of the entire fabric (image area and non-image area) is performed using this non-alkali pretreatment liquid, and a fixing accelerating composition and an ink containing an alkaline agent are ejected from the printer head to the image area. Accordingly, since no alkali agent is present in the pre-treated fabric, yellowing does not occur even if the pre-treated fabric is stored for a long period of time, and the non-image area is also yellowed by the fixing process after the printing process. Does not occur.

[Fixing accelerating composition]
The fixing accelerating composition according to the present invention includes at least an alkali agent, a humectant, and water. Further, it is adjusted so that it can be discharged from a printer head for ink jet recording. That is, the fixing accelerating composition according to the present invention always contains an alkali agent among various blending components contained in the pretreatment agent in conventional ink jet printing, and does not contain a highly viscous blending component (for example, a paste). Further, the fixing accelerating composition according to the present invention is contained in a pretreatment agent in conventional ink jet textile printing in addition to the alkali agent and humectant as long as it can be adjusted so as to be ejectable from a printer head for ink jet recording. Optional ingredients can be included.

(1) Alkaline agent An alkali agent is contained in a pretreatment agent in conventional inkjet printing, and is used for the purpose of improving the fixing reaction rate of the inkjet reactive dye ink. Accordingly, as the alkali agent contained in the fixing accelerating composition according to the present invention, any alkali agent having a function of accelerating the reaction of the reactive dye during fixing can be used. Specifically, the same compound as the alkaline agent contained in the pretreatment agent in the conventional inkjet printing can be used, and examples thereof include sodium ash, sodium hydroxide, sodium triphosphate, sodium acetate, and the like. Particularly preferred is sodium bicarbonate.
The content of the alkali agent is not particularly limited, but is preferably 1 to 7% by weight, more preferably 2 to 5% by weight, based on the total weight of the fixing accelerating composition. If the content of the alkaline agent is less than 1% by weight, the fixing reaction promoting effect may be reduced, and if it exceeds 7% by weight, animal fibers such as silk may be damaged.

(2) Moisturizer A moisturizer is used for the purpose of imparting physical properties that can be ejected from the printer head for ink jet recording to the fixing accelerating composition. Therefore, a humectant used in a normal ink composition for inkjet recording can be used. Specifically, it is preferable to use a polyhydric alcohol having a boiling point of 150 ° C. or higher at normal pressure, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1 , 6-hexanediol, 1,2,6-hexanetriol, 1,8-octanediol, 1,2-octanediol, mesoerythritol, pentaerythritol, thioglycol and the like.

式（Ｉ）中において、ＥＰ１、ＥＰ２、及びＥＰ３は、それぞれ独立してエチレンオキシ基又はプロピレンオキシ基を表す。従って、同一分子中にエチレンオキシ基、プロピレンオキシ基が混在してもよく、またそのいずれかのみ存在していてもよい。ｌ、ｍ、及びｎは独立して０又は１以上の自然数を表すが、ｌ、ｍ、及びｎの少なくとも一つは１以上であり、かつインク組成物中に含まれる式（Ｉ）の化合物全体の平均値としてのｌ＋ｍ＋ｎが１以上３０以下であり、より好ましくはその下限は２以上であり、その上限は２８以下である。また、その好ましい範囲は３〜２６である。ｌ＋ｍ＋ｎが上記範囲にあることで、プリントヘッドに定着促進組成物を充填し長時間放置しても直ちに安定した吐出が可能となり、またインク組成物の粘度が調整が行いやすい。 In the case where the fixing acceleration composition and the ink for inkjet printing containing a reactive dye as a coloring material are ejected from the same inkjet recording head, it is preferable to use a humectant that hardly reacts with the reactive dye. . Specific examples include compounds of formula (I).

In the formula (I), EP1, EP2, and EP3 each independently represent an ethyleneoxy group or a propyleneoxy group. Therefore, an ethyleneoxy group and a propyleneoxy group may be mixed in the same molecule, or only one of them may be present. l, m, and n independently represent a natural number of 0 or 1 or more, but at least one of l, m, and n is 1 or more, and the compound of the formula (I) contained in the ink composition L + m + n as an overall average value is 1 or more and 30 or less, more preferably the lower limit is 2 or more, and the upper limit is 28 or less. Moreover, the preferable range is 3-26. When l + m + n is in the above range, even when the print head is filled with the fixing accelerating composition and allowed to stand for a long time, stable ejection can be immediately performed, and the viscosity of the ink composition can be easily adjusted.

The compound of the formula (I) can be produced by adding a target molar amount of ethylene oxide or propylene oxide, preferably using glycerin as a starting material in an atmosphere such as an alkali. The compound of formula (I) obtained by this method is generally a mixture, but may be made into a single compound by a process such as distillation.
Moreover, it is also possible to utilize a commercial item as a compound of Formula (I), for example, Lipo Chemicals Inc. Liponic EG-1 (a compound of formula (I) in which EP1, EP2, and EP3 are all ethyleneoxy groups and l + m + n is 26) available from (New Jersey, USA), EG-7 (EP1, EP2, And EP3 are ethyleneoxy groups, and l + m + n is a compound of formula (I) of 26).

  The content of the humectant is not particularly limited, but is preferably 5 to 40% by weight, more preferably 5 to 30% by weight, based on the total weight of the fixing accelerating composition. If the content of the humectant is less than 5% by weight, dry clogging may occur, and if it exceeds 40% by weight, bleeding may occur after fixing.

(3) Water In the fixing accelerating composition of the present invention, water is the main solvent. As the water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, or distilled water, or ultrapure water can be used. Further, the use of water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferable because the generation of mold and bacteria can be prevented when the fixing accelerating composition is stored for a long period of time.

(4) Thickener The fixing accelerating composition of the present invention can contain a thickener, if necessary. As the thickener, a compound having an excellent affinity with water is preferable, and it is necessary that the ejection characteristics of the fixing accelerating composition are not adversely affected. As the thickener, for example, polyethylene glycol can be used.

(5) Ejectability Since the fixing accelerating composition of the present invention is used by being ejected from an inkjet recording printer head onto an image area of a fabric pretreated with a non-alkali pretreatment liquid described later, an inkjet recording printer is used. It is necessary to have various physical properties that enable ejection from the head. As such physical properties, for example, the viscosity is 20 ° C., preferably 8.0 m · Pa · s or less, and more preferably 1.5 to 6.0 m · Pa · s. If it is 8.0 m · Pa · s or less, ink can be ejected at normal ambient temperature without any problem. Ink exceeding 8.0 m · Pa · s at 20 ° C. has poor ejection stability in a low temperature region.

[Non-alkaline pretreatment liquid]
The non-alkaline pretreatment liquid used in the present invention corresponds to a pretreatment agent used in conventional inkjet printing, in which a high viscosity substance such as a paste is included and an alkali agent is removed. It can be used in the same manner as the pretreatment agent in ink jet textile printing. Therefore, this non-alkali pretreatment liquid preferably contains at least a paste and a hydrotropic agent. Moreover, a reduction inhibitor can also be contained. Furthermore, in order to improve the printing density, silica may be contained.

(1) Glue Glue is contained in a pretreatment agent in conventional ink jet textile printing, and is effective for fixing ink and preventing bleeding. Therefore, in the non-alkaline pretreatment liquid used in the present invention, any paste that is usually contained in a pretreatment agent for conventional inkjet printing can be used. For example, natural gums such as guar and locust bean, Starches, seaweeds such as sodium alginate, funari, plant skins such as pectic acid, fibrin derivatives such as methyl fibrin, ethyl fibrin, hydroxyethylcellulose, carboxymethylcellulose, roasted starch, alpha starch, carboxymethyl starch, carboxy Processed starches such as ethyl starch and hydroxyethyl starch, processed natural gums such as shiraz gum and roast bean gum, algin derivatives, synthetic glues such as polyvinyl alcohol and polyacrylate, emulsions and the like can be used. In particular, a paste having a poor dyeing property with the reactive dye to be used is preferably used. The content of the paste is preferably 0.5 to 20% by weight in terms of solid content with respect to the total weight of the non-alkali pretreatment liquid. If the content of the paste is less than 0.5% by weight, the ink may not be sufficiently fixed and bleeding may occur. If the content exceeds 20% by weight, the viscosity becomes high and the non-alkaline pretreatment liquid is used. It may not spread throughout the fabric and may cause imprinting.

(2) Water In the non-alkali pretreatment liquid used in the present invention, water is the main solvent. As the water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, or distilled water, or ultrapure water can be used. Further, the use of water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferable because the generation of mold and bacteria can be prevented when the fixing accelerating composition is stored for a long period of time.

(3) Non-alkaline The non-alkali pretreatment liquid used in the present invention does not contain an alkali agent, and the pH is preferably 9 or less, more preferably 8 or less. If the pH exceeds 10, yellowing may occur in the non-image area.
The non-alkaline pretreatment liquid used in the present invention is used in the same manner as the pretreatment agent in conventional ink jet textile printing and does not need to be discharged from the printer head for ink jet recording, so the viscosity and the like are not limited.

[Fixing promoting composition and other components of non-alkali pretreatment liquid]
The fixing accelerating composition and the non-alkali pretreatment liquid according to the present invention are obtained by dividing the pretreatment agent in conventional ink jet printing into two parts. Accordingly, it is satisfied that the fixing accelerating composition contains (1) an alkali agent, a humectant, and water, and (2) that the composition can be ejected from a printer head for inkjet recording. As long as 1) the paste is included, and (2) the alkali-free agent is satisfied, the fixing accelerating composition and the non-alkali pretreatment liquid usually contain a pretreatment agent in conventional inkjet printing. Can be included in either or both. The following is a description of representative examples of these blending components.

(1) Hydrotropy agent A hydrotropic agent is included in a pretreatment agent in conventional ink jet printing, and improves steaming efficiency, printing density, stability of fabric after padding, or padding cloth. Effective in stabilizing the surface state. Therefore, a hydrotropic agent can be contained in either one or both of the fixing accelerating composition and the non-alkali pretreatment liquid according to the present invention. As the hydrotropic agent, any hydrotropic agent usually contained in a pretreatment agent for conventional inkjet printing can be contained, and specifically, urea, dimethylurea, thiourea, monomethylthiourea, or Alkyl ureas such as dimethylthiourea can be used.
The content of the hydrotropic agent is not particularly limited, but is preferably 5 to 20% by weight, more preferably 5 to 15% by weight based on the total weight of the fixing accelerating composition or the non-alkaline pretreatment liquid. %. When the content of the hydrotropic agent is less than 5% by weight, it is difficult to obtain the above effect sufficiently, and when it exceeds 20% by weight, it may cause bleeding.

(2) Anti-reducing agent Both the fixing accelerating composition and the non-alkaline pretreatment liquid used in the present invention, or either one of them, can also contain an anti-reducing agent. This is effective for improving the hue reproducibility. When the fixing accelerating composition and / or the non-alkaline pretreatment liquid contains a reduction inhibitor, it is effective for improving the storage stability. By previously adding a reduction inhibitor into the fixing accelerating composition and / or the non-alkaline pretreatment liquid, it is possible to prevent spots that occur when the inkjet printing ink is steamed on the fabric and dyed. In particular, when the textile printing ink is composed of a plurality of dyes, the hue may change in a low density region, but such a problem can be prevented by the reduction inhibitor.
When a fabric treated with a non-alkaline pretreatment liquid containing a reduction inhibitor is printed with a fixing accelerating composition containing a reduction inhibitor and an ink jet printing ink containing a reduction inhibitor, both reduction prevention effects act. Thus, it is possible to obtain a printed matter with extremely excellent color reproducibility.

  In particular, a fabric treated with a non-alkali pretreatment liquid containing an anti-reducing agent is excellent in storage stability. For example, color reproducibility hardly deteriorates even after being placed under high temperature and high humidity for a long time. The amount of the reduction inhibitor in the non-alkali pretreatment liquid is preferably 15% by weight or less, and more preferably 1 to 8% by weight with respect to the non-alkali pretreatment liquid. When the content of the reducing inhibitor exceeds 15% by weight, the powdered reducing inhibitor may be deposited from the fabric treated with the non-alkali pretreatment liquid.

(3) Silica The non-alkaline pretreatment liquid used in the present invention can contain silica, and the silica is effective for improving color developability. Silica preferably has a surface covered with a hydroxyl group. Since the hydroxyl group has a strong affinity for water, the fixing efficiency of the reactive dye can be improved. Further, by combining silica and urea, a synergistic effect works, and this color developability is remarkably improved. The content of silica is preferably 0.5 to 8% by weight with respect to the fixing accelerating composition or the non-alkaline pretreatment liquid. If it is less than 0.5% by weight, the coloring effect is reduced. This effect is particularly remarkable in magenta. On the other hand, if it exceeds 8% by weight, uneven color tends to occur in the magenta printing portion. Further, the color density is lowered in cyan and blue. Furthermore, the silica is easily separated from the fabric, and ink jet discharge defects are likely to occur.
(4) Other additives In addition to the above components, either or both of the fixing accelerating composition and the non-alkaline pretreatment liquid used in the present invention may contain additives. Can be contained. Examples of such additives include preservatives or chelating agents (metal sequestering agents). Preferable examples of the preservative include proxel CRL, proxel BDN, proxel GXL, proxel XL-2, proxel IB, and proxel TN. The preservative not only stabilizes the fixing accelerating composition and the non-alkali pretreatment liquid itself, but is also effective for the stability of the non-alkali pretreatment liquid after padding drying.
Further, the chelating agent (metal sequestering agent) traps heavy metals on the fabric and is effective in preventing dyeing spots. As the chelating agent, ethylenediaminetetraacetate, nitrilotriacetate, hexametaphosphate, pyrophosphate, or metaphosphate is preferable. In addition, TRILON TA, DEKOL SN, and Calgon T commercially available from Benkies, which are commercially available from BASF, are excellent in biodegradability and are suitable for the environment.

[Ink composition for inkjet textile printing]
The ink composition for inkjet printing used in the present invention is not essentially different from the ink composition used in conventional inkjet printing. Representative examples of the components of the ink composition for inkjet textile printing used in the present invention will be described below.

(1) Dye The fixing accelerating composition and non-alkaline pretreatment liquid of the present invention are preferably used in combination with a printing inkjet ink containing a reactive dye. The reactive dye contained in the ink composition for ink jet textile printing used in the present invention is not particularly limited as long as it has the property of being fixed by being chemically bonded to the fabric by heat vapor deposition. A dye having a reactive group such as a chloropyrimidyl group or a vinylsulfone group is preferred. These dyes are selected according to individual purposes. For example, when a high concentration of black is particularly desired, a vinylsulfone reactive dye is suitable. Further, when it is necessary to store the ink composition for inkjet textile printing for a long time, a dye having a monochlorotriazinyl skeleton, that is, a monochloro-substituted 1,3,5-triazin-2-yl skeleton is preferable. Reactive dyes having a monochlorotriazinyl skeleton are particularly suitable as ink-jet ink dyes that require long-term storage stability because they are relatively excellent in thermal stability. Specific examples of the reactive dye contained in the ink composition for inkjet textile printing are listed below.
C. I. Reactive Yellow 3, 6, 12, 18, 86
C. I. Reactive Orange 2, 5, 12, 13, 20,
C. I. Reactive Red 3, 4, 7, 12, 13, 15, 16, 24, 29, 31, 32, 33, 43, 45, 46, 58, 59,
C. I. Reactive violet 1, 2,
C. I. Reactive Blue 2, 3, 5, 7, 13, 14, 15, 25, 26, 39, 40, 41, 46, 49, 176
C. I. Reactive Green 5, 8,
C. I. Reactive Brown 1, 2, 7, 8, 9, 11, 14, and C.I. I. Reactive Black 1, 2, 3, 8, 10, 12, 13
In the present specification, the reactive dye refers to a compound classified as a reactive dye in the color index.

  In the ink composition for ink-jet textile printing used in the present invention, the content of reactive dye is not particularly limited and can be appropriately determined, but is preferably about 1 to 15% by weight, more preferably based on the total weight of the ink composition. Is about 6 to 12% by weight. If the content of the reactive dye is less than 6% by weight, a sufficient printing density cannot be obtained, and if it exceeds 15% by weight, the ejection stability required for the ink-jet ink composition deteriorates, particularly at high temperatures. In this case, ejection failure may occur. In addition, when it is desired to obtain printing gradation, the medium to low density gradation can be improved by adding a light color ink having a dye concentration of 6% by weight or less in addition to the ink composition.

(2) Buffering Agent The ink composition for ink jet textile printing used in the present invention preferably has a pH stabilized by adding a buffering agent. Further, by adjusting the pH to 9 or less, hydrolysis of the reactive dye in the ink composition can be delayed. The progress of hydrolysis not only lowers the fixing density of the fabric, but also advances the ink to a strongly acidic region, which tends to corrode the printing press. In particular, the corrosion of the print head portion causes great damage to the inkjet system. The pH of the ink composition for ink jet textile printing used in the present invention is preferably 6 to 9, more preferably 7 to 8.5. If the pH is too high, hydrolysis of the reactive dye tends to proceed. For example, when it is necessary to leave at 30 ° C. for 1 year or longer, the pH is preferably 9 or less. However, when the ink is used up in a short period of time, the pH of the ink may exceed 10.

  These pHs can be adjusted using a buffer. Examples of these buffering agents include 2-hydroxy-3-monoforinopropanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid (CAPS), N-cyclohexyl-2-aminoethanesulfonic acid, 2- [ Examples include sodium or potassium salts such as 4- (2-hydroxyethyl) -1-piperazinyl] ethanesulfonic acid, N, N-Bis- (2-hydroxyethyl) glycine, phosphoric acid, or tripolyphosphoric acid. In the ink composition for inkjet textile printing used in the present invention, it is preferable to use a phosphate buffer as the buffer.

(3) Water In the ink composition for ink jet textile printing used in the present invention, any water can be used as water, but pure water is preferably used. Pure water can be easily produced by ion exchange or distillation. Further, it is more preferable that the pure water is further sterilized with ultraviolet rays or the like.

(4) Reduction inhibitor The ink composition for inkjet printing used in the present invention may contain a reduction inhibitor. As the reduction inhibitor, nitrobenzene sulfonate is preferably used, and metanitrobenzene sulfonate is more preferably used. The salt is, for example, an alkali metal salt, preferably a sodium salt. In addition, this effect is effective for C.I. I. When reactive blue 176 is included, the effect is particularly great.

(5) Metal sequestering agent Further, the ink composition for ink jet printing used in the present invention may contain a metal ion sequestering agent. As the metal sequestering agent, ethylenediaminetetraacetic acid (EDTA), EDTA salt (for example, sodium salt), hydroxyethylethylenediaminetriacetic acid (EDTA-OH) and the like are suitable.

(6) Other additives The ink composition for inkjet textile printing used in the present invention has an alkylene glycol monoalkyl ether (for example, for the purpose of improving the ejection stability of the ink (particularly, the ejection stability with a piezo head)). , Triethylene glycol mono-n-butyl ether).
In addition, the ink composition for inkjet printing used in the present invention preferably contains a preservative in addition to the above components. Preferable antiseptics include, for example, proxel CRL, proxel BDN, proxel GXL, proxel XL-2, proxel IB, or proxel TN.
Furthermore, the ink composition for inkjet textile printing increases the solubility of the dye by containing a pyrrolidone-based solvent (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone) or thioglycol, and can be applied to a high-concentration dye ink. Excellent discharge stability can be imparted.

  Furthermore, the ink composition for ink jet textile printing used in the present invention contains the above-mentioned constituents as appropriate, but has a viscosity of 8.0 m · Pa · s or less at 20 ° C., preferably 1.5 to 6.0 m · Pa · s is preferred. If it is 8.0 m · Pa · s or less, ink can be ejected at normal ambient temperature without any problem. Ink exceeding 8.0 m · Pa · s at 20 ° C. has poor ejection stability in a low temperature region.

[Inkjet printing set]
The inkjet textile printing set according to the present invention is
(1) the fixing accelerating composition;
It comprises a combination of (2) the non-alkali pretreatment liquid and (3) the ink composition for ink jet textile printing.
In the inkjet printing set, when all the blending components contained in both the fixing accelerating composition (1) and the non-alkaline pretreatment liquid (2) are combined, the blending components of the pretreatment agent in the conventional inkjet printing It is preferable to become the composition similar to. However, as described above, the fixing accelerating composition (1) includes at least an alkali agent, a humectant, and water, but does not include a paste, and the non-alkali pretreatment liquid (2) includes at least a paste. Contains water but does not contain alkaline agent.
The non-alkaline pretreatment liquid (2) is used for pretreatment of the fabric and applied to the entire fabric (image region and non-image region) in the same manner as the pretreatment agent in conventional inkjet printing, and the fixing accelerating composition. (1) and the ink composition for ink jet textile printing (3) are each applied by being ejected only from the printer head for ink jet recording to the image area.

[Inkjet printing method]
The ink jet textile printing method according to the present invention is a process in which a fixing promoting composition and an ink composition for ink jet textile printing are ejected and adhered in an arbitrary order to a fabric that has been pretreated with the non-alkali pretreatment liquid. It is mainly composed of a fixing process and a cleaning process. In each step, known methods and operations can be used. Hereinafter, specific modes of each step will be exemplified.

(1) Pretreatment method As a method of attaching the non-alkaline pretreatment liquid to the entire fabric (that is, the image region and the non-image region), a coating or padding method is desirable as usual. For example, the pick-up rate at the time of padding can be appropriately determined by the thickness of the fabric, the thickness of the fiber, etc., and is preferably 50% or more, and more preferably 65% or more.

(2) Fabric The fabric that can be printed by the method of the present invention is a fabric composed of vegetable fiber, animal fiber, amide fiber, or a blend composed of at least one of these fibers. A fabric made of animal fibers (for example, silk or wool) is preferable.

(3) Inkjet printing The fabric treated with the non-alkali pretreatment liquid is printed with the fixing accelerating composition and the ink composition for inkjet printing by an inkjet method. The order of printing is not limited. Even if the fixing accelerating composition is printed first, and then the ink-jet printing ink composition is printed, the ink-jet printing ink composition is printed first, followed by the printing. The fixing accelerating composition may be printed. The fixing accelerating composition and the ink-jet printing ink composition are printed only in the image area and not in the non-image area.

(4) Fixing After printing, fixing is performed with high heat or high heat steam. As the fixing condition, for example, in the case of a cellulosic fabric, it is preferable to treat at 95 to 105 ° C. near saturated steam for 4 to 12 minutes. In addition, with amide fibers such as silk and wool, it is preferable to treat at 95 to 105 ° C. in the vicinity of saturated steam for 20 to 40 minutes.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.

<Examples 1-3 and Comparative Example 1>
(1) Preparation of fixing accelerating composition Four fixing accelerating compositions having the composition shown in Table 1 below were prepared. Specifically, three types of fixing acceleration compositions (Examples 1 to 3) containing sodium hydrogen carbonate (alkali agent) and one type of fixing acceleration composition (Comparative Example 1) not containing sodium hydrogen carbonate were prepared. did.

表１に記載の数値は重量％である。また、「ポリエチレングリコールＮｏ．１０００」は、関東化学社製であり、「グリセレス」（リポケミカル社）は、エチレンオキシドが付加されたグリセリンである。

The numerical values shown in Table 1 are% by weight. "Polyethylene glycol No. 1000" is manufactured by Kanto Chemical Co., and "Glyceres" (Lipochemical Co.) is glycerin to which ethylene oxide is added.

(2) Preparation of non-alkaline pretreatment liquid In the following physical property evaluation, four types of non-alkali pretreatment liquid used in combination with each fixing accelerating composition described in (1) above were prepared. Specifically, as shown in Table 2 below, three non-alkaline pretreatment liquids (A1 to A3) containing a paste (sodium alginate or carboxymethylcellulose) and not containing sodium hydrogen carbonate (alkali agent), And a paste (sodium alginate), and a pretreatment liquid (C1) that does not contain sodium bicarbonate.

表２に記載の数値は重量％である。

The numerical values described in Table 2 are% by weight.

(3) Preparation of ink composition for ink jet printing In the following physical property evaluation, an ink composition for ink jet printing used in combination with the fixing accelerating composition of (1) above and the non-alkali pretreatment liquid of (2) above (hereinafter, Ink composition B1) was prepared with the composition shown in Table 3 below.

表３に記載の数値は重量％である。「オルフィンＰＤ００２Ｗ」（日信化学工業社）は、アセチレングリコール系界面活性剤である。

The numerical values shown in Table 3 are% by weight. “Orphine PD002W” (Nisshin Chemical Industry Co., Ltd.) is an acetylene glycol surfactant.

"Evaluation of the physical properties"
(A) Yellowing experiment Using the non-alkaline pretreatment liquid A1 (containing no alkali agent) and the pretreatment liquid C1 (containing an alkali agent) prepared in the previous section (2), paddle treatment of Haedo (silk) by a conventional method did.
Subsequently, the padded fabric was left for 1 month in an environment of 40 ° C./60% RH. This condition is an experiment assuming that the padded fabric is left in a normal market for two years. When evaluated visually after one month, the fabric treated with the non-alkali pretreatment liquid A1 (containing no alkali agent) showed no yellowing, whereas the fabric treated with the pretreatment liquid C1 (containing the alkali agent). A clear yellowing was observed.
Furthermore, the fabric after the padding treatment was steamed for 30 minutes at 102 ° C. and near saturated humidity immediately after the padding treatment. This condition is an experiment assuming a case where Haedae (silk) is fixed by a conventional method after printing. When visually evaluated, the fabric treated with the non-alkali pretreatment liquid A1 (containing no alkali agent) is not yellowed, whereas the fabric treated with the pretreatment liquid C1 (containing the alkali agent) A clear yellowing was observed.
As described above, it can be seen that when the pretreatment liquid contains an alkali agent, yellowing occurs in the fabric by long-term storage or fixing treatment.

(B) Inkjet printing test It was confirmed by the following test that a favorable inkjet printing can be obtained by the inkjet printing set according to the present invention.
As an ink jet printing set, the fixing accelerating composition prepared in the preceding item (1) and the pretreatment liquid prepared in the preceding item (2) are variously combined, and the ink composition B1 prepared in the preceding item (3) is further used. A seed printing set was prepared. The breakdown was four kinds of ink jet printing sets (P1 to P4) according to the present invention and two kinds of ink jet printing sets for comparison (R1 and R2).
The printing procedure is as follows.
First, Seika Palace (silk) was padded by a conventional method with the pretreatment liquid prepared in the preceding item (2). Subsequently, the ink composition B1 prepared in the previous item (3) was printed on the padded fabric by the ink jet recording method, and then the fixing accelerating composition prepared in the previous item (1) was printed by the ink jet recording method. . Further, the printed fabric was fixed by steam heat at 102 ° C. and around the saturated vapor pressure for 30 minutes, washed by a conventional method, and dried. With respect to the printed material thus obtained, an OD value (Gretag Colorimeter) was measured, and yellowing of the non-image area was visually evaluated. The results are shown in Table 4.

As is clear from comparison between the results of the printing set R1 and other results, a sufficient printing density cannot be obtained unless an alkali agent is contained in either the fixing accelerating composition or the pretreatment liquid. I understand that. Further, as is apparent from the results of the textile printing set R2, when an alkali agent is contained in both the fixing accelerating composition and the pretreatment liquid, yellowing occurs in the non-image area.
On the other hand, as is clear from the results of the printing sets P1 to P4, according to the printing set of the present invention, a good printing density can be obtained and yellowing does not occur. In particular, as is clear from the results of the printing sets P1 to P3, in the printing set according to the present invention, it is further preferable that the fixing promoting composition and / or the pretreatment liquid contain a hydrotropic agent. High printing density can be obtained.

  According to the present invention, it is possible to effectively prevent yellowing of a non-image area of a pretreated fabric in conventional ink jet printing.

It is a typical perspective view which shows the image area | region and non-image area | region by textile printing.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Image area | region; 2 ... Non-image area | region; 10 ... Fabric.

Claims (6)

A pretreatment agent for ink jet textile printing comprising a fixing accelerating composition that can be ejected from a printer head for ink jet recording, and a non-alkali pretreatment liquid,
The fixing accelerating composition includes an alkali agent, a humectant, and water,
The humectant is a polyhydric alcohol having a boiling point of 150 ° C. or higher at normal pressure,
The non-alkaline pretreatment liquid includes a paste and water,
The pretreatment agent for ink jet printing, wherein the paste contains at least one selected from sodium alginate and carboxymethylcellulose fiber. The fixing accelerating composition and / or the non-alkaline pretreatment liquid further includes a hydrotropic agent,
The hydrotropic agent is at least one selected from the group consisting of urea, dimethylurea, thiourea, monomethylthiourea, and dimethylthiourea.
The pretreatment agent for inkjet printing according to claim 1.   An ink jet printing set comprising a combination of the fixing accelerating composition and the non-alkali pretreatment liquid according to claim 1 or 2 and an ink composition for ink jet printing.   The ink-jet printing set according to claim 3, wherein the ink composition for ink-jet printing comprises a reactive dye whose fixability is improved by steaming with an alkali agent. The entire fabric is treated with the non-alkaline pretreatment liquid, and subsequently, the fixing accelerating composition and the ink-jet printing ink composition according to claim 1 or 2 are applied to the image area from the ink-jet recording printer head (1 Or an ink jet textile printing method, wherein the ink jet textile printing is performed in the order described in (2).
(1) First printing the fixing accelerating composition and then printing the ink composition for inkjet printing (2) First printing the ink composition for inkjet printing and then the fixing accelerating composition Imprint The inkjet printing method according to claim 5 , which is applied to a fabric made of animal fibers.

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