JP2011174007A - Ink for inkjet textile printing, inkjet textile printing method, and textile-printed product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide ink for inkjet textile printing excellent in continuous discharge reliability in an inkjet drawing, excellent in recovery from nozzle clogging, and having little uneven dyeing in a textile-printed image, and an inkjet textile printing method. <P>SOLUTION: The ink for inkjet textile printing includes a disperse dye, a dispersant, water, and a water-soluble organic solvent, and acetylene diol and acetylene glycol. Preferably, the acetylene diol and the acetylene glycol are represented by specific formulae (1) and (2), respectively. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ink for ink jet textile printing, an ink jet textile printing method, and a printed matter.

  2. Description of the Related Art Conventionally, a technique for dyeing cloth, leather, and the like by printing using an inkjet method is known. Ink-jet dyeing has the advantages of excellent productivity and quick response to design changes.

  On the other hand, in the inkjet method, ink is ejected onto a line that can move the chromosome, and dyeing is performed using a collection of dots, so it is difficult to ensure ejection stability associated with ink stability. It is disadvantageous for highly uniform dyeing. Furthermore, there is not enough time to penetrate fabrics, leather, and other objects to be dyed, and uneven dyeing occurs due to poor dyeing such as discoloration due to color transfer and washing, surface shape, and thickness variation after dyeing. There was a thing.

Among these, in the dyeing | staining of the polyester fiber using a disperse dye, these problems are especially easy to manifest, and there exists a case where it is difficult with the conventional dyeing agent.
Conventionally, various surfactants have been used to improve the wettability of fabrics, leathers and other objects to be dyed. However, the stability of disperse dyes is impaired, and aggregates are used for inkjet discharge. Problems may occur. Further, depending on the surfactant, bubbles are likely to be generated, resulting in uneven dyeing.

  Thus, for example, in Patent Document 1, when printing is performed by an ink jet method, an ink jet ink composition containing a dialkyl succinate and not containing a compound having a urea skeleton is excellent in ink ejection properties and ink storage properties. It is disclosed.

JP 2004-315733 A

However, regarding the dyeing failure in the ink jet dyeing process, no decisive solution has been found even in the invention described in Patent Document 1, and it is still recognized in the industry that this is still one of the problems that are difficult to solve. .
In view of the above, the problem to be solved by the present invention is to provide an ink for ink jet printing and an ink jet printing method that are excellent in continuous discharge reliability in ink jet drawing, excellent in recovery from nozzle clogging, and less dyeing unevenness in a printed image. It is to be.

The above problem has been solved by the following means <1>, <8> and <10>. They are listed together with <2> to <7> and <9>, which are preferred embodiments.
<1> an ink for inkjet textile printing, comprising a disperse dye, a dispersant, water and a water-soluble organic solvent, and acetylene diol and acetylene glycol;
<2> The ink for inkjet textile printing according to <1>, wherein the acetylene diol and the acetylene glycol are respectively represented by the following formulas (1) and (2):

式（１）及び式（２）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、炭素数１〜２２のアルキル基又は炭素数６〜１２のアリール基を表し、Ｒ¹とＲ²、又はＲ³とＲ⁴が結合して環を形成してもよく、ｍ及びｎは、それぞれ独立に、１〜１００の整数を表す。
＜３＞前記アセチレンジオール及び前記アセチレングリコールがそれぞれ以下の式（３）及び式（４）で表される、＜１＞又は＜２＞に記載のインクジェット捺染用インク、

In formula (1) and formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R ¹ and R ² , or R ³ and R ⁴ may combine to form a ring, and m and n each independently represent an integer of 1 to 100.
<3> The ink for inkjet textile printing according to <1> or <2>, wherein the acetylenic diol and the acetylene glycol are respectively represented by the following formulas (3) and (4):

式（４）中、ｍ及びｎは、それぞれ独立に、１〜１００の整数を表す。
＜４＞前記アセチレンジオールの含有量及び前記アセチレングリコールの含有量が、それぞれ、インク組成物中で、０．０１〜２．５重量％である、＜１＞〜＜３＞いずれか１つに記載のインクジェット捺染用インク、
＜５＞前記水溶性有機溶剤が、少なくとも１種の多価アルコールである、＜１＞〜＜４＞いずれか１つに記載のインクジェット捺染用インク、
＜６＞少なくともシアン、イエロー、マゼンタ、及び、ブラックの４色を含むインクセットとした、＜１＞〜＜５＞いずれか１つに記載のインクジェット捺染用インク、
＜７＞オレンジ、グリーン及びバイオレットよりなる群から選ばれた少なくとも１つの特色インクを更に含む、＜６＞に記載のインクジェット捺染用インク、
＜８＞＜１＞〜＜７＞いずれか１つに記載のインクジェット捺染用インクを被染色体上に吐出する吐出工程、前記インクジェット捺染用インクを被染色体に定着する定着工程、及び、未定着染料を水洗除去する除去工程、を含むことを特徴とするインクジェット捺染方法、
＜９＞被染色体が、ポリエステル繊維を含有する布帛である、＜８＞に記載のインクジェット捺染方法、
＜１０＞＜８＞又は＜９＞に記載のインクジェット捺染方法によって染色された捺染物。

In formula (4), m and n each independently represent an integer of 1 to 100.
<4> The content of the acetylene diol and the content of the acetylene glycol are each 0.01 to 2.5% by weight in the ink composition, and any one of <1> to <3> Ink for ink-jet textile printing,
<5> The inkjet printing ink according to any one of <1> to <4>, wherein the water-soluble organic solvent is at least one polyhydric alcohol;
<6> Ink for ink-jet textile printing according to any one of <1> to <5>, which is an ink set including at least four colors of cyan, yellow, magenta, and black,
<7> Ink jet textile printing ink according to <6>, further comprising at least one special color ink selected from the group consisting of orange, green and violet.
<8><1> to <7> An ejection process for ejecting the ink for inkjet printing onto a chromosome, a fixing process for fixing the inkjet printing ink on the chromosome, and an unfixed dye An ink-jet textile printing method comprising:
<9> The inkjet printing method according to <8>, wherein the chromosome is a fabric containing polyester fibers,
<10> Printed matter dyed by the inkjet printing method according to <8> or <9>.

ADVANTAGE OF THE INVENTION According to this invention, the ink for inkjet printing and the inkjet textile printing method which were excellent in the continuous discharge reliability in inkjet drawing, were excellent in the resetting | recovery property of nozzle clogging, and were less dyeing | staining unevenness of a printing image were able to be provided.
The ink of the present invention is presumed to be excellent in long-term continuous discharge and restoration of nozzle clogging based on the improvement of the stability of disperse dye, suppression of foaming and prevention of contamination of the nozzle plate by using a specific nonionic surfactant together. The In addition, it is possible to obtain a printed matter with less dyeing unevenness by preventing bleeding even with respect to a polyester fiber not subjected to pretreatment for ink jet drawing.

  The ink for inkjet textile printing (hereinafter also simply referred to as “ink composition” or “ink”) of the present invention contains a disperse dye, a dispersant, water and a water-soluble organic solvent, and acetylene diol and acetylene glycol. It is characterized by that.

The inkjet printing method of the present invention comprises a discharging step of discharging the inkjet printing ink of the present invention onto a chromosome, a fixing step of fixing the inkjet printing ink to the chromosome, and a removing step of removing unfixed dye by washing. , Including.
Hereinafter, the ink and the ink jet textile printing method of the present invention will be described in detail.

<Disperse dye>
The disperse dye used for the ink of the present invention will be described.

  The disperse dye used in the present invention is sparingly soluble in water, has an azo, anthraquinone or other condensed chemical structure, has a molecular weight of 2,000 or less, and has no water-soluble group. It is a dye.

  In the present invention, any conventionally known disperse dye satisfying such conditions can be used.

Specific examples of disperse dyes that can be preferably used in the present invention are shown below.
C. I. Disperse Yellow 3, 4, 5, 7, 9, 13, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224,

  C. I. Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142,

  C. I. Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 2 5,227,229,239,240,257,258,277,278,279,281,288,289,298,302,303,310,311,312,320,324,328,

  C. I. Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77,

C. I. Disperse Green 6: 1, 9,
C. I. Disperse Brown 1, 2, 4, 9, 13, 19,

C. I. Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79, 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146, 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 97,301,315,330,333, etc.,
C. I. Disperse Black 1, 3, 10, 24.

The content of the disperse dye in the ink is 0.1 to 20% by weight in the ink (meaning “relative to the total weight of the ink”) when the two or more types are used in combination. Is preferable, 0.2 to 14% by weight is more preferable, and 1 to 10% by weight is particularly preferable. By setting the disperse dye content within the above range, the color density can be sufficient and the storage stability of the ink can be ensured.
Although the disperse dye may be used as it is on the market, it is preferable to carry out purification treatment as appropriate. As a purification method, a known recrystallization method, washing or the like can be used.
Disperse dyes can be obtained in the form of wet cakes or slurries in addition to powder or lump dry state, and may contain a small amount of a surfactant or the like for the purpose of suppressing aggregation of the dye particles.

The disperse dye is uniformly dispersed into small particles by a medium disperser or the like and used as an ink. As the particle diameter of the dye particles, the number average particle diameter is preferably 150 to 400 nm, and more preferably 150 to 350 nm. It is preferable that the maximum particle size does not include particles having a maximum particle size of 1,000 nm or more, and the maximum particle size is 900 nm or less. If the proportion of particles having a particle size of 200 nm or less is 80% by weight or less, changes in physical properties due to aggregation are caused. Can be prevented. The coarse particles can be removed by filter filtration.
When the number average particle size, particle distribution, or maximum particle size is within the above range, ink can be stably discharged from a fine nozzle, and clogging is prevented and ink is stably discharged in an inkjet printing method. be able to. The number average particle size and particle distribution can be determined by a commercially available particle size measuring device using a laser light scattering method. Measurement is performed by integrating 200 times using a 3 mm square cell.

<Dispersant>
The ink of the present invention contains a dispersant in order to stably disperse the fine particles of the disperse dye in the aqueous medium. As the dispersant, a low molecular weight ionic surfactant and / or nonionic surfactant, and a polymer dispersant can be used. As the surfactant, anionic surfactants and nonionic surfactants are preferably used, and nonionic surfactants are more preferably used. As the polymer dispersant, an anion water-soluble resin is preferably used.
Examples of the low molecular weight nonionic surfactant preferably used in the present invention include polyoxyalkylene alkyl ethers, wherein the alkyl group preferably has 12 to 20 carbon atoms, cetyl ether of polyoxyethylene, Examples thereof include lauryl ether and oleyl ether. A cetyl ether having an addition mole number of oxyethylene of 15 to 25 and an addition mole number of oxypropylene of 2 to 6 is more preferable.
These cetyl ethers are commercially available from Nikko Chemicals under the trade name NIKKOL and from Kao Corporation under the trade name Emulgen.

Anionic water-soluble resins preferably used as polymer dispersants include styrene and its derivatives, vinyl naphthalene and its derivatives, aliphatic alcohol esters of α, β-unsaturated carboxylic acids, acrylic acid and its derivatives, maleic acid and At least two monomers selected from derivatives thereof, itaconic acid and derivatives thereof, fumaric acid and derivatives thereof, vinyl acetate, vinyl alcohol, vinylpyrrolidone, acrylamide, and derivatives thereof (at least one of them) Is a hydrophilic monomer.), Block copolymers, random copolymers, and graft copolymers, and salts thereof.
In the present invention, a low molecule means a molecule having a molecular weight of 1,000 or less, and a polymer means a molecule having a molecular weight exceeding 1,000.

  These resins are preferably alkali-soluble resins that are soluble in an aqueous solution in which a base is dissolved. Of these, water-soluble polymer compounds having a carboxyl group or a sulfonic acid group and salts thereof in the side chain are particularly preferable.

  The blending amount of the dispersant is preferably 0.1 to 30% by weight, and more preferably 1 to 10% by weight in the ink.

<Water>
The ink of the present invention preferably contains 10 to 90% by weight of water and more preferably 20 to 70% by weight with respect to the total weight of the ink from the viewpoint of viscosity adjustment. As water, ion-exchanged water is preferably used. Water is useful as a medium for dispersing the dispersed dye particles.

<Water-soluble organic solvent>
The water-soluble organic solvent is an organic solvent having compatibility with water, and means an organic solvent in which water and an organic solvent equal to or more in weight are uniformly compatible at room temperature.
There are various kinds of water-soluble organic solvents, but monohydric alcohols such as methanol, ethanol and isopropyl alcohol, polyhydric alcohols described below, ketones such as acetone and diacetone alcohol, or keto alcohols; tetrahydrofuran, Cyclic ethers such as dioxane are included.

(Polyhydric alcohols)
In the present invention, the aqueous organic solvent preferably used is a polyhydric alcohol. Polyhydric alcohols are aliphatic compounds having two or more hydroxyl groups. An unmodified polyhydric alcohol in which any hydroxyl group is not derived from ether or ester is preferred.
Examples of the polyhydric alcohol used in the ink of the present invention include oxyethylene or oxypropylene addition polymers such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol; ethylene glycol, Alkylene glycols such as propylene glycol, trimethylene glycol, butylene glycol, hexylene glycol and the like in which the alkylene group contains 2 to 6 carbon atoms; triols such as 1,2,6-hexanetriol; thiodiglycol; included.
The total content of polyhydric alcohols is preferably 2 to 50% by weight, more preferably 10 to 40% by weight, based on the total weight of the ink.
Polyhydric alcohols are useful for suppressing volatilization and preventing solidification of ink in an inkjet apparatus including a nozzle part and a tube.

The ink of the present invention may contain an ether of a polyhydric alcohol, an ether of an alkylene glycol containing an alkylene group having 2 to 6 carbon atoms, an ether of an oxyethylene or oxypropylene addition polymer (or more). These may be collectively referred to as “glycol ether compounds”.
Examples of the glycol ether compound include mono-lower alkyl ethers of alkylene glycol such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether; triethylene glycol dimethyl (or ethyl And lower dialkyl ethers of polyhydric alcohols such as ether and tetraethylene glycol dimethyl (or ethyl) ether. Here, lower means an alkyl group having 1 to 5 carbon atoms.

The glycol ether compound optionally added to the ink of the present invention preferably has a viscosity of 1 to 40 cP at 25 ° C., more preferably 2 to 30 cP. It is preferable that the viscosity is within the above range since it effectively acts on the cleaning in the head.
In the present invention, the glycol ether compound preferably has a boiling point of 50 to 150 ° C, more preferably 60 to 130 ° C. When the boiling point is within the above range, there is no remaining ink after use, and it can be used safely and effectively by suppressing volatilization during use.

  In the ink of the present invention, the addition amount of the glycol ether compound is preferably 0 to 70% by weight, more preferably 0 to 50% by weight, and particularly preferably 0 to 40% by weight.

<Acetylene diol and acetylene glycol>
The ink for inkjet printing of the present invention contains acetylene diol and acetylene glycol.
The acetylene diol and the acetylene glycol are preferably represented by the following formulas (1) and (2), respectively.

In formula (1) and formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R ¹ and R ² , or R ³ and R ⁴ may combine to form a ring, and m and n each independently represent an integer of 1 to 100.
The alkyl group may have a substituent, and includes an aralkyl group that is an alkyl group substituted with a phenyl group. The substituent allowed for the alkyl group includes a halogen atom and an alkoxy group in addition to the aryl group.
(M + n), which is the number of moles of ethylene oxide added in the formula (2), is preferably 5 to 60, and more preferably 6 to 40.

  The acetylene diol and the acetylene glycol are preferably represented by the following formulas (3) and (4), respectively.

式（４）中、（ｍ＋ｎ）は、好ましくは、６〜２０であり、より好ましくは、６〜１６である。

In formula (4), (m + n) is preferably 6 to 20, and more preferably 6 to 16.

Commercially available products can be obtained for the compounds represented by formula (3) and formula (4). This includes Surfynol 104 series and 400 series, and Olfin E series and PD series, which are manufactured by Air Products of the United States and sold by Nissin Chemical Industry Co., Ltd.
The amount of the acetylene diol used is preferably 0.01 to 2.5% by weight and more preferably 0.15 to 1.0% by weight in the ink for inkjet printing.
The amount of the acetylene glycol used is preferably 0.01 to 5% by weight and more preferably 0.3 to 2.5% by weight in the ink for inkjet printing.

In general, acetylene diol and acetylene glycol are often used separately. In combination with these inks for inkjet textile printing, in addition to the effects of surface activity and defoaming, it is possible to suppress nozzle plate deterioration of the inkjet head and to ensure stable ejection properties for a long period of time.
It is known that the nozzle plate deterioration of the inkjet head is caused by metal ions (Na ^+, etc.), which are trace impurities in the ink, and the nozzle plate deterioration can be prevented by the metal ion trap effect due to the inclusion action of acetylene glycol. It is estimated to be.

(Other ingredients)
The inkjet textile printing ink of the present invention can contain other components as optional components.
The ink of the present invention may contain a sensitizer, a co-sensitizer, an ultraviolet absorber, an antioxidant, an anti-fading agent, a conductive salt, a solvent, a polymer compound, a basic, in addition to the above components, as necessary. A compound etc. can be contained. These are described in JP2009-185186A.

The ink of the present invention can be obtained by uniformly mixing a disperse dye, a dispersant, water and a water-soluble organic solvent, and acetylene diol and acetylene glycol. After dispersing the above-mentioned disperse dye and dispersant as fine particles in water to prepare a concentrated dye dispersion, uniform with necessary additives such as this concentrate, water, water-soluble organic solvent, acetylene diol and acetylene glycol It is preferable to prepare an ink by mixing them.
As a method for dispersing the dye, a sand mill (bead mill), a roll mill, and an ultrasonic disperser are used, and a sand mill (bead mill) can be preferably used.

The ink for inkjet textile printing of the present invention is preferably an ink set containing at least four colors of cyan, yellow, magenta and black. This ink set enables full color printing.
More preferably, the ink for inkjet textile printing of the present invention further contains at least one special color ink selected from the group consisting of orange, green and violet. By adding such special color ink to the ink set, the color reproducible region can be expanded.

Next, the inkjet printing method of the present invention will be described.
The inkjet printing method of the present invention comprises a discharging step of discharging the inkjet printing ink of the present invention onto a chromosome, a fixing step of fixing the inkjet printing ink to the chromosome, and a removing step of removing unfixed dye by washing. , Including.
The above-described ink jet textile printing method will be described below.

The inkjet textile printing method of the present invention includes three steps as an essential step: an ink ejection step, a fixing step of a disperse dye in the ink, and a removal step of an unfixed dye.
In the above discharge step, the ink for inkjet printing of the present invention is discharged onto the chromosome.
A commercially available apparatus can be used as the ink jet apparatus used to eject ink. Such an ink jet apparatus includes an ink head unit for ejecting the ink, a data input unit for inputting print image information, and at least C (cyan), M (magenta), Y (yellow), And a calculation unit for calculating the droplet ejection amount of the ink set including each of the B (black) inks, and the ink so that each color ink of the appropriate amount calculated by the calculation unit is ejected to a predetermined place. It is preferable to include a drive unit that drives the head unit. In addition to CMY and B, which are the three primary colors of the subtractive color method, it is preferable to use special color inks such as green, orange and violet together with the ink set.

  In the inkjet printing method of the present invention, a chromosome to be dyed with a disperse dye is used. As the chromosome, a cloth mainly composed of polyester fibers is preferable. The phrase “mainly comprising polyester fibers” means that the polyester fibers are contained in an amount of 50% by weight or more in any form such as woven fabric, knitted fabric, and non-woven fabric. Therefore, it is preferable that the polyester fiber is 100%, but a blended woven fabric or a blended nonwoven fabric with rayon, cotton, polyurethane, acrylic, nylon, wool, silk, or the like can also be used. Further, the thickness of the yarn constituting the fabric is preferably in the range of 10 to 100d.

  In the ink-jet printing method of the present invention, in order to obtain a uniform dyed product, natural impurities (oil, fat, wax, pectin, natural pigment, etc.) adhering to the fabric fibers are used in the fabric manufacturing process prior to the ink ejection process. It is preferable to carry out a refining step for washing and removing the processing agent, treatment agent or dirt. Details are described in the Chemical Society of Japan, “Chemical Handbook”, published by Maruzen (1986).

  As the cleaning agent used for cleaning, an alkali such as sodium hydroxide or sodium carbonate, a surfactant such as an anionic surfactant or a nonionic surfactant, or a bleaching agent is used.

  In the ink jet textile printing method of the present invention, pretreatment can be performed by a known method for preventing bleeding of an image. The pretreatment includes a method in which 0.2 to 50% by weight of at least one substance such as a water-soluble polymer, a water-soluble metal salt, a polycation compound, and a surfactant is added to the chromosome. It is. Here, a method suitable for the fiber material of the chromosome is appropriately selected, and is not particularly limited.

As the water-soluble metal salt, inorganic salts or organic acid salts of alkali metals or alkaline earth metals such as KCl and CaCl ₂ can be used. Moreover, as a polycation compound, the polymer or oligomer of various quaternary ammonium salts, a polyamine salt, etc. can be used. However, some water-soluble metal salts and polycation compounds change the color tone of the dyed product or reduce the light fastness, and therefore are preferably selected according to the target dyed product.

  Water-soluble polymers include natural polymers (for example, starches such as corn and wheat, cellulose derivatives such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose, sodium alginate, guar gum, tamarind gum, locust bean gum, gum arabic, etc. Polysaccharides, gelatin, casein, keratin and other protein substances), and synthetic polymers (eg, polyvinyl alcohol, polyvinyl pyrrolidone, acrylic acid polymers, etc.).

  As the surfactant, for example, anionic, cationic, amphoteric, and nonionic surfactants are used. Typically, anionic surfactants include higher alcohol sulfates, sulfonates of naphthalene derivatives, and the like. The cationic surfactants include quaternary ammonium salts, the amphoteric surfactants include imidazoline derivatives, and the like, and the nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene propylene block polymer, sorbitan. Fatty acid esters and polyoxyethylene sorbitan fatty acid esters are included.

Since these water-soluble polymers and surfactants that are preliminarily applied to the fabric as a pretreatment agent do not cause stains due to tarring and the like when coloring at high temperature after inkjet printing, It is preferable that it is stable. Moreover, those water-soluble polymers and surfactants that are previously imparted to the fabric are preferably those that can be easily removed from the fabric by a cleaning treatment after ink-jet printing and color development at a high temperature.
In the present invention, a dyed product with little dyeing unevenness in a dyed image can be obtained even if a fabric not subjected to the pretreatment agent is used.

After the ink ejection process, a process of applying heat to the ejected inkjet ink for printing and fixing the inkjet textile printing ink on the chromosome is performed.
After winding up the fabric printed by ink ejection continuously or once after winding, the chromosome having ink for inkjet printing discharged is heated to dry the ink and disperse the disperse dye on the chromosome. Carry out colonization of the chromosome to diffuse into the fiber.

  The printed chromosome can be immediately heat-treated, or left for a while and then heat-treated, or can be dried and colored according to the intended use. As the heat treatment method, a method suitable for the application, such as an oven (dry heat), a heat roll, or steaming (steam heat) is selected.

  Although heating conditions can be selected as appropriate, when the chromosome is polyester, it is preferably 1 to 2 minutes at 170 to 200 ° C. Moreover, in a high pressure steamer, the heat processing for 30 to 40 minutes at 125-130 degreeC are preferable.

After the heat treatment, a removal step is performed in which the unfixed dye is decomposed and washed away with water. By removing unfixed dyes that were not involved in dyeing, dyeing stability and fastness are improved. Moreover, when there exists the pre-processing thing given to the fabric, it is also preferable to remove this together.
As a method for removing unfixed dye from the chromosome, a conventionally known washing method can be used, but reduction washing is particularly preferred, and alkali reduction treatment is more preferred.

  It is preferable to dry the chromosome after the removal step. After the washed fabric is dehydrated, it is dried or dried using a dryer, heat roll, iron or the like.

  Through this series of steps, a dyed product in which beautiful features are dyed can be obtained by making use of the characteristics of the ink for ink jet textile printing.

Concentrates of yellow dye, cyan dye and magenta dye were prepared as follows.
In addition, all of Kayalon used the product by Nippon Kayaku Co., Ltd.
(Preparation of disperse dye concentrated dispersion)
-Yellow concentrated dispersion-
Kayalon Microester Yellow AQ-LE 30g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 8g
62g of ion exchange water

  The above material was stirred with a Silverson high-speed stirrer for 20 minutes, and after the preliminary dispersion was completed, the dye dispersion was filled in a ball mill and dispersed at room temperature for 12 hours. Thereafter, the mixture was filtered through a 2 μm filter to prepare a yellow concentrated dispersion A1.

-Cyan concentrated dispersion-
Kayalon Microester Blue AQ-LE 30g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 8g
62g of ion exchange water
A cyan concentrated dispersion A1 was prepared from the above material in the same manner as the yellow concentrated dispersion.

~ Magenta concentrated dispersion ~
Kayalon Polyester Red BL-E 30g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 8g
62g of ion exchange water
A magenta concentrated dispersion A1 was prepared from the above material in the same manner as the yellow concentrated dispersion.

~ Black concentrated dispersion ~
Kayalon Polyester Black EX-SF 200 30g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 8g
62g of ion exchange water
A black concentrated dispersion A1 was prepared from the above material in the same manner as the yellow concentrated dispersion.

~ Magenta concentrated dispersion ~
Kayalon Polyester Red BL-E 30g
Emulgen 120 (manufactured by Kao Corporation) 8g
62g of ion exchange water
A magenta concentrated dispersion A2 was prepared from the above material in the same manner as the yellow concentrated dispersion.

(Ink for textile printing)
~ Yellow ink ~
Yellow concentrated dispersion A1 3g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5g
Surfynol 465 (Nissin Chemical Industry Co., Ltd.) 0.25g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion-exchanged water 63.25g
The above materials were put into a polypropylene container, and stirred for about 30 minutes while mixing with a Silverson high-speed stirrer to control the internal temperature to 40 ° C. or lower and mixed. Thereafter, the mixture was filtered through a 2 μm filter to prepare yellow ink B1.

~ Cyan ink ~
3g cyan concentrated dispersion A1
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5g
Surfynol 465 (Nissin Chemical Industry Co., Ltd.) 0.25g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion-exchanged water 63.25g
The above materials were agitated and mixed in the same manner as the yellow ink B1 to prepare cyan ink B1.

~ Magenta ink ~
Magenta concentrated dispersion A1 3g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5g
Surfynol 465 (Nissin Chemical Industry Co., Ltd.) 0.25g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion-exchanged water 63.25g
The above materials were agitated and mixed in the same manner as the yellow ink B1 to prepare a magenta ink B1.

~ Black ink ~
Black concentrated dispersion A1 3g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5g
Surfynol 465 (Nissin Chemical Industry Co., Ltd.) 0.25g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion-exchanged water 63.25g
The above materials were stirred and mixed in the same manner as the yellow ink B1 to prepare a black ink B1.

~ Magenta ink ~
Magenta concentrated dispersion A2 3g
Emulgen 120 (manufactured by Kao Corporation) 3g
Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5g
Surfynol 465 (Nissin Chemical Industry Co., Ltd.) 0.25g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion-exchanged water 63.25g
The above materials were agitated and mixed in the same manner as the yellow ink B1 to prepare a magenta ink B2.

~ Magenta ink ~
Magenta concentrated dispersion A1 3g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion exchange water 63.5g
The above materials were agitated and mixed in the same manner as the yellow ink B1 to prepare a comparative magenta ink B3.

~ Magenta ink ~
Magenta concentrated dispersion A1 3g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfynol 465 (Nissin Chemical Industry Co., Ltd.) 0.25g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
63.75 g of ion-exchanged water
The above materials were agitated and mixed in the same manner as the yellow ink B1 to prepare a comparative magenta ink B4.

~ Magenta ink ~
Magenta concentrated dispersion A1 3g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfinol 104E (Nissin Chemical Industry Co., Ltd.) 0.02g
Surfynol 465 (Nissin Chemical Industry Co., Ltd.) 0.25g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion exchange water 63.98g
The above materials were agitated and mixed in the same manner as the yellow ink B1 to prepare a magenta ink B5.

~ Magenta ink ~
Magenta concentrated dispersion A1 3g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) 4.8g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion-exchanged water 59.2g
The above materials were agitated and mixed in the same manner as the yellow ink B1 to prepare a magenta ink B6.

~ Magenta ink ~
Magenta concentrated dispersion A1 3g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) 0.01g
Surfynol 465 (Nissin Chemical Industry Co., Ltd.) 0.25g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion exchange water 63.99g
The above materials were agitated and mixed in the same manner as the yellow ink B1 to prepare a magenta ink B7.

~ Magenta ink ~
Magenta concentrated dispersion A1 3g
NIKKOL PBC-34 (Nikko Chemicals Co., Ltd.) 3g
Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) 5.1g
Surfynol 465 (Nissin Chemical Industry Co., Ltd.) 0.25g
Ethylene glycol (Wako Pure Chemical Industries, Ltd.) 10g
Glycerin (Wako Pure Chemical Industries, Ltd.) 20g
Ion exchange water 58.9g
The above materials were agitated and mixed in the same manner as the yellow ink B1 to prepare a magenta ink B8.

<Example 1>
The yellow ink B1 was recorded on a chromosome as Example 1 (Ex1) using an inkjet recording experimental apparatus having a piezo inkjet nozzle. The ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion. Temperature sensors were provided near the ink supply tank and the nozzle of the ink jet head, respectively, and temperature control was performed so that the nozzle portion was always 45 ° C. ± 2 ° C. The piezo ink jet head was driven so that 60 pl size dots could be ejected at a resolution of 150 × 150 dpi. After drawing, a heat treatment at 180 ° C. for 30 seconds, a reduction treatment with a reducing agent, washing with water, and a drying process were performed. In the present invention, dpi represents the number of dots per 2.54 cm. As a chromosome, a polyester cloth (thickness 600 μm, primary fiber 17 μm, secondary fiber 320 μm) was used.

~ Evaluation ~
<Dischargeability>
The following three types (A, B, C) were evaluated using the above-described ink jet drawing apparatus.
[Evaluation A (Continuous discharge reliability)]
Before the ink jet apparatus was operated, the liquid circulation with the ink was repeated for 15 minutes to remove the ink remaining in the ink contact portion in the apparatus. Thereafter, continuous use for 1 hour was carried out, and the number of nozzles causing drawing defects (non-ejection, intermittent non-ejection, etc.) was counted.
4 ... No discharge failure 3 ... Discharge failure 1 or 2 nozzles 2 ... Discharge failure 3 nozzles or more and less than 10 nozzles 1 ... Discharge failure 10 nozzles or more All were counted per head.

[Evaluation B (cleaning property)]
In the evaluation A, the nozzle plate of the head that was continuously used for 20 hours or more was cleaned to remove ink adhering by non-contact suction, and the discharge state at the start was evaluated.
4 ... No discharge failure 3 ... Discharge failure 1 or 2 nozzles 2 ... Discharge failure 3 nozzles or more and less than 10 nozzles 1 ... Discharge failure 10 nozzles or more All were counted per head.

[Evaluation C (Displacement in discharge direction)]
The ejection evaluation was performed in the same manner as in evaluation A, and the number of nozzles whose ejection direction was shifted from the drawn image was counted.
4 ... No discharge displacement nozzle 3 ... Discharge displacement nozzle 1 or 2 nozzle 2 ... Discharge displacement nozzle 3 nozzles or more and less than 10 nozzles 1 ... Discharge displacement nozzle 10 nozzles or more All of them were counted per head.

<Dyeing unevenness>
The condition of the dyed and fixed polyester cloth surface was visually evaluated.
4 ・ ・ ・ No unevenness 3 ・ ・ ・ Almost no unevenness 2 ・ ・ ・ Partial unevenness is observed 1 ・ ・ ・ Almost entire surface unevenness is observed

<Fixability>
The surface of the dyed and fixed polyester cloth was rubbed with the same undyed polyester cloth, and the color transfer to the unfixed polyester cloth was visually evaluated.
3 ・ ・ ・ No color transfer 2 ・ ・ ・ Slight color transfer is observed 1 ・ ・ ・ Color transfer is observed

(Examples 2 to 4)
Examples 2 to 4 were carried out in the same manner as in Example 1 except that the yellow ink B1 was replaced with a cyan ink B1, a magenta ink B1, or a black ink B1, and recording on a polyester cloth was performed.

(Examples 5 to 11)
Except that the yellow ink B1 in Example 1 was replaced with the ink described in Table 1, recording was performed on a polyester cloth in the same manner, and Examples 5 to 11 (Ex 5 to 11) were carried out.
In Table 1, Y represents yellow ink, M represents magenta ink, C represents cyan ink, and B represents black ink.
104E is an abbreviation for Surfinol 104E (manufactured by Nissin Chemical Industry Co., Ltd.), 465 is an abbreviation for Surfinol 465 (manufactured by Nissin Chemical Industry Co., Ltd.), 420, 440, 485, 104A, 104BC and 104PA also represent the model numbers of Surfinol (manufactured by Nissin Chemical Industry Co., Ltd.).

(Comparative Examples 1-3)
As shown in Table 1, Comparative Example 1 was carried out in the same manner as in Example 1 except that Compound (1) and Compound (2) were changed to single use of Compound (1) or single use of Compound (2) as shown in Table 1. And 2 were performed.

Examples 1 to 11 showed good results in ejection stability, fixability, and dyeing unevenness. In all the examples, the dyeing defects in the ink-jet printing process were improved and showed satisfactory levels.
On the other hand, when only one kind of Surfynol 104E is used as in Comparative Examples 1 and 2 (C1 and C2), there arises a problem in cleaning performance and landing position accuracy due to contamination of the head nozzle plate, and Surfinol. Even when only one type of 465 was used, there was a problem in continuous discharge properties due to foaming. Further, in Comparative Example 3 (C3) using the conventionally used funnel oil A, the stability of the ink was impaired, the ejection stability was greatly deteriorated, and the fixing property and uneven dyeing were also in a tendency to deteriorate.
In addition, when the amount of the compound of the present invention was outside the optimum range, there was a tendency that the discharge stability and the generation of bubbles were observed during dyeing, and the dyeing unevenness was generated.

Claims (10)

Disperse dyes,
Dispersant,
Water and water-soluble organic solvents, and
Containing acetylene diol and acetylene glycol,
Ink for inkjet printing. The ink for inkjet textile printing according to claim 1, wherein the acetylene diol and the acetylene glycol are represented by the following formulas (1) and (2), respectively.

In formula (1) and formula (2), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R ¹ and R ² , or R ³ and R ⁴ may combine to form a ring, and m and n each independently represent an integer of 1 to 100. The ink for inkjet textile printing according to claim 1 or 2 in which said acetylene diol and said acetylene glycol are denoted by a following formula (3) and a formula (4), respectively.

In formula (4), m and n each independently represent an integer of 1 to 100.   The ink for inkjet printing according to any one of claims 1 to 3, wherein a content of the acetylene diol and a content of the acetylene glycol are each 0.01 to 2.5% by weight in the ink.   The ink for inkjet textile printing according to any one of claims 1 to 4, wherein the water-soluble organic solvent is at least one polyhydric alcohol.   The ink for inkjet printing according to any one of claims 1 to 5, wherein the ink set includes at least four colors of cyan, yellow, magenta, and black.   The ink for inkjet printing according to claim 6, further comprising at least one spot color ink selected from the group consisting of orange, green and violet. A discharge step of discharging the ink for inkjet printing according to any one of claims 1 to 7 onto a chromosome,
A fixing step for fixing the ink-jet printing ink to a chromosome, and
An ink-jet printing method comprising: a removal step of removing unfixed dye by washing with water.   The inkjet printing method according to claim 8, wherein the chromosome is a fabric containing polyester fibers. A printed product dyed by the ink jet printing method according to claim 8 or 9.