WO2011013503A1

WO2011013503A1 - Ink composition and method for printing textile using same

Info

Publication number: WO2011013503A1
Application number: PCT/JP2010/061748
Authority: WO
Inventors: 慎介清水; 真理子梅田; 祐司鈴木; 明宮田
Original assignee: 日本化薬株式会社
Priority date: 2009-07-30
Filing date: 2010-07-12
Publication date: 2011-02-03
Also published as: TW201120151A; JP5580824B2; CN102471623A; BR112012001611A2; JPWO2011013503A1; TWI478991B; CN102471623B

Abstract

Provided is a reactive dye ink which exhibits ejection stability independent of a change in the environmental temperature when used in a printer equipped with an industrial ink jet head that necessitates high-viscosity ink and which ensures excellent image quality of printed matter and exhibits excellent dyeing properties. Specifically provided is an ink composition for textile printing, which comprises at least one reactive dye, a compound having a structure formed by addition polymerization of diglycerin with ethylene oxide and/or propylene oxide, a nonionic surfactant, an anionic surfactant, and water. The ink composition exhibits excellent ejection stability independent of a change in the environmental temperature in continuous ejection at a high driving frequency, and has good dyeing performance.

Description

Ink composition and textile printing method using the same

The present invention relates to a dye ink composition and a textile printing method using the same, and more particularly to a textile printing method for cellulose fibers and polyamide fibers.

Compared with textile printing methods such as screen textile printing, roller textile printing, rotary textile printing, etc.
(1) The plate making process is unnecessary and the process can be shortened.
(2) The ability to print the digitized design as it is via a computer;
(3) It is possible to produce a wide variety of products even in small quantities.
(4) Dye color paste waste liquid can be greatly reduced,
There are many merits such as. On the other hand, compared to conventional plate-making and printing, there are problems such as a slower printing speed and difficulty in reproducing dark colors, and they are often used in the range of sample production and small-scale production.
In recent years, the printing speed of inkjet printers has been greatly improved due to technological advances in computer image processing and print head (also called inkjet heads) manufacturing, digitization of printing designs, and printing. Ink-jet textile printing has been popularized against the background of the diversification of processing and the demand for small lots in the market.

As dye inks for inkjet printing, acid dye inks for polyamide fibers such as silk and nylon; disperse dye inks for polyester fibers; reactive dye inks for cellulose fibers such as cotton and rayon; ing.
These ink-jet printing dye inks are generally water-based inks in which a dye is dissolved or dispersed in water. For the purpose of suppressing the drying of the ink due to water evaporation and adjusting the viscosity of the ink, ethylene glycol, diethylene glycol, A glycol such as triethylene glycol, a compound such as a monoalkyl ether of these glycols, or an organic solvent such as glycerin is added to the ink.

However, the reactive dye is fixed to the fiber by reacting a reactive group that reacts with the fiber present in the dye molecule with a hydroxy group or the like present in the fiber. Therefore, when the above organic solvent is added to the ink containing the reactive dye, the above organic solvent is used in the reactive fixing step by heat for the purpose of fixing the dye during the storage of the ink or after printing. The reactive dye reacts with the hydroxy group and / or carboxy group, etc. possessed by the resin and the like, and the problem of a decrease in the fixing rate of the dye to the fiber tends to occur. Therefore, the organic solvent to be added to the reactive dye ink is selected from those having low reactivity with the reactive dye, or those having low reactivity with the dye are added to suppress the reaction between the dye and the solvent. And such organic solvents have been proposed.
Specific examples thereof include thiodiglycol (patent document 1), propylene glycol (patent document 2), 1,3-butanediol (patent document 3), EO adduct of glycerin (patent document 4), polypropylene glycol (patent document) An example in which 5) is added to ink is known.
Here, as an ink composition containing a dye or pigment other than a reactive dye as a colorant, one containing polyoxyalkylene diglyceryl ether is also known. Although these ink compositions have different uses because they do not use reactive dyes and the object to be colored is not a fiber or a fabric that is a structure thereof, examples of such inks are as follows. Examples thereof include water-based ink compositions for writing instruments and ink-jet ink compositions disclosed in Patent Documents 6 to 8.

In addition, the inclusion of a surfactant as one of the additives in an ink composition is generally performed regardless of the use of the ink composition. For example, together with polyoxyalkylene diglyceryl ether, Patent Documents 6 and 7 contain a nonionic surfactant, and Patent Document 8 contains an anionic surfactant. Patent Document 9 substantially discloses an ink composition for ink jet printing using a nonionic surfactant and an anionic surfactant in combination.
The surfactant is known to have a function of reducing the surface tension of the ink. For example, in the case of an inkjet application, the surfactant is used for the purpose of improving the ink ejection performance and the quality of the printed material.

On the other hand, in recent years, industrial-use highly durable inkjet heads and high-speed printers equipped with them have been developed, which require a viscosity of about 8 to 20 mPa · s as a physical property of ink to ensure ejection stability. ing.
Also, as one of the methods for improving the quality of printed matter, the surface tension of the ink is adjusted by adding a surfactant to control the penetration and bleeding of the ink into the recording medium. Methods for improving the image quality are known. In general, by reducing the surface tension, it is possible to increase the permeability of the recording medium such as fibers and reduce the graininess of the printed product, but if the surface tension is too low, the fine line portion of the printed product will blur, The problem is that the printed image is disturbed.
As described above, even if the surface tension of the ink is too high or too low, there is a problem in the image quality. Therefore, it is necessary to adjust to an appropriate range depending on the type of the recording medium.
Patent Document 5 discloses an ink composition for ink jet printing containing a reactive dye, a nonionic surfactant, water, and a polyhydric alcohol.
Patent Document 10 discloses an ink composition for ink-jet printing containing a reactive dye, a compound represented by a specific formula, a nonionic surfactant, and water.

Furthermore, ink compositions for inkjet textile printing are required to obtain good ejection properties and good image quality of printed textiles regardless of temperature fluctuations. For example, when used in an environment where there is a large temperature difference between summer and winter, one problem is that ink that exhibits good ejection performance in summer has poor ejection in winter. Improving the discharge performance in winter often causes problems such as insufficient dyeing performance this time. Providing reactive dye ink that combines both discharge performance and dyeing performance regardless of temperature fluctuations Has become a big market demand.
However, a reactive dye ink that satisfies the continuous ejection performance and the image quality of printed matter that are required for industrial high-speed ink jet printers regardless of temperature fluctuation at a high driving frequency has not been obtained at present.

Japanese Patent No. 3323549 (Example 1) Japanese Patent Laid-Open No. 2002-241639 (Example 3) JP 2003-306627 A (Example 2) Japanese Patent No. 3582434 JP 2005-520015 A JP-A-4-36362 JP 2004-346134 A JP 2004-155869 A JP 2007-238687 A (Production Examples 4 to 9) International Publication No. 2009/104547

The present invention has a viscosity suitable for a printer equipped with an industrial inkjet head (industrial inkjet printer), and is concerned with temperature changes both at a normal room temperature of 25 ° C. and a low temperature environment of 10 ° C. It is an object of the present invention to provide a reactive dye ink composition for dyeing cellulose fibers and polyamide fibers having excellent continuous discharge stability at a high driving frequency and good dyeing performance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that at least one reactive dye, a specific compound represented by the following formula (1), a nonionic surfactant and an anionic surfactant The present inventors have found that a water-based ink composition containing two kinds of surfactants as an agent can solve the above-mentioned problems.

That is, the present invention
1)
An ink composition containing at least one reactive dye, a compound having a structure in which ethylene oxide and / or propylene oxide is added to diglycerin, a nonionic surfactant, an anionic surfactant, and water;
2)
The ink composition according to 1), wherein the compound having a structure obtained by addition polymerization of ethylene oxide and / or propylene oxide to the diglycerin is a compound represented by the following formula (1):

[Where:
X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a hydrogen atom or a methyl group,
j, k, m, and n represent a total number of 4 to 40 in total. ]

3)
The ink composition according to 1) or 2), wherein the nonionic surfactant is an acetylene glycol surfactant or an acetylene alcohol surfactant, and the anionic surfactant is a sulfosuccinic acid surfactant,
4)
The ink composition according to 2) or 3), wherein all of X ₁ , X ₂ , X ₃ , and X _{4 in} the formula (1) are methyl groups;
5)
0.5 to 35% by mass of reactive dye, 3 to 50% by mass of a compound having a structure in which ethylene oxide and / or propylene oxide is added to diglycerin, and nonionic surfactant based on the total mass of the ink composition The ink composition according to any one of 1) to 4) above, wherein 0.05 to 2% by mass, 0.05 to 2% by mass of an anionic surfactant are contained, and the balance is water.
6)
The ink composition according to any one of 1) to 5) above, further comprising a water-soluble organic solvent,
7)
The ink composition according to any one of 1) to 6) above, further containing 0.05 to 3% by mass of a pH adjusting agent with respect to the total mass of the ink composition;
8)
Using the ink composition described in the above 1) to 7) as an ink, ejecting ink droplets of the ink by an ink jet printer and applying the ink to a fiber, and adding the dye in the ink composition applied in the step to a heat A method of printing a fiber, comprising a step of reactively fixing to the fiber and a step of washing unfixed dye remaining in the fiber,
9)
The above 8) further includes a fiber pretreatment step of impregnating the fiber before application of the ink composition with an aqueous solution containing one or more types of glue, a pretreatment pH adjuster, and a hydrotropic agent. Textile printing method according to the description,
10)
A printed product printed by the fiber printing method described in 8) or 9) above;
About.

According to the ink composition of the present invention and the printing method using the same, a printer equipped with an industrial inkjet head that requires high-viscosity ink is used at a normal room temperature of 25 ° C. and a low-temperature environment of 10 ° C. In any case, it is possible to provide a reactive ink composition for dyeing cellulose fibers and polyamide fibers having excellent continuous discharge stability at a high driving frequency regardless of temperature changes and having good dyeing performance.

The ink composition of the present invention contains a reactive dye as a pigment, and further contains a compound having a structure obtained by addition polymerization of ethylene oxide and / or propylene oxide to diglycerin, a nonionic surfactant, and an anionic surfactant. It is a substantially aqueous ink composition in solution.
A reactive dye is generally used as a dye for dyeing cellulose fibers, and an acid dye is generally used as a dye for dyeing polyamide fibers. However, reactive dyes are used for dyeing polyamide fibers. Can also be used.
When cellulosic fibers are dyed with reactive dyes, reactive groups contained in the reactive dye in the molecule react with hydroxy groups of the cellulosic fibers to form covalent bonds, thereby dyeing the fibers. On the other hand, the polyamide-based fiber has an amino group in the fiber, and the amino group and an acidic functional group such as a sulfo group in the dye molecule form an ionic bond, thereby dyeing the fiber. Therefore, any reactive dye having an acidic functional group (preferably a sulfo group) can be used as a pigment contained in the ink composition of the present invention.

Since the ink composition of the present invention is intended for full-color printing, ink compositions having various hues such as yellow, orange, brown, red, violet, blue, green, and black are prepared, and these are used as inks. Can be used together as a set.

The dye used in the ink composition of the present invention is not particularly limited as long as it is a reactive dye, but is a dye whose reactive group that reacts with the fiber is a monochlorotriazinyl group, that is, a monochlorotriazine-based reactive dye. Preferably there is. Specific examples of reactive dyes include C.I. I. Yellow dyes such as Reactive Yellow 2, 3, 18, 81, 84, 85, 95, 99, 102; I. Orange dyes such as Reactive Orange 5, 9, 12, 13, 35, 45, 99; I. Brown dyes such as Reactive Brown 2, 8, 9, 17, 33; I. Red dyes such as Reactive Red 3, 3: 1, 4, 13, 24, 29, 31, 33, 125, 151, 206, 218, 226, 245; I. Violet dyes such as Reactive Violet 1, 24; I. Blue dyes such as Reactive Blue 2, 5, 10, 13, 14, 15, 15: 1, 49, 63, 71, 72, 75, 162, 176; I. Green dyes such as Reactive Green 5, 8, 19; I. And black dyes such as Reactive Black 1, 8, 23, 39, and the like. These may be used alone or in combination of two or more.

In the reactive dye, a mixed dye composed mainly of a blue dye and an orange dye and a red dye can also be used as a black dye. In addition, other reactive dyes may be added to the black dye for the purpose of fine-tuning to a high-quality color tone.

As the reactive dye, a powdery or lumpy dye such as a dry or wet cake can be used. Commercially available reactive dyes have various qualities such as powder for industrial dyeing, liquid products for textile printing, ink-jet textile printing, etc., and the production method, purity, etc. are different. The ink composition of the present invention is preferably prepared using a dye having as few impurities as possible in order to reduce adverse effects on storage stability and ejection accuracy from an inkjet printer. In general, inorganic salts such as sodium chloride are often mixed during the synthesis of reactive dyes. In addition, since water and the like that are not particularly subjected to purification operations contain metal ions such as calcium ions and magnesium ions, even when such water or the like is used in the preparation of the ink composition, the ions and the like may be present in a trace amount. Mixed. Hereinafter, in the present specification, for convenience, the inorganic salt and the metal ion are referred to as “inorganic impurities”. These inorganic impurities not only significantly deteriorate the solubility of the dye in the ink and the storage stability of the ink, but also cause corrosion, abrasion, nozzle clogging, and the like of the ink jet printer head. In order to remove these inorganic impurities, it is desirable to remove the inorganic impurities contained in the ink composition as much as possible by using a known method such as an ultrafiltration method, a reverse osmosis membrane method, or an ion exchange method. The content of inorganic impurities in the total mass of the ink composition is usually 1% by mass or less, preferably 0.1% by mass or less, and more preferably 0.01% by mass or less. The lower limit may be equal to or lower than the detection limit of the detection device, that is, 0%. And after removing an inorganic impurity, adjusting to a desired dye density | concentration by dilution or concentration, and obtaining an ink composition is also performed preferably.

The total content of reactive dyes contained as pigments in the ink composition of the present invention is usually 0.5 to 35% by mass, preferably 1 to 20% by mass, more preferably based on the total mass of the ink composition. The content is preferably 5 to 20% by mass, and more preferably 5 to 15% by mass.

The compound having a structure obtained by addition polymerization of ethylene oxide and / or propylene oxide to diglycerin is not particularly limited as long as it has the structure, and preferred examples include compounds represented by the above formula (1).
The compound represented by the formula (1) is a compound having an average molecular weight of 340 to 2200, and X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a hydrogen atom or a methyl group; j, k , M, and n represent a total number of 4 or more and 40 or less.
X ₁ to X ₄ may be independently identical or different, but are preferably the same. Further, it is more preferable that all of X _{1 to} X ₄ are hydrogen atoms or methyl groups, and it is particularly preferable that all of them are methyl groups.
The compound represented by Formula (1) is a compound obtained by addition polymerization of propylene oxide or ethylene oxide to diglycerin, and k, j, m, and n are average values of addition polymerization.
K, j in the compound represented by the formula (1) obtained by addition polymerization of propylene oxide to diglycerin, that is, the compound in which all of X _{1 to} X ₄ are represented by methyl in the formula (1) , M, and n represent approximately 4 or more and 24 or less in total. The respective values of k, j, m, and n are difficult to specify because they are average values, but are preferably the same value. Specifically, all of k, j, m, and n are preferably in the range of about 1 to 6. In this case, the average molecular weight of the compound represented by the formula (1) is generally about 340 to 2200, preferably 380 to 2000, and more preferably 400 to 1600.
The compound represented by the above formula (1) is a compound obtained by addition polymerization of ethylene oxide to diglycerin, that is, a compound in which all of X _{1 to} X ₄ are represented by hydrogen atoms in formula (1). , J, m, and n represent about 6 to 40 in total. Each value of k, j, m, and n is preferably the same value as described above. Specifically, all of k, j, m, and n are preferably in the range of 1.5 to 10. In this case, the average molecular weight of the compound represented by the formula (1) is generally about 390 to 2200, preferably 430 to 2200, and more preferably 450 to 2000.

The compound represented by the above formula (1) is generally known as polyoxypropylene diglyceryl ether or polyoxyethylene diglyceryl ether, and can also be obtained from the market. Specific examples thereof include, for example, trade names SC-P400 manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. [in the above formula (1), k + j + m + n = 4, compound having an average molecular weight of 400], SC-P750 [similarly k + j + m + n = 9. , Compounds with an average molecular weight of 750], SC-P1000 [similarly k + j + m + n = 14, compounds with an average molecular weight of 1000], SC-P1200 [similarly k + j + m + n = 18, compounds with an average molecular weight of 1200], SC-P1600 [similarly k + j + m + n = 24, a compound having an average molecular weight of 1600] and the like; SC-E450 [in the above formula (1), k + j + m + n = 6, a compound having an average molecular weight of 450], SC-E750 [similarly k + j + m + n = 13, average Compound with molecular weight of 750], SC-E100 [Similarly k + j + m + n = 20, compound with average molecular weight 1000], SC-E1500 [similarly k + j + m + n = 30, compound with average molecular weight 1500], SC-E2000 [similarly k + j + m + n = 40, compound with average molecular weight 2000], etc. Oxyethylene diglyceryl ether; and the like.
Among these specific examples, those having an average molecular weight of about 340 to 2200, preferably 400 to 2000 are preferable. The average molecular weight can be measured by GPC (gel permeation chromatography).

The compound represented by the above formula (1) is used for the purpose of adjusting the viscosity of the ink composition of the present invention. The compound makes it possible to adjust the viscosity of the ink composition to a range of values suitable for industrial inkjet heads that require high-speed ejection response and the like, particularly to the high viscosity side.

The content of the compound represented by the above formula (1) is usually 3 to 50% by mass, preferably 4 to 40% by mass, more preferably 5%, based on the total mass of the ink composition of the present invention. ~ 30% by mass.

The ink composition of the present invention has a viscosity at 25 ° C. measured with an E-type viscometer for the purpose of improving discharge response at high speed when used in a printer equipped with an industrial inkjet head. Sometimes it is usually 3 to 20 mPa · s, preferably 8 to 20 mPa · s.

The ink composition of the present invention is characterized by containing both a nonionic surfactant and an anionic surfactant. By containing both, an ink composition for ink jet printing having excellent continuous discharge stability at a high driving frequency regardless of temperature change and having good dyeing performance can be obtained.

Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; Acetylene alcohols such as 3,5-dimethyl-1-hexyn-3-ol; 2,4,7,9-tetramethyl-5-decyne-4,7-di 3,6-dimethyl-4-octyne-3,6-diol, manufactured by Air Products, trade names Surfinol 104, 104PG50, 82, 420, 440, 465, 485; Olphine STG Acetylene glycol type such as;
Among the above, acetylene glycol type or acetylene alcohol type is preferable, acetylene glycol type is more preferable, and trade name Surfynol series manufactured by Air Products is particularly preferable.

The content of the nonionic surfactant is usually 0.05 to 2% by mass, preferably 0.05 to 1.5% by mass, and more preferably based on the total mass of the ink composition of the present invention. 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass.

Examples of anionic surfactants include alkyl sulfocarboxylates; α-olefin sulfonates; polyoxyethylene alkyl ether acetates; N-acyl amino acids or salts thereof; N-acyl methyl taurates; alkyl sulfates polyoxyalkyl ethers Sulfate; Alkyl sulfate Polyoxyethylene alkyl ether phosphate; Rosin acid soap; Castor oil sulfate ester; Lauryl alcohol sulfate ester; Alkyl phenol type phosphate ester; Alkyl type phosphate ester; Alkyl aryl sulfonate; And salts of sulfosuccinic acid such as salts, diethylhexyl sulfosuccinate and dioctyl sulfosuccinate. Sulfosuccinic acid type is preferable, and examples of commercially available products thereof include products manufactured by Lion Corporation, trade names Ripal 835I, 860K, 870P, NTD, MSC; manufactured by Adeka Corporation. Adeka Coal EC8600; manufactured by Kao Corporation, trade name: Perex OT-P, CS, TA, TR; Shin Nippon Rika Co., Ltd., Rica Mild ES-100, ES-200, Rika Surf P-10, M-30, M-75, M-300, G-30, G-600; manufactured by Toho Chemical Co., Ltd., Kohakunol L-300, L-40, L-400, NL-400; and the like. Among these commercially available products, Adeka Coal EC8600 and Perex series (preferably Perex OT-P) are particularly preferable.

The content of the anionic surfactant is usually 0.05 to 2% by mass, preferably 0.05 to 1.5% by mass, more preferably based on the total mass of the ink composition of the present invention. 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass.

The ink composition of the present invention is intended to improve image quality when used in a printer equipped with an industrial inkjet head, and is usually 20 to 20 when the surface tension at 10 ° C. and 25 ° C. is measured by the plate method. The range is 40 mN / m, preferably 25 to 35 mN / m.

The ink composition of the present invention is intended to improve continuous discharge performance at a low temperature environment and at a high speed when used in a printer equipped with an industrial inkjet head, at 10 Hz at 10 ° C. and 25 ° C. The dynamic surface tension is usually in the range of 25 to 45 mN / m, preferably 30 to 45 mN / m, more preferably 30 to 40 mN / m when measured by the maximum bubble pressure method. This dynamic surface tension and its measurement are also disclosed in Japanese Patent Application Laid-Open No. 2007-162006.

The ink composition of the present invention is a composition containing the reactive dye, the compound represented by the formula (1), a nonionic surfactant, and an anionic surfactant, with the balance being water.
In addition to these, examples of additives that may be contained in the ink composition of the present invention include water-soluble organic solvents and ink preparation agents.

Examples of the water-soluble organic solvent that may be contained in the ink composition of the present invention include polyhydric alcohols and pyrrolidones.
Examples of polyhydric alcohols include C2-C6 alcohols having 2 or 3 alcoholic hydroxyl groups, and poly C2-C3 alkylene glycols having a repeating unit of 4 or more and a molecular weight of about 20,000 or less, preferably a liquid polyhydric alcohol. Examples include alkylene glycol. Specific examples thereof include C2-C6 alcohols having two or three alcoholic hydroxyl groups such as glycerin, 1,3-pentanediol, 1,5-pentanediol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, And di- or tri-C2-C3 alkylene glycol such as polyethylene glycol; poly-C2-C3 alkylene glycol such as polypropylene glycol; and the like.
Examples of pyrrolidones include 2-pyrrolidone and N-methyl-2-pyrrolidone.
The water-soluble organic solvent may be used alone, but is preferably used in combination.
The water-soluble organic solvent is used in anticipation of effects such as prevention (wetting) of drying of the ink composition; adjustment of viscosity and / or surface tension; defoaming; promotion of penetration into fibers; The ink composition of the present invention is preferably contained.
The total content of the water-soluble organic solvent is usually 1 to 50% by mass, preferably 5 to 40% by mass, and more preferably 10 to 35% by mass with respect to the total mass of the ink composition. However, when only one kind of reactive dye is contained as a pigment, it is more preferable in some cases that the content of the water-soluble organic solvent is 10 to 20% by mass.

Examples of the ink preparation agent include antiseptic / antifungal agents and pH adjusters. The total amount of the ink preparation agent is usually about 0 to 10%, preferably about 0.05 to 5%, based on the total mass of the ink composition.

Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, 1-benzisothiazoline- Examples include 3-one amine salt, Proxel GXL manufactured by Arch Chemicals, and preferably Proxel GXL.

Examples of pH adjusters include hydroxides of alkaline earth metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide; triethanolamine, diethanolamine, dimethylethanolamine, diethylethanolamine, tris (hydroxymethyl) amino And tertiary amines such as methane, preferably mono-, di-, or tri-C1-C4 alkylamines optionally substituted with a hydroxy group. Of these, tris (hydroxymethyl) aminomethane is preferred.
The ink composition of the present invention preferably contains a pH adjuster, and its content is usually 0.05 to 3% by mass, preferably 0.05 to 2.5%, based on the total mass of the ink composition. % By mass, more preferably 0.1 to 2% by mass.

In the ink composition of the present invention, a dye, a compound represented by the above formula (1), a nonionic surfactant, and an anionic surfactant are added to water, and the water-soluble organic solvent and ink preparation described above are added as necessary. It is obtained by further adding the agent and stirring, and mixing until the solids such as the dye are dissolved.
The order in which each component is added is not particularly limited, and the ink composition of the present invention may be prepared by mixing until stirring until it is substantially in solution. As described above, the water used in preparing the ink composition is preferably water with few inorganic impurities, such as distilled water or ion-exchanged water.
When the ink composition of the present invention is used for ink jet textile printing, the ink composition of the present invention is finely filtered using a membrane filter or the like, and the filtrate from which impurities are removed is preferably used as the ink. The pore size of the filter when performing microfiltration is usually 1 to 0.1 μm, preferably 0.8 to 0.1 μm.

The textile printing method of the present invention comprises the ink composition of the present invention, preferably by filtering the ink composition with a membrane filter or the like to remove impurities, and then using this ink to produce a fiber, preferably a cellulosic system. In this method, printing is performed on fibers or polyamide-based fibers and then subjected to a treatment such as heating. There are no particular restrictions on the print head, ink nozzles, and the like used for printing, and they can be appropriately selected according to the purpose. More specifically, it is preferable to print on a fabric mainly composed of cellulosic fibers or polyamide fibers as the fibers to be printed.
Examples of the cellulosic fibers include natural fibers such as cotton and hemp; regenerated cellulose fibers such as rayon; and blended fibers containing these.
Examples of the polyamide fibers include natural polyamide fibers such as silk and wool; synthetic polyamide fibers such as nylon; and blended fibers containing these.

Examples of a method for printing on a fiber using the ink composition of the present invention include a method of sequentially performing the following three steps.
[Step 1]
A step of using the ink composition of the present invention as an ink and ejecting the ink droplets of the ink by an ink jet printer to apply to the fiber (printing step).
[Step 2]
A step of reacting and fixing the dye in the ink composition applied in step 1 to the fibers by heat.
[Step 3]
Cleaning the unfixed dye remaining in the fiber.

As a method of applying the ink composition of the present invention to the fibers in the above step 1, a container filled with the ink composition of the present invention is loaded in a predetermined position of an ink jet printer and used as an ink. An ink jet printing method in which ink droplets are ejected according to a recording signal and applied to a fiber can be used.

As the step of reacting and fixing the dye in the ink composition to the fiber by heat in the above step 2, the fiber to which the ink composition of the present invention has been applied is allowed to stand at room temperature to 150 ° C. for 0.5 to 30 minutes. And a method of further performing a steaming treatment after the preliminary drying. The conditions for the steaming treatment are preferably conditions in which the fibers are placed for 5 to 40 minutes in an environment of 80 to 100% humidity and 95 to 105 ° C.

As the step of washing the unfixed dye remaining in the fiber in the step 3, it is preferable to wash the fiber with cold water. In washing, the water may contain a surfactant.
The target printed matter can be obtained by drying the fiber after washing the unfixed dye at 50 to 120 ° C. for 5 to 30 minutes.

As a textile printing method, a method including a pretreatment step for the fiber before performing the above three steps, that is, before applying the ink composition is preferable. In this pretreatment step, an aqueous solution containing one or more types of paste material, a pH adjuster contained in the pretreatment liquid, and a hydrotropic agent is used as a pretreatment liquid. For example, the ink composition is prepared by a padding method (pad method). The process of impregnating the fiber before providing is mentioned. The padding drawing ratio is preferably about 40 to 90%, more preferably about 60 to 80%.
Although this pretreatment process is not essential, an effect of preventing dye bleeding may be obtained at the time of printing including at the time of printing, and therefore a printing method in which four steps including the pretreatment process are sequentially performed is preferable.
The pH adjusting agent contained in the pretreatment liquid has the same purpose of use as the pH adjusting agent contained in the ink composition of the present invention, but preferred specific examples thereof are different. For this reason, in this specification, the pH adjuster contained in the ink composition of the present invention is simply “pH adjuster”, and the pH adjuster contained in the pretreatment liquid is “pH adjuster for pretreatment”. Describe and distinguish between the two.

Examples of the paste include natural gums such as guar and locust bean, starches, seaweeds such as sodium alginate and fungi, plant skins such as pectic acid, methyl fibrin, ethyl fibrin, hydroxyethylcellulose, carboxymethylcellulose, etc. Fiber derivatives, processed starches such as carboxymethyl starch, processed natural gums such as shiratsu gum and roast bean gum, and synthetic glues such as polyvinyl alcohol and polyacrylate.
Of these, preferable agglutinating agents include sodium alginate for cellulosic fibers, natural gums such as guar and locust bean for polyamide fibers; and / or processed natural gums such as shiraz gum and roast bean gum. Respectively.

As the pH adjuster for pretreatment in the pretreatment step of the cellulosic fiber, those which show alkalinity when made into an aqueous solution are preferable, for example, alkali metal salts of inorganic acids or organic acids; alkaline earth metal salts; and Examples include compounds that liberate alkali when heated. In particular, alkali metal hydroxides and alkali metal salts of inorganic or organic acids are suitable. Specific examples include sodium hydroxide, calcium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium formate, sodium phosphate, and the like. Among these, sodium hydrogen carbonate is preferable.

As the pH adjuster for pretreatment in the pretreatment step of the polyamide-based fiber, those which show acidity when made into an aqueous solution are preferable, and specific examples include ammonium salts such as ammonium sulfate, ammonium tartrate, and ammonium acetate. Of these, ammonium sulfate is preferable.

Examples of the hydrotropic agent in the pretreatment step include urea derivatives such as urea, dimethylurea, thiourea, monomethylthiourea, and dimethylthiourea, preferably urea.

These pretreatment agents in the pretreatment step may be used alone, but are preferably used in combination.

For the total mass of the pretreatment liquid, the contents of the paste, the pH adjusting agent for pretreatment, and the hydrotropic agent should be determined in accordance with, for example, the blend ratio of each of the cellulose fibers and polyamide fibers. However, as a guideline, the amount of paste is 0.5 to 5% on the mass basis, the pH adjuster for pretreatment is 0.5 to 5%, The tropic agent is 1 to 20% by mass, and the balance is water.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified in the examples, “parts” means parts by weight, and “%” means mass%.

In the following present invention, the compound represented by the above formula (1) was used as a compound having a structure in which ethylene oxide and / or propylene oxide was added to diglycerin. As the compound represented by the formula (1), the following two systems of compounds, both commercially available from Sakamoto Yakuhin Kogyo Co., Ltd., were used. Among these, the compounds of “SC-P” are all polyoxypropylene diglyceryl ether, and the compounds of “SC-E” are all polyoxyethylene diglyceryl ether.
Product name 1) SC-P400: Average molecular weight 400
2) SC-P1000: Average molecular weight 1000
3) SC-P1600: Average molecular weight 1600
4) SC-E450: Average molecular weight 450
5) SC-E2000: Average molecular weight 2000

[Examples 1 to 6]
The components described in each of the following examples were mixed and stirred for about 1 hour until the solid content was dissolved to obtain each ink composition, and then a 0.45 μm membrane filter (trade name cellulose acetate filter paper). The ink for a test was prepared by filtering with Advantech). The ink preparations are referred to as Examples 1 to 6, respectively.
The reactive dye used as a pigment in each ink is a monochlorotriazine reactive dye manufactured by Nippon Kayaku Co., Ltd. The word “Reactive” immediately after “CI” is a well-known word. As usual, it means “reactive dye”.

[Example 1 (yellow ink)]
C. I. Reactive Yellow 2 10 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-P400 25 parts Propylene glycol 10 parts 2-Pyrrolidone 5 parts Surfinol 104PG50 0.1 part Adekacol EC8600 0.5 part Proxel GXL 0.1 part Ion 48.8 parts of replacement water

[Example 2 (magenta ink)]
C. I. Reactive Red 3: 1 10 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-P1000 15 parts Propylene glycol 10 parts 2-Pyrrolidone 3 parts Surfinol 440 0.3 part Adekacol EC8600 0.3 part Proxel GXL 0.1 Part Ion-exchanged water 60.8 parts

[Example 3 (cyan ink)]
C. I. Reactive Blue 15: 1 10 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-P1600 25 parts Propylene glycol 10 parts 2-Pyrrolidone 3 parts Surfynol 485 0.1 part Adekacol EC8600 0.2 part Proxel GXL 0.1 Part Ion-exchanged water 51.1 parts

[Example 4 (orange ink)]
C. I. Reactive Orange 13 10 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-E450 25 parts Propylene glycol 10 parts 2-Pyrrolidone 3 parts Surfynol 440 0.3 part Plex OT-P 0.1 part Proxel GXL 0.1 Part Ion-exchanged water 51 parts

[Example 5 (cyan ink)]
C. I. Reactive Blue 49 10 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-E2000 20 parts Propylene glycol 10 parts 2-Pyrrolidone 3 parts Surfynol 485 0.5 parts Plex OT-P 0.5 parts Proxel GXL 0.1 Part 55.4 parts ion-exchanged water

[Example 6 (black ink)]
C. I. Reactive Blue 176 9 parts C.I. I. Reactive Red 3: 1 3 parts C.I. I. Reactive Orange 12 3 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-E2000 5 parts Ethylene glycol 15 parts Propylene glycol 10 parts 2-Pyrrolidone 10 parts Surfynol 485 0.5 parts Adekacol EC8600 0.1 part Proxel GXL 0 .1 part 43.8 parts ion-exchanged water

[Comparative Examples 1 to 4]
A comparative ink was prepared in the same manner as in Example 2 except that the nonionic surfactant and the anionic surfactant were not used in combination and each was used alone. This comparative ink is referred to as Comparative Examples 1 and 2.
Similarly, a comparative ink was prepared in the same manner as in Example 5 except that the surfactant was used alone. This comparative ink was prepared as Comparative Examples 3 and 4.
Comparative Examples 1 and 3 are inks using only a nonionic surfactant and an increased amount of ion-exchanged water instead of an anionic surfactant, and Comparative Examples 2 and 4 are using only an anionic surfactant, Ink with increased amount of ion-exchanged water instead of surfactant.

[Comparative Example 1]
C. I. Reactive Red 3: 1 10 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-P1000 15 parts Propylene glycol 10 parts 2-pyrrolidone 3 parts Surfynol 440 0.3 part Proxel GXL 0.1 part Ion-exchanged water 61. 1 copy

[Comparative Example 2]
C. I. Reactive Red 3: 1 10 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-P1000 15 parts Propylene glycol 10 parts 2-pyrrolidone 3 parts Adekacol EC8600 0.3 part Proxel GXL 0.1 part Ion-exchanged water 61.1 Part

[Comparative Example 3]
C. I. Reactive Blue 49 10 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-E2000 20 parts Propylene glycol 10 parts 2-Pyrrolidone 3 parts Surfinol 485 0.5 part Proxel GXL 0.1 part Ion-exchanged water 55.9 parts

[Comparative Example 4]
C. I. Reactive Blue 49 10 parts Tris (hydroxymethyl) aminomethane 0.5 part SC-E2000 20 parts Propylene glycol 10 parts 2-Pyrrolidone 3 parts Plex OT-P 0.5 part Proxel GXL 0.1 part Ion-exchanged water 55.9 Part

[Comparative Examples 5 to 7]
In Example 4, Comparative Examples 5 to 7 were carried out in the same manner as Example 4 except that 25 parts of each of the compounds shown below were used instead of 25 parts of the compound represented by the above formula (1) (SC-E450). The comparative ink was prepared.
Comparative Example 5: Glycerol Comparative Example 6: Polyglycerin 750 (polyglycerin having an average molecular weight of 750, manufactured by Sakamoto Pharmaceutical Co., Ltd.)
Comparative Example 7: Propylene glycol

Using the inks of Examples 1 to 5 and Comparative Examples 1 to 7 obtained as described above, measurement of basic physical properties, preparation of dyed cloth, and evaluation were performed as follows.

[Evaluation of ink]
For each of the inks prepared in Examples 1 to 5 and Comparative Examples 1 to 7, the following seven tests (1) to (7) were conducted to evaluate the ink performance. Among the test results, (1) Viscosity test to (3) Dynamic surface tension, which is a measurement test of basic physical property values of ink, is shown in Table 1 below, and (4) Continuous ejection test is an ink performance test. (7) Dyeability test 2 is shown in Table 2 below.

(1) Viscosity test The viscosity of the ink of each Example and each comparative example was measured at 10 ° C. and 25 ° C. using an E-type viscometer (R115 viscometer, manufactured by Toki Sangyo Co., Ltd.). In addition, the unit of the numerical value in following Table 1 is mPa * s.

(2) Surface tension The surface tension of the inks of the examples and comparative examples was measured at 10 ° C. and 25 ° C. by the plate method (CBVP-Z surface tension meter, manufactured by Kyowa Interface Science Co., Ltd.). In addition, the unit of the numerical value in the following Table 1 is mN / m.

(3) Dynamic surface tension The dynamic surface tension of the ink of each Example and each Comparative Example was measured using a maximum bubble pressure method (SITA SCIENCE LINE 60 type dynamic surface tension meter, SITA at 10 Hz of 10 ° C. and 10 Hz of 25 ° C. Measured by Messtechnik GmbH). In addition, the unit of the numerical value in the following Table 1 is mN / m.

(4) Continuous ejection property test Each example and each comparative example ink were used individually on a cotton cloth pretreated by the pad method using an aqueous solution containing sodium alginate, urea, and sodium bicarbonate. , On-demand type inkjet printer (Apollo 2 printer system, manufactured by Fujifilm Dimatics) equipped with industrial inkjet head (NOVA, manufactured by Fujifilm Dimatics) Ink ejection properties were evaluated. The ejection property was obtained by continuously printing 5 m with a solid pattern on a cotton fabric having a width of 7.5 cm using an ITI Web Transport (inkjet printing cloth conveyance machine, manufactured by ITI Corporation) to obtain a printing cotton cloth. The test results were evaluated according to the following criteria depending on the state of the obtained printed image.
○: Can be printed well to the end.
Δ: streaks are confirmed in the printed image or printing is unstable, but printing can be performed to the end.
X: Scattering of printed images, streaks are severe, or printing is unstable, and printing cannot be performed to the end.

(5) Low-temperature continuous discharge test In the above (4) continuous discharge test, printing was performed in the same manner except that the ambient temperature was changed to a low-temperature environment of 25 ° C. to 10 ° C. to obtain a printed cotton fabric. The test results were evaluated according to the same criteria as in the above (4) continuous discharge test according to the state of the obtained printed image.

(6) Dyeability test 1
<Test with cotton cloth>
The initial printing portion 30 cm of each printing cotton cloth obtained in the above (4) continuous discharge test was subjected to intermediate drying at 60 to 80 ° C. and then steaming treatment at 100 to 103 ° C. for 10 minutes. After washing with water, it was washed with boiling water at 95 to 100 ° C. for 10 minutes, washed with water and dried to obtain a printed cotton fabric for testing.
<Test with silk cloth>
The silk fabric pretreated by the pad method using an aqueous solution containing guar, ammonium sulfate, and urea was subjected to the above (4) continuous discharge test, and the initial printing portion 20 cm of the obtained silk fabric was After intermediate drying at 60 to 80 ° C., a steaming treatment was performed at 100 to 103 ° C. for 20 minutes. After washing with water and drying, a printed silk fabric for testing was obtained. The test results were evaluated according to the following criteria depending on the state of each obtained dyed fabric.
In Comparative Examples 5 and 7, since good printing could not be performed in the above (4) continuous discharge test, this dyeability test 1 was not performed.
○: The printed image has no graininess, and the printed dyed fabric is not irritated.
X: The printed image has a graininess, and the printed dyed fabric is irritated.

(7) Dyeability test 2
For the purpose of investigating the influence of the compound represented by the formula (1) on the fixation of the reactive dye to the cellulose fiber, Example 4 and Comparative Examples 5 to 7 were marked with the marks obtained in the above (5) low-temperature continuous ejection test. A 20 cm initial printing portion of the cotton fabric was subjected to intermediate drying at 60 to 80 ° C. and then steaming at 100 to 103 ° C. for 10 minutes. After washing with water, it was washed with boiling water at 95 to 100 ° C. for 10 minutes, washed with water and dried to prepare a printed cotton dyed fabric.
Using a colorimeter (SpectroEye, manufactured by GRETAG-MACBETH), the Macbeth reflection density of the printed cotton dyed fabric obtained as described above was measured, and each fixing rate was determined by the following formula.
Adhesion rate = (A / B) × 100 (%)
A: Reflection density of the cotton dyed fabric printed in Example 4 or Comparative Examples 5 to 7.
B: Reflection density of the cotton dyed fabric printed in Example 4.
The test result of the adhesion rate was evaluated according to the following criteria.
○: 95% or more △: 90% or more and less than 95% ×: less than 90%

As is apparent from the results in Table 1, the inks of the respective examples in which the nonionic surfactant and the anionic surfactant were used in combination had surface tensions in the range of 25 to 35 mN / m at 25 ° C. and 10 ° C. The dynamic surface tension at a temperature of 10 Hz is in the range of 30 to 40 mN / m.
In all the test items, each example showed the best result.
On the other hand, Comparative Examples 1 and 3 using only the nonionic surfactant have good ejection properties, but (6) the printed image has a grainy feeling in the dyeability test 1, and the printed dyed fabric There was also annoyance, and it turned out that it was inferior in quality. In addition, it was found that Comparative Examples 2 and 4 using only an anionic surfactant cannot obtain good dischargeability in the (5) low temperature continuous dischargeability test.
In addition, in Comparative Example 5 using glycerin, Comparative Example 6 using polyglycerin 750, and Comparative Example 7 using propylene glycol instead of the compound represented by Formula (1), the ink viscosity at 25 ° C. Low (4) In any of the continuous discharge tests, good discharge properties were not obtained.
In Comparative Examples 5 to 7, (5) the low-temperature continuous discharge test showed good discharge, but the obtained printed cotton fabric was used. (7) In the dyeability test 2, Comparative Examples 5 and 6 The dyeing performance of was very poor.
From the above results, the ink composition of the present invention is suitable as a textile printing ink excellent in continuous discharge property and good dyeability regardless of temperature change, particularly as a textile textile printing ink using an industrial inkjet head.

The ink composition of the present invention can be suitably used as an ink for textile printing, preferably for inkjet printing, particularly for inkjet printing using an industrial inkjet head.

Claims

An ink composition containing at least one reactive dye, a compound having a structure obtained by addition polymerization of ethylene oxide and / or propylene oxide to diglycerin, a nonionic surfactant, an anionic surfactant, and water.
The ink composition according to claim 1, wherein the compound having a structure in which ethylene oxide and / or propylene oxide is addition-polymerized to diglycerin is a compound represented by the following formula (1):

[Where:
X 1 , X 2 , X 3 , and X 4 each independently represent a hydrogen atom or a methyl group,
j, k, m, and n represent a total number of 4 to 40 in total. ]
The ink composition according to claim 1 or 2, wherein the nonionic surfactant is an acetylene glycol surfactant or an acetylene alcohol surfactant, and the anionic surfactant is a sulfosuccinic acid surfactant.
The ink composition according to claim 2 or 3, wherein all of X 1 , X 2 , X 3 , and X 4 in the formula (1) are methyl groups.
0.5 to 35% by mass of reactive dye, 3 to 50% by mass of a compound having a structure in which ethylene oxide and / or propylene oxide is added to diglycerin, and nonionic surfactant based on the total mass of the ink composition The ink composition according to any one of Claims 1 to 4, wherein 0.05 to 2 mass% of anionic surfactant, 0.05 to 2 mass% of an anionic surfactant are contained, and the balance is water.
The ink composition according to any one of claims 1 to 5, further comprising a water-soluble organic solvent.
The ink composition according to any one of claims 1 to 6, further comprising 0.05 to 3% by mass of a pH adjuster based on the total mass of the ink composition.
A step of applying the ink composition according to any one of claims 1 to 7 as an ink, ejecting ink droplets of the ink by an ink jet printer to a fiber, and a dye in the ink composition applied by the step by heat. A fiber printing method comprising a step of reactively fixing to the fiber and a step of washing unfixed dye remaining in the fiber.
9. The fiber pretreatment step of impregnating the fiber before applying the ink composition with an aqueous solution containing one or more kinds of paste material, a pretreatment pH adjuster, and a hydrotropic agent. The textile printing method as described.
A printed matter printed by the fiber printing method according to claim 8 or 9.