JPH0535191B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an inkjet recording ink composition, and particularly to cotton, linen, viscose, wool,
This invention relates to an inkjet recording ink composition suitable for printing woven or non-woven fabrics made of fibers dyeable with reactive dyes, such as silk and nylon, or blended woven fabrics or blended non-woven fabrics made of these fibers and other synthetic fibers. . (Prior art) Conventionally, woven or non-woven fabrics made of fibers that can be dyed with reactive dyes, such as cotton, hemp, viscose, wool, silk, nylon, etc., or blended fabrics of these fibers and other synthetic fibers. For printing cloth, etc., printing methods such as roller printing, screen printing, and transfer printing are used, and some printing methods using inkjet recording methods have also been proposed. (Problem to be solved by the invention) However, in the conventional general textile printing method, it is necessary to create printing plates for printing, and the creation of these printing plates, such as printing plate cylinders and screen plates, is expensive. Also, in transfer printing, it is expensive to create a plate for printing transfer paper, so it is not cost-effective unless a large quantity is produced. In addition, since the fashion period for printed cloth patterns is generally short, making plates each time increases the cost, and there is a serious problem in that it is not possible to respond quickly to trends, and a large amount of inventory may be required. In order to solve these drawbacks, printing using an inkjet method has been proposed, but printing using this inkjet method causes various problems such as clogging of the ink ejection section of the recording device.
Practical implementation was not always easy. Furthermore, depending on the type and concentration of the reactive dye, even if the dye is completely dissolved at the time of ink preparation, there are problems with the storage stability of the ink, such as the formation of precipitates if left to stand. Therefore, an object of the present invention is to solve the above-mentioned economical problems in the conventional general textile printing method, various troubles in the printing method using inkjet recording, and the problem of accurate and stable printing at the same time. An object of the present invention is to provide an ink composition for inkjet recording. These objects and other objects of the present invention are achieved by the present invention described below. (Disclosure of the Invention) That is, the present invention provides an inkjet textile printing method that includes the steps of applying ink to fabrics by an inkjet method, then performing a reaction fixing treatment, and then removing unreacted dye by a washing treatment. an ink containing a reactive dye and an aqueous medium, the polyvalent metal content of which is 100 ppm or less (however, polyvalent metals in the metal-containing dye are not taken into account)
The present invention provides an inkjet textile printing ink, and an inkjet textile printing method using such an ink. To explain the present invention in more detail, the present invention
The second feature is that a reactive dye is used as a coloring component of the inkjet recording ink composition, and the second feature is that the polyvalent metal content of the ink composition containing the reactive dye is reduced.
The point is that it has been adjusted to below 100ppm. As a result of various studies on textile printing using the inkjet method, the present inventor has found that various problems with the above-mentioned equipment and problems with the storage stability of the ink are caused by alkaline earth metals and other polyvalent metals present in the ink composition. We found that this is due to the presence of inorganic metal salts or their colloids. Furthermore, it has been found that when a large amount of this polyvalent metal ion is present in the ink, the dyeing on the woven fabric becomes uneven and the level dyeing property deteriorates. This problem is particularly noticeable when using reactive dyes. In other words, reactive dyes are dyes that are more unstable due to the presence of reactive groups than other types of dyes (acidic, direct, dispersed), and they are dyes that are more unstable due to the presence of reactive groups after recording on woven fabrics due to hydrolysis. This is thought to be because dye molecules that cannot be dyed (reacted) onto woven fabrics are likely to be generated, and this hydrolysis is facilitated by the presence of polyvalent metal ions. The reactive dye that first characterizes the present invention and is used in the present invention is a material that is known per se, and is a water-soluble azo-based or anthraquinone-based material that is widely used in fiber dyeing or conventional textile printing methods. , phthalocyanine and other dyes.
These reactive dyes have a water-soluble group such as a sulfonic acid group or a carboxyl group in their structure, and a group that can react with the hydroxyl group or amino group of the fiber to form a covalent bond with the fiber, such as di Chlortriazine group, monochlortriazine group, trichlorpyrimidine group, monochlordifluoropyrimidine group, chlorbenzothiazole group, dichlorpyridazone group, dichloropyridazine group, dichloroquinoxaline group, epoxy group, 3-carboxypyridiniotriazine group , −SO ₂ CH ₂ CH ₂ OSO ₃ H, −
SO ₂ NHCH ₂ CH ₂ OSO ₃ H, −
NHCOCH ₂ CH ₂ OSO ₃ H, −NHCOCH ₂ CH ₂ Cl, −
NHCOCH= _CH2 , _-SO2CH = _CH2 ,-
CH ₂ NHCOCCl=CH ₂ , -NHCOCBr=CH ₂ , -
It has groups such as NHCOCH ₂ Cl, -NHCH ₂ OH, and -PO ₃ H. In the present invention, any of these conventionally known reactive dyes can be used, and preferable reactive dyes in the present invention include CI Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23 ,
24, 25, 26, 27, 29, 35, 37, 41, 42, 49, 50,
52, 54, 55, 57, 58, 63, 64, 75, 76, 77, 79,
81, 82, 83, 84, 85, 87, 88, 91, 92, 93, 95,
96, 111, 115, 116, 131, 135, CI reactive orange 5, 7, 10, 11, 12, 13, 15, 16,
20, 30, 34, 35, 41, 42, 44, 45, 46, 56, 57,
62, 63, 64, 67, 69, 71, 72, 73, 74, 78, 82,
84, 87, CI reactive bracelet 3, 13, 17,
19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43,
45, 49, 55, 56, 58, 63, 67, 80, 81, 82, 85,
86, 87, 104, 106, 108, 109, 110, 111, 112,
113, 114, 117, 118, 119, 120, 123, 124, 126,
128, 130, 131, 132, 141, 147, 158, 159, 170,
171, 174, 176, CI Reactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22,
23, 24, 26, 27, 33, CI reactive blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19,
21, 25, 26, 27, 28, 29, 38, 39, 40, 42, 43,
49, 51, 52, 65, 66, 67, 68, 71, 73, 74, 75,
77, 78, 79, 80, 89, 98, 100, 101, 104, 105,
112, 113, 114, 116, 119, 147, 148, 158, 160,
162, 169, 170, 171, 179, 182, 187, CI reactive green 5, 8, 12, 14, 15, 16, 19,
21, CI reactive brown 2, 5, 6, 7,
8, 9, 16, 17, 18, 19, 21, 24, 26, 30,,C.
I. Reactive black 4, 5, 8, 14, 21,
23, 26, 31, 32, 34, and various dyes in the Kayaseron React series (Nippon Kayaku Co., Ltd.). If the fiber to be printed is wool or nylon, CI Reactive Yellow 21, 34, 39, 69,
98, 125, 127, CI Reactive Orange 29,
53, 68, CI reactive bracelet 28, 65, 66,
78, 83, 84, 100, 116, 136, 147, 154, 172, C.
I. Reactive Violet 34, CI Reactive Blue 50, 69, 94, 177, CI Reactive Brown 12, etc. are suitable. In the present invention, as the medium for dissolving the above-mentioned reactive dye, any medium used in conventional general dyeing or medium used in conventional inkjet recording ink can be used. For example, water or water and water can be used. Mixtures with water-soluble organic solvents are preferred, such as methyl alcohol,
Ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Alkyl alcohols with 1 to 4 carbon atoms such as sec-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketone or keto alcohols such as acetone and diacetone alcohol; tetrahydrofuran, dioxane, etc. ethers; polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
Alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms, such as 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol; glycerin; ethylene glycol methyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether; N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and the like. Although the above-mentioned media can be used alone or as a mixture, the most preferred media composition consists of water and one or more water-soluble organic solvents, where the water-soluble solvent is at least one water-soluble high-boiling organic solvent, e.g. It contains polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin. The amount of these media used is such that when the ink composition is prepared, the content of the aforementioned reactive dye is approximately
The amount is 0.1 to 15% by weight. The essential components of the ink composition of the present invention are as described above, but various other conventionally known dispersants, surfactants, and viscosity modifiers can be added as necessary. Dispersants or surfactants that can be added as necessary include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin. Anionic dispersants or surfactants such as condensates, polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters,
Nonionic dispersants or surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethylene oxypropylene block copolymer are important. As the viscosity modifier, mainly water-soluble natural or synthetic polymers such as carboxymethylcellulose, sodium polyacrylate, polybenylpyrrolidone, gum arabic, and starch are preferred, and these viscosity modifiers can be used or not used. The viscosity of the ink composition of the present invention was 50 cps at 25°C.
Hereinafter, preferably 1 to 15 cps. Further, in order to prepare ink used in an inkjet recording method of the type in which the ink is charged, resistivity adjusters such as inorganic salts such as lithium chloride, ammonium chloride, and sodium chloride are added. When applied to an inkjet method that ejects ink through the action of thermal energy, the thermal properties (e.g., specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted. . Further, other than the above three types of additives, for example, an antifoaming agent, a penetrating agent, a fungicide, a PH regulator, etc. can be appropriately added as necessary. The inkjet recording ink composition of the present invention can be obtained by simply adding the necessary components to a medium and dissolving them. The inkjet recording ink composition of the present invention is obtained as described above, but what is particularly important in the present invention is that when the above-mentioned essential components and optional components are blended, the resulting ink composition has a polyvalent component. The purpose of the present invention is to adjust the metal content to 100 ppm or less, and the object of the present invention is mainly achieved by making the ink composition have the polyvalent metal content as described above. Such adjustment of the polyvalent metal content can be achieved by limiting the material of the device for dissolving the reactive dye used in the present invention, by limiting the material of the device for dissolving the reactive dye used in the present invention, by refining the reactive dye by any known method, and by adjusting the water used as a medium. This is achieved by using distilled or deionized water as Purification methods include conventionally known salting-out methods, extraction methods, fractional precipitation methods, methods using ion exchange membranes,
Preferably, an ultrafiltration method, a reverse osmosis method, a method using a microfilter, a method using a chelating agent, a recrystallization method, a method using a flocculant, or a combination of these methods are suitable. In the inkjet recording ink composition of the present invention, if the polyvalent metal content is 100 ppm or more, it may cause clogging. In addition, the ejection stability of the ink is poor, the storage stability of the ink itself is problematic, and the level dyeing of woven fabrics is not sufficient, but when the concentration is lower than the above, these various problems occur rapidly. It will be resolved in The above ink composition for inkjet recording of the present invention is useful for printing woven or nonwoven fabrics by inkjet recording, and is particularly useful for printing textiles such as cotton, linen, viscose, wool, silk, nylon, etc. with reactive dyes. It is useful for printing woven fabrics or nonwoven fabrics made of available fibers, or mixed woven fabrics or nonwoven fabrics made of these fibers and synthetic fibers such as polyester fibers, acetate fibers, polypropylene fibers, and vinylon fibers. Any conventionally known woven or nonwoven fabric can be used, but in addition, these woven or nonwoven fabrics may be pretreated for inkjet printing. Such pretreatment can be carried out by applying a water-soluble or water-dispersible polymer or the like that can quickly absorb and retain the applied ink composition to the surface of the fibers constituting the woven fabric. The inkjet recording method used to apply the inkjet recording ink composition of the present invention to the above-mentioned woven fabric, nonwoven fabric, or molded article is such that the ink composition is effectively removed from a nozzle, Any method may be used as long as it can be applied to cloth or non-woven fabrics, and representative examples of these methods include, for example, IEEE Trans actions on Industry Applications.
Industry Applications) Vol.JA−13, No.1
(February/March 1977 issue), Nikkei Electronics No.
No. 305 (December 6, 1982 issue).
The methods described in these are suitable for use with the inkjet recording ink composition of the present invention,
To explain some of them, there is the electrostatic suction method. In this method, a strong electric field is applied between the nozzle and an accelerating electrode placed several mm in front of the nozzle, and the ink is pulverized from the nozzle into particles one after another. There is a method in which an information signal is applied to the deflection electrodes while the drawn ink composition flies between the deflection electrodes for recording, and a method in which ink particles are ejected in response to the information signal without deflecting the ink particles. All of these are effective for application of the inkjet recording ink of the present invention. The second method is to forcibly eject minute ink particles by applying high pressure to the ink with a small pump and mechanically vibrating the nozzle with a crystal oscillator. At the same time as the injection, it is charged according to the information signal. When the charged ink particles pass between the deflection electrode plates, they are deflected according to the amount of charge. Another method using this method is called the microdot inkjet method. In this method, ink pressure and excitation conditions are kept within a certain range of values, and two types of ink liquid, large and small, are injected from the nozzle tip. Droplets are generated, and only the small and medium-sized droplets are used for recording. The feature of this method is that it is possible to obtain a group of minute droplets even with a conventionally large nozzle diameter. A third method is a piezo element method, in which a piezo element is used as a pressure means for applying pressure to the ink, rather than a mechanical means such as a pump as in other methods. This method applies an electric signal to a piezo element to cause mechanical displacement, thereby applying pressure to the ink and ejecting it from a nozzle. Further, the ink composition of the present invention is
A method of printing using the inkjet method, which is described in Publication No. 51837, in which the ink subjected to the action of thermal energy undergoes a sudden volume change, and the acting force resulting from this state change causes the ink to be ejected from a nozzle. It also shows excellent ejection stability. Any of the various inkjet recording methods described above can be used, and by employing any of these methods, characters, figures, and other patterns are formed using colored ink compositions on fabrics such as woven fabrics and nonwoven fabrics. However, in the inkjet recording ink composition of the present invention, since the polyvalent metal content is controlled below a certain concentration as described above, uniform printing is possible. Therefore, a clear and fine pattern can be formed even through the subsequent dyeing process using alkali treatment or heat treatment. On the other hand, when conventional inkjet recording ink compositions are used, they not only cause the above-mentioned equipment problems, but also have poor level dyeing properties, making it difficult to form fine patterns on woven fabrics. Ta. As described above, with the inkjet recording ink composition of the present invention, the ink composition can be deposited on a woven fabric or the like according to the image signal, and the reactive dye in the ink composition in this state is Since the dye is simply attached to the woven fabric, it is preferable to subsequently perform a process of reaction-fixing the dye to the fiber and removing the unfixed dye. Such reactive fixing and unreacted dye removal methods may be conventionally known methods, such as steaming method, HT steaming method, thermofix method, alkaline pad steam method, alkaline blot steam method, alkali shock method, etc. After treatment by a method, an alkali cold fix method, etc., cleaning can be carried out according to a conventionally known method. According to the present invention as described above, there is no need to create expensive printing plates as in conventional general textile printing, and images to be printed can be created and modified extremely easily using a computer. , it is possible to respond to changes in fashion at any time without requiring expensive plates as in the prior art. Therefore, sufficient profits can be secured even with small-scale production without mass production as in the prior art. Further, it has the advantage that it can be applied not only to industrial textile printing methods but also to hobby print printing in ordinary households. Next, the present invention will be explained in more detail with reference to Examples. Note that the numbers in the middle of the sentence and % are based on weight. Example 1 Kayaseron Reactored CN-3B 3 parts Ethylene glycol 15 parts Methyl cellosolve 10 parts N-methyl-2-pyrrolidone 10 parts Water 62 parts All the above components were mixed, and the mixed solution was diluted with acetic acid to pH 4.2.
After stirring for 5 hours, the mixture was filtered using Fluoropore Filter FP-100 (manufactured by Sumitomo Electric Industries, Ltd.) to obtain the aqueous ink (A) of the present invention. Example 2 Reactive dye (CIReactive Red22) 5 parts diethylene glycol 10 parts diethylene glycol methyl ether 25 parts Nonionic surfactant (Nitsukol NP-15,
(manufactured by Nikko Chemicals) 0.05 parts water 6.0 parts A water-based ink (B) of the present invention was obtained in the same manner as in Example 1 except that all the above components were used. Example 3 Reactive dye (CIReactive Blue26) 4 parts Reactive dye (CIReactive Yellow 2) 1 part ethylene glycol 10 parts Polyethylene glycol 200 10 parts Diethylene glycol butyl ether 10 parts N-methyl-2-pyrrolidone 5 parts Water 60 parts All of the above ingredients An aqueous ink (C) of the present invention was obtained in the same manner as in Example 1 except for the following. Example 4 Reactive dye (CIReactive Yellow64) 7 parts ethylene glycol 20 parts diethylene glycol 5 parts N-methyl-2-pyrrolidone 10 parts water 58 parts Using all the above components, the other methods were the same as in Example 1. Aqueous ink (D) of the present invention was obtained. Comparative Example 1 The formulation was the same as in Example 1, but a dye from a different manufacturing lot was used, and a comparative ink (E) was used.
I got it. The properties of each aqueous ink (A to E) of Examples 1 to 4 and Comparative Example 1 are shown in Table 1 below. Usage Example 1 Each water-based ink (A to E) of Examples 1 to 4 and Comparative Example 1 was applied to (1) an inkjet printer ( Nozzle size 40×
(50μ), (2) Equipped with an inkjet printer PJ-1080A (manufactured by Canon, nozzle size 65μφ) that uses piezo elements to continuously print 10 dots on 100% cotton jersey fabric with 10 nozzles. Summer. Further, 100 c.c. of each aqueous ink (A to E) was placed in a glass bottle and stored at 40°C for one week to evaluate the storage stability of the ink. The results are shown below in Part 2.
Shown in the table. Furthermore, water-based inks (A to D) of Examples 1 to 4,
The aqueous ink (E) of Comparative Example 1 was loaded onto an inkjet printer PJ-1080A (manufactured by Canon, nozzle size 65μφ) using a piezo element, and
% dioset fabric, then fixed by steaming for 1 minute at 100°C in an alkaline atmosphere, washed with a neutral detergent, dried, and evaluated for level dyeing. The results are shown in Table 2 below.

[Table] Shows the results.

【table】

Claims (1)

[Scope of Claims] 1. An inkjet printing ink comprising the steps of applying ink to fabrics by an inkjet method, then performing a reaction fixing treatment, and then removing unreacted dye by a washing treatment. Inkjet printing, characterized in that the ink contains a reactive dye and an aqueous medium, and has a polyvalent metal content of 100 ppm or less (however, polyvalent metals in the metal-containing dye are not taken into account). ink. 2 A method of printing by applying ink to fabrics using the inkjet method, which includes a reactive dye and an aqueous medium, and whose polyvalent metal content is 100 ppm or less (however, the content of polyvalent metals in the metallic dye is 100 ppm or less). Polyvalent metals are not taken into account) The ink can be applied to any fabric selected from woven fabrics, non-woven fabrics made of fibers that can be dyed with reactive dyes, blended woven fabrics made of these fibers and other synthetic fibers, and blended non-woven fabrics made of these fibers and other synthetic fibers. An inkjet textile printing method characterized in that the unreacted dye is removed by a washing treatment after being applied to the fabric and then subjected to a reactive dyeing treatment. 3. The inkjet textile printing method according to claim 2, wherein the reaction fixing treatment is a steaming treatment in an alkaline atmosphere. 4. The fabric is cotton, linen, viscose, wool, silk,
and woven fabrics or non-woven fabrics made of any of nylon, or blended woven fabrics made of these fibers and synthetic fibers such as polyester fibers, acetate fibers, polypropylene fibers, vinylon fibers, etc.
The inkjet printing method according to claim 2, which is a blended nonwoven fabric. 5. The inkjet textile printing method according to claim 2, wherein the ink is applied after previously applying a water-soluble or water-dispersible polymer to the surface of the fabric.