JPS61179270A - Ink composition for ink jet recording - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent storage stability and can form uniform and stable prints on woven or nonwoven fabric, consisting of a reactive dye and an aq. medium and having a specified polyvalent metal content. CONSTITUTION:0.1-15wt% reactive dye (e.g. C.I. Reactive Yellow 2) and optionally additives such as dispersant, surfactant, viscosity modifier, resistivity modifier, anti-foaming agent, penetrant, mildewproofing agent, pH adjustor, etc. are dissolved or dispersed in an aq. medium composed of water alone or water and a water-soluble high-boiling org. solvent (e.g. ethylene glycol) to obtain an ink compsn. for ink jet recording, which has a polyvalent metal content of 100ppm or below (excluding the quantity of a polyvalent metal in a metal- contg. dye).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an ink composition for inkjet recording,
In particular, woven or non-woven fabrics made of fibers that can be dyed with reactive dyes, such as cotton, linen, viscose, wool, silk, nylon, etc., or blended woven fabrics or blended non-woven fabrics made of these fibers and other synthetic fibers. The present invention relates to an inkjet recording ink composition suitable for textile printing.

(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 and the like, 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.

(The problem that the invention is trying to solve) However,
Conventional general textile printing methods require the creation of printing plates for printing, and the creation of these plates, such as printing plate cylinders and screen plates, is expensive, and transfer paper is also required for printing in transfer printing. Since the production of plates for this is expensive, it is not cost-effective unless large quantities are produced. Also,
In general, the fashion period for printed cloth patterns is short, so 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, inkjet printing has been proposed, but this inkjet printing causes various problems such as clogging of the ink ejection section of the recording device, and it is not necessarily easy to put it into practical use. Ta. 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 simultaneously solve the economical problems in the conventional general textile printing method as described above, various troubles in the textile printing method using inkjet recording, and the problem of accurate and stable printing. 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 as described below.

(Disclosure of the Invention) That is, 1 the present invention consists of a reactive dye and an aqueous medium, the polyvalent metal content of which is 100 ppm or less (however,
(The polyvalent metal in the metal-containing dye is not considered).

To explain the present invention in more detail, the first feature of the present invention is that a reactive dye is used as a coloring component of the inkjet recording ink composition, and the second feature is that a reactive dye is used as a coloring component of the inkjet recording ink composition. The point is that the polyvalent metal content of the ink composition containing the sexual dye is adjusted to 100 ppm or less.

As a result of various studies on textile printing using the inkjet method, the present inventor has found that the various troubles with the above-mentioned equipment and the storage stability problems of the ink are caused by the presence of alkaline earth metals and other polyvalent metals present in the ink composition. The object of the present invention was mainly achieved by finding out that this is due to the presence of inorganic salts or colloids thereof, and adjusting the content of these polyvalent metals to below a certain concentration.

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 water-soluble groups such as sulfonic acid groups and carboxyl groups in their structures, and #l! Groups that can react with the hydroxyl or amine groups of fibers to form covalent bonds with the fibers, such as dichlortriazine groups, monochlortriazine groups, trichloropyrimidine groups, monochlorodifluoropyrimidine groups, chlorobenzothiazole groups, dichloropyridazone groups , dichloropyridazine group, dichloroquinoxaline group, epoxy group, 3-carboxypyridiniotriazine group, -S O2CH, CH2OS O, Hl
-S O,N HCH2CH2OS O,Hl-N H
COCH,CH,OS 03H1-NHCOCH2CH
2C9-1-N) (COCH= CH2, -S O2C
H= CH2, -CH,N HCoccL=cH2, -
NHCOCBr=CH,, -NHCOCH, (4,, -
It has groups such as NHCHOHl-P O,H.

In the present invention, any of these conventionally known reactive dyes can be used, and preferred reactive dyes in the present invention include C,1, Reactive Yellow 2.3
．． 13.14.15.17.18.23.24.25.
26.27.29, 35, 37, 41, 42, 49,
5 o, 52, 54, 55, 57, 58, 63, 64.
75, 76, 77, 79, 81, 82, 83.84, 8
5, 87, 88, 91, 92, 93.95, 96, 11
1, 115, 116, 131.135, C, 1, Reactive Orange 5.7.10.11.12.13.15
．． 16.2o, 30.34.35, 41, 42, 44.
．． 45°46.56.57.62.63.64.67.
69.71.72.73.74.78.82.84.8
7.C.1.Reactive Trend 3.13.17.1
9.21.22.23.24.29.35.37.40
．． 41.43.45.49.55.56.58.63.
67.8o, 81.82.85.86.87.104.
1゜6.108.109.110.111.112.1
13.114.117.118.119.120.12
3.124.126.128.130.131.132
．． 141.147.1.58.159.170.171
．． 174.176, C, I.

Reactive Violet l, 3.4.5.6.7.8
．． 9.16.17.22.23.24.26.27.3
3, C, 1, Reactive Blue 2.3.5.8.10
．． 13.14.15.17.18.19.21.25.
26.27.28.29.38.39.40.42.4
3.49.51.52.65.66.67.68.71
．． 73.74.75.77.78.79.80.89.
98, Zoo, 101.104.105.112.11
3.114.116.119.147.148.158
．． 160.162.169.170.171.179.
182.187, C, 1, Reactive Green 5.8
．． 12.14.15.16.19.21. C, 1, Reactive Brown 2.5.6.7.8.9.16.17
．． 18.19.21.24.26.30, C6■, Reactive Black 4.5.8.14.21.23.26
．． 31, 32, 34 and various dyes in the Kayaseron React series (Nippon Kayaku ■). If the fiber to be printed is wool or nylon, C, 1, Reactive Yellow 21.34.39.69.98.125
．． 127, C, 1, Reactive Orange 29.53.
68, C, 1, Reactive Red 28.65.66.
78.83.84.100.116.136.147.
154.172, C,I.

Reactive Violet 34, C.1, Reactive Blue 50.69.94.177, C0■, 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 Mixtures with water-soluble organic solvents are preferred, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Carbon e 1-4 alkyl alcohols such as ec-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 gelicol, triethylene glycol, 1.
2. Alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms, such as 6-hexandriol, thiodiglycol, hexylene glycol, diethylene glycol, etc.
・Glycerin; Lower alkyl ethers of polyhydric alcohols such as ethylene glycol methyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether; N-methyl-2-pyrrolidone ,
Examples include 1,3-dimethyl-2-imidazolidinone.

The above-mentioned media can be used alone or as a mixture, but
The most preferred medium composition consists of water and one or more water-soluble organic solvents, where the water-soluble solvent contains at least one water-soluble high-purity organic solvent, such as a polyhydric alcohol such as ethylene glycol, propylene glycol, or glycerin. It contains. The amount of these media used is such that when the ink composition is prepared, the content of the above-mentioned reactive dye is about 0.
The amount is 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, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acids Nonionic dispersants or surfactants such as esters, polyoxyethylene alkyl amines, glycerin fatty acid esters, oxyethylene oxypropylene block copolymer, etc. are important.

As the viscosity modifier, mainly water-soluble natural or synthetic polymers such as carboxymethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, gum arabic, and starch are preferred, and using these viscosity modifiers,
Alternatively, the viscosity of the ink composition of the present invention may be reduced to 2.
The temperature is 50 cps or less, preferably 1-15 cps at 5°C.

Further, in order to prepare ink used in an inkjet recording method of the type in which the ink is charged, a resistivity adjuster such as inorganic salts such as lithium chloride, ammonium chloride, and sodium chloride is added.

Note that when applied to an inkjet system in which ink is ejected by the action of thermal energy, thermal physical property values (eg, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted.

In addition, additives other than the above three types may be used as necessary.
For example, antifoaming agents, penetrants, antifungal agents, pH adjusters, etc. can be added as appropriate.

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 essential components and optional components are blended, the resulting ink composition is 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 purifying the reactive dye by any known method, and by using the medium. This is achieved by using distilled water or deionized water as the water.

Purification methods include conventionally known salting out methods, extraction methods, fractional precipitation methods, methods using ion exchange membranes, ultrafiltration methods,
Suitable methods include 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.

In the inkjet recording ink composition of the present invention,
When the polyvalent metal content is 100 p, pm or more,
This may cause clogging, etc. In addition, the ejection stability of the ink is poor, the storage stability of the ink itself becomes a problem, and the level dyeing of woven fabrics becomes insufficient.However, when the concentration is lower than the above, these various problems suddenly occur. It will be resolved.

The above inkjet recording ink composition of the present invention is
It is useful for printing woven or non-woven fabrics by inkjet printing, especially cotton, linen, viscose, wool, silk,
For printing woven or non-woven fabrics made of fibers that can be dyed with reactive dyes, such as nylon, or mixed woven fabrics or non-woven fabrics made of these fibers and synthetic fibers such as polyester fibers, acetate fibers, polypropylene fibers, vinylon fibers, etc. Useful. 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 ink composition applied 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 effectively removes the ink composition from a nozzle and Any method may be used as long as it can be applied to cloth or nonwoven fabric, and representative methods include, for example, IEEE Tr
ans action industry
Applications Vol, JA-13, N
o, 1 (February/March 1877 issue) and Nikkei Electronics No. 305 (December 6, 1982 issue). The methods described above are suitable for use with the inkjet recording ink composition of the present invention.To explain some of them, there is an electrostatic suction method. A strong electric field is applied between the accelerating electrode placed in front of the nozzle, and the ink particles are drawn out one after another from the nozzle. While the drawn ink composition flies between the deflection electrodes, information signals are given to the deflection electrodes and recorded. There are two methods: a method in which ink particles are ejected in response to an information signal without deflecting the ink particles, and both methods are effective in applying the inkjet recording of the present invention.

The second method is to apply high pressure to the ink with a small pump and mechanically vibrate the nozzle with a crystal oscillator, etc., to forcibly eject minute ink particles, and the ejected ink particles Simultaneously with the injection, the fuel is charged in accordance with 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 droplets, large and small, are produced from the nozzle tip. is generated, and only these medium- and small-diameter 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 nozzle diameter that is conventionally large.

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 disclosed in Japanese Patent Application Laid-open No. 54-5183.
In the method described in Publication No. 7, the ink subjected to the action of thermal energy undergoes a rapid volume change, and the ink is ejected from the nozzle by the action force caused by this state change. suitable,
Shows excellent discharge chamber quality.

Any of the various inkjet recording methods described above can be used, and any of these methods can be used to record woven fabrics,
Patterns such as characters and figures are formed on fabrics such as non-woven fabrics using colored ink compositions, but as described above, the inkjet recording ink composition of the present invention has polyvalent metal content controlled to a certain concentration or less. This makes it possible to print uniformly.

Therefore, a clear and fine pattern can be formed through a 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, the ink composition for inkjet recording of the present invention allows the ink composition to 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 simply Since the dye is merely attached to the woven fabric, it is preferable to subsequently perform a step of reaction-fixing the dye onto 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, alkali pad steam method, alkali blotch 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 an expensive printing plate as in conventional general textile printing, and the image to be printed can be created and modified extremely easily using a computer. It is possible to respond to changes in fashion from time to time without requiring expensive technology. Therefore, sufficient profits can be secured even with small-scale production without mass production as in the prior art. Furthermore, 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 React Red CN-3B 3 parts ethylene glycol 15 parts methyl cellosolve
io part N-methyl-2-pyrrolidone 10 parts water
Mixing the above plenary sessions in 62 parts,
The mixed solution was adjusted to pH 4.2 with acetic acid, stirred for 5 hours, and then filtered using a Fluorobor filter FP-Zoo (manufactured by Sumitomo Electric).
The aqueous ink (A) of the present invention was obtained by filtration.

Example 2 Reactive dye (C,1, Reactive Red 22
) 5-part diethylene glycol
10 parts diethylene glycol methyl ether 25 parts nonionic surfactant (Kkkor NP-15, manufactured by Nikko Chemicals) 0.05 part water

An aqueous ink (B) of the present invention was obtained in the same manner as in Example 1 except that 60 parts of the above-mentioned sample were used.

Example 3 Reactive dye (C,1, Reactive Blue 2B)
4-part reactive dye (C, 1, Reactive Yellow 2)
1 part ethylene glycol 1
0 parts Polyethylene glycol 200 parts 10 parts Diethylene glycol butyl ether 10 parts N-methyl-2-pyrrolidone 5 parts A water-based ink (C) of the present invention was obtained in the same manner as in Example 1 except that all the above components were used.

Example 4 Reactive dye (C, 1, Reactive Yellow 84)
7 parts ethylene glycol
20 parts Diethylene glycol 5 parts N-methyl-2-pyrrolidone 10 parts An aqueous ink (D) of the present invention was obtained in the same manner as in Example 1 except that the above-mentioned product was used.

Comparative Example 1 A comparative ink (E) was obtained using the same formulation as in Example 1, but using a dye with a different production loft.

Each water-based ink (A-E) of Examples 1 to 4 and Comparative Example 1
The properties are shown in Table 1 below.

Usage Example 1 Each water-based ink of Examples 1 to 4 and Comparative Example 1 (A-E)
(1) An inkjet printer using thermal energy according to the method described in JP-A-54-51837 (nozzle size: 4 ox 50 p), (2)
Inkjet printer PJ- that uses piezo elements
108OA (manufactured by Canon, nozzle size 65ILφ)
10 dots were continuously printed on 100% cotton georgette fabric using 10 nozzles. Also, put 100cc of each water-based ink (A-E) into a glass bottle,
The ink was stored at 40'O for one week, and the storage stability of the ink was evaluated. The results are shown in Table 2 below.

In addition, the water-based inks (A-D) of Examples 1 to 4 were applied to an inkjet printer PJ-108 using a piezo element.
A (manufactured by Canon, nozzle size 6511, φ), (1) prints on 100% cotton georgette fabric, then fixes by steaming for 1 minute at 100°C in an alkaline atmosphere, and then After washing with a neutral detergent, clear prints were obtained.

(Margin below) -Negative (-1-J-Kiyo-Length-JL-Kiku Comparative Example)kKfkPikanf Perfectf' dne/cm 45
37 42 57 45 Jodan
4. '2' 4.2 4.
2 4.2 4.2- Kaku Zero 1 ' 7
8 53 80 18 135*I ICP
(The results are shown using an inductively coupled plasma emission spectrometer.

- Angle ffl Yo Real - One Example Comparative Example Prison F Complete FK Pi1 Bi Complete F Book 1 Once Stuck)lJ7Tani■U)000110Py2
Tani name) OOOO8 Book g-Storage stability ooo, o
x*1 10 each with 10 nozzles for each type of printer
Number of nozzles that became clogged when printing dots one after another*2 After storing the ink at 40° C. for one week, it was visually determined whether or not foreign matter was generated in the glass bottle.

0: No foreign matter ×: Foreign matter occurs Procedural amendment (own ship) April 26, 1985

Claims (1)

[Claims] (1) An inkjet recording ink composition comprising a reactive dye and an aqueous medium and having a polyvalent metal content of 100 ppm or less (however, polyvalent metals in the metal-containing dye are not taken into account) thing.