JPS61266470A - Ink composition for ink jet recording - Google Patents

Abstract

PURPOSE:To obtain the titled compsn. capable of being uniformly incorporated and eliminating the need for use of an expensive printing plate and suitable for use in printing for mixed (non)woven fabric etc., by dispersing a reactive disperse dye in a medium. CONSTITUTION:Reactive disperse dyes of the formula I-IV, etc. such as azo dye, anthraquinone dye, etc., which are difficultly water-soluble is ground into a power having a particle diameter of 30mu or less. The powder is dispersed in a medium comprising water or a medium comprising a mixture of water with a water-soluble org. solvent (e.g.: ethyl alcohol) optionally containing a water-soluble high b.p. org. solvent (e.g.: ethylene glycol), if necessary, using a dispersant or a surface active agent (e.g.: alkylbenzenesulfonate), a viscosity modifier (e.g.: CMC), etc. so as to have a powder content of 0.1-15wt% of an medium to thereby obtain the titled compsn. having a viscosity of 50cP or less (25 deg.C).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an ink composition for inkjet recording,
Particularly suitable for printing mixed woven fabrics or blended non-woven fabrics made of easily dyeable reactive fibers such as cotton, hemp, viscose, wool, silk, nylon, etc. and difficult-to-dye non-reactive fibers such as polyester and acetate. The present invention relates to an ink composition suitable for inkjet recording.

(Prior Art) Conventionally, blended woven fabrics, etc., are made of easily dyeable reactive fibers such as cotton, hemp, viscose, wool, silk, nylon, etc., and difficult-to-dye non-reactive fibers such as polyester and acetate. For printing, printing methods such as roller printing, screen printing, and transfer printing using a blend of reactive dyes (or thren dyes) and disperse dyes are used, and some printing methods include printing methods using inkjet recording methods. has 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. The production of plates for this is expensive, so it is not cost-effective unless a large quantity is produced, and
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, an inkjet printing method has been proposed, but in this inkjet printing method, the blended disperse dye and water-soluble dye do not mix uniformly in the ink, especially in the ink ejected from the nozzle. However, since the mixing ratio of the two is not always constant, there is a problem in that there are differences in shading in some areas during the dyeing process after printing, making it impossible to obtain uniformly dyed products, and it is not always easy to put it into practical use. Ta.

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, the present invention is an ink composition for inkjet recording characterized by comprising a reactive dispersion dye and a medium.

To explain the present invention in more detail, the first feature that characterizes the present invention is that a reactive dispersion type dye is used as a coloring component of an ink composition for inkjet recording.

As a result of various studies on textile printing using the inkjet method, the present inventor has found that the above-mentioned drawbacks include, firstly, the inability to maintain a uniform blend of disperse dyes and water-soluble dyes in the ink; Knowing that when passing through a nozzle, the uniform blending properties of these dyes are further reduced, we have developed dyes that dye the different fibers that make up the blended fabric at the same time, i.e., reactive dispersion dyes, instead of these blended dyes. The objects of the present invention have been primarily achieved by employing type dyes.

The reactive dispersion dye that mainly characterizes the present invention and is used in the present invention is a material that is known per se, and is a water-soluble 7 These are zo-based, anthraquinone-based, and other dyes. This) Herera's reactive disperse dyes have a molecular weight within a certain range, do not have water-soluble groups such as sulfonic acid groups or carboxyl groups in their structure, and do not react with the hydroxyl or amino groups of fibers. Groups that can form covalent bonds with fibers, such as ethyleneimine groups, azide groups, sulfoneethyleneimine groups, dichlorotriazine groups, monochlorotriazine groups, trichloropyrimidine groups, monochlorodifluoropyrimidine groups, chlorobenzothiazole groups, dichlor Pyridazone group, dichloropyridazine group, dichloroquinoxaline group, epoxy group, 3-carboxypyridiniotriazine group, -S O20H, CH2OS O, Hl-3O, N 1
(CI(2CH2OS O,)I, -N HCOCH2
CHρSo, Hl -NHCOCH,CH2Cl, -N HCOCH= CH,, -S O20H= CH2゜-CH, NHCOCC1=CH2, -NHCOCBr=CH,, -N)ICOCH2C1, -N HCH2OHl-P O,H.

-S O, CH, CH, OCOCH3, -S O20H
It has groups such as 2CH, OCOOC4H, etc.

In the present invention, any of these conventionally known reaction-dispersion dyes can be used, and the preferred reaction-dispersion dye in the present invention is LIUH.

Dyes and derivatives thereof having the following structures are suitable.

In the present invention, any of the media used in conventional general dyeing and the media used in conventional inkjet recording inks can be used as the medium for dispersing the above-mentioned reactive dispersion dye. Alternatively, a mixture of water and a water-soluble organic solvent is preferable, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol. Amides such as dimethylpolamide and dimethylacetamide; Ketone or keto alcohols such as acetone and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Polymers such as polyethylene glycol and polypropylene glycol Alkylene glycols: ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexandriol, thiodiglycol, hexylene glycol, diethylene glycol, etc., where the fullylene group has 2 to 6 carbon atoms Alkylene glycols containing atoms: 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- Examples include 2-pyrrolidone and 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-boiling 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 reactive dispersion type dye is about 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.

Ah, yes, Aika. , 6 Dispersant Ah, I, Yo Kai Tsuo
As the sexing agent, fatty acid salts, alkyl sulfate ester salts,
Anionic dispersants or surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfate ester salts; polyoxyethylene Nonionic dispersants such as alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxypropylene block polymer, etc. Alternatively, surfactants 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.
5°cps or less, preferably 1-15cps 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 thermal properties (eg, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted for materials used in inkjet systems in which ink is ejected by the action of thermal energy.

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

The ink composition for inkjet recording of the present invention can be obtained by mixing the above-mentioned essential components and optional components and subjecting the mixture to a grinding process using conventionally known grinding means such as a ball mill, sand mill, speed line mill, etc. This is common, and the particle size of the disperse dye is usually 30 pm or less, preferably 20 ILm or less. If the particle size is too large, problems such as nozzle clogging may occur during inkjet recording.
Problems arise with level dyeing in the subsequent dyeing process.

Furthermore, when a medium that dissolves the reactively dispersed dye is selected as the medium, the ink composition of the present invention can be obtained only by the dissolving action of heating.

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,
Blended woven fabrics or blended non-woven fabrics consisting of reactive fibers that can be dyed with reactive dyes, such as nylon, and non-reactive fibers that can be dyed with disperse dyes, such as polyester fibers, acetate fibers, polypropylene Iara, vinylon fibers, etc. Useful for textile printing. 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 fabrics, nonwoven fabrics, or articles is such that the ink composition is effectively removed from a nozzle and a projectile is used. Any method may be used as long as it can be applied to woven or non-woven fabrics, and representative methods include, for example, IEEE Tr
ans action industry
Ap, plications Vol, JA-13,
No. 1 (February/March 1977 issue) and Nikkei Electronics 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 an electrostatic suction method.In this method, the number of nozzles is 1. A strong electric field is applied between the accelerating electrode placed in front of the layer, and the ink is made into particles and drawn out one after another from the nozzle, and the drawn ink composition flies between the deflection electrodes.In the meantime, an information signal is sent to the deflection electrode. 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 ink composition for inkjet recording of the present invention.

The second method is to forcibly eject minute ink particles by applying high pressure to the inlet with a small pump and mechanically vibrating the nozzle with a crystal oscillator. 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 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 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.

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 the inkjet recording ink composition of the present invention is not a mixture of a disperse dye and a water-soluble dye as in the past, but a single dye. Since it consists of a single component dye, the liquid composition of the ink is always constant and uniform printing is possible.

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 dispersion type dye in the ink composition in this state is Since the dye is merely attached to the woven fabric, it is preferable to subsequently perform a step of reactively fixing the dye to the fiber and removing the unfixed dye. Conventionally known methods may be used, such as steaming method, HT steaming method,
After treatment by a thermofix method, an alkali pad steam method, an alkali blotch steam method, an alkali shock 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 Dye of the structural formula (2) 5 parts Anionic surfactant (dispersant) (Demol N, manufactured by Chemical Soap ■) 4 parts;
1 ethylene glycol 15 parts diethylene glycol 13 parts water
65 parts After dispersing all the above ingredients in an alumina ball mill for about 36 hours, the pH was adjusted to 4.7 with acetic acid, and flJ1 dispersion was further performed for 3 hours in an alumina ball mill, and then the fluorobore filter FP-1000 (manufactured by Sumitomo Electric)
Coarse particles with a particle size of 10 ILm or more were removed to obtain an aqueous ink (A) of the present invention.

Example 2 Dye of the structural formula (7) 4 parts anionic surfactant and 0.05 parts anionic surfactant (Kokkor 0TP-100s, manufactured by Nikko Chemicals) 1. 5 parts nonionic surfactant (Emulgen 981, manufactured by Kako Soap ■)
0.2 parts 1so-propyl alcohol 0.5 parts propylene glycol
15 parts polyethylene glycol 400 5
fi water
75 parts After dispersing all the above ingredients in an alumina ball mill for about 40 hours, the pH was adjusted to 5.6 with acetic acid.
After further dispersing for 2 hours, the particle size was adjusted to 5 g, m using Fluorobor Filter FP-500 (manufactured by Sumitomo Electric)
By removing the above coarse particles, the aqueous ink CB' of the present invention
) was obtained.

Example 3 7 parts of the dye of the structural formula (14) 2 parts of the dye of the structural formula (15) Nonionic surfactant (Emulgen 707, manufactured by Chemical Soap ■)
1.5 parts nonionic surfactant (Rheodol T
W-P120, manufactured by Kako Soap Co., Ltd.) 2.0 parts Ethylcarpitol 20 parts Water
A water-based ink (C) of the present invention was obtained from 70 copies of the above assembly in the same manner as in Example 2.

Example 4 Dye of the structural formula (9) 6 parts anionic surfactant (Ionet D-2, manufactured by Sanyo Chemical Industries, Ltd.)
5.5 parts ethylene glycol
25 parts glycerin
5 parts 1,3-dimethylimidazolidinone 5 parts water

Aqueous ink (D) of the present invention was obtained from 60 copies of the above assembly in the same manner as in Example 1.

Comparative Example 1 In place of the reactive dispersion dye in Example 1, a comparative ink (E
) was obtained.

Comparative Example 2 In place of the reactive dispersion dye in Example 2, 542 parts of C0■, Disbirds Red and Active Red 222 were added.
Comparative ink C was prepared in the same manner as in Example 2.
F) was obtained.

The properties of the inks of Examples and Comparative Examples are shown in Table 1 below.

Usage Example 1 Each water-based ink (A
-The ink of F) was loaded onto an inkjet printer using thermal energy according to the method described in JP-A No. 54-51837, printed on various blended fabrics, and then heat-treated at 180°C for 90 seconds. did. Further, dyeing was carried out by treatment at 90°C for 20 seconds in an alkaline bath prepared with sodium carbonate and potassium chloride.

A print was obtained by washing with a neutral detergent. The results are shown in Table 2.

(Margin below)! ``Testimony 2L'' 42 IJLI Upper JJI Prison f4C and r 4. , yr 1 もf etc.f book 1 1
The results of analysis using CPCMIa combined plasma emission myum are shown.

-1≧1” 3-Rokumin Ippon 1 Kai 2 Ll! 1 ”MuJ Botate 2 Ink (
A) 80% polyester, IIEα (pro
〇 〇Ink (B) Polyester 85
View cotton part 1 blow)) o Oi 7ri (C)
Pol) x Stell 50L + II [c blow))
OO ink (D) Polyester 85$, 65% (
Broad) 0 0 Main JLJ Ink (E) 85% polyester, The (Broad) XX Ink CF) Polyester 6! a. Cotton 5
z (Broad) 0 x Book 1 Visually judge the sharpness of the thin line (width approx. 11) on the print. Pond 0: Good I (asahi 0: good, ×: poor)

Claims (1)

[Claims] (1) An ink composition for inkjet recording characterized by comprising a reactive dispersion dye and a medium.