JPS61266686A - Printing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a textile printing method using an inkjet recording method, and in particular, to printing easily dyeable reactive fibers such as cotton, linen, viscose, wool, silk, nylon, etc. The present invention also relates to a printing method using an inkjet recording method suitable for printing blended woven fabrics or blended nonwoven fabrics made of non-reactive fibers that are difficult to dye, such as polyester or acetate.

(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. 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 of printed cloth patterns is short, so making plates each time increases the cost, and there is a serious problem 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 was also proposed, but in this inkjet printing, the blended disperse dye and water-soluble dye do not mix uniformly in the ink, especially when the ink is ejected from the nozzle. Inside, the mixing ratio of the two is not always constant, so in the dyeing process after printing, there are local differences in shading and it is not possible to obtain a uniformly dyed product, which makes it difficult to put it into practical use. There wasn't.

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 a textile printing method using an inkjet recording method.

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 provides a textile printing method in which a recording liquid containing a dye is applied to a fabric by an inkjet method, and then a dyeing process is performed, wherein the dye is a reactive dispersion dye. It's a method.

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

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 poorly water-soluble azo dye that is used in conventional printing of polyester/cotton blend fabrics. , anthraquinone and other dyes. These reactive disperse dyes have a molecular weight within a certain range, have water-soluble groups such as sulfonic acid groups and carboxyl groups in their structure, and react with the hydroxyl or amino groups of the fibers to form a shared bond with the fibers. Groups capable of forming a bond, such as an ethyleneimine group, an azide group, a sulfone ethyleneimide group, a dichlorotriazine group, a monochlorotriazine group, a trichlorpyrimidine group, a monochlorodifluoropyrimidine group, a chlorobenzothiazole group, a dichloropyridazone group, Dichloropyridazine group, dichloroquinoxaline group, epoxy group, 3-carboxypyridiniotriazine group, -502CH2CH2OS O,H5 -SO□N HCH2CH,OS O, Hl-N HC
OCH, CH2OS O, Hl-N HCOC) I, C
H2CI, -NHCOCH=CH,.

-S O,CH= CH,, -CH,NHCOCCl =CH,, -NHCOCB r = CH,, -NHCOC)
12CI, -NHCH,OHl -PO,H5 -SO,CH,CH,OCOCH,, -SO,CH
, CH, OCOOC, H, etc.

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

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, such as water or water. and a water-soluble organic solvent, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ec-butyl alcohol, tart-butyl alcohol, isobutyl alcohol, etc. Number 1 to 4 alkyl alcohols; amides such as dimethylformamide and dimethylacetamide; ketone or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol ; Ethylene glycol, propylene glycol, butylene glycol, 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; 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.

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.

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, polydecoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, vine-bitan fatty acid esters, polyoxyethylene Seven-ion type dispersants or surfactants such as 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 carboxymethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, gum arabic, and starch are preferred, and using these viscosity modifiers,
Alternatively, the viscosity of the ink composition used in the present invention is set to 50 cpg or less at 25°C, preferably 1 to 15 cpg without using it.
cps.

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

Furthermore, when a medium that dissolves the reactive dispersion type dye is selected as the medium, the ink composition of the present invention can be obtained only by the dissolving action of heating and stopping.

The above ink composition for inkjet recording used in the present invention is useful for printing woven or nonwoven fabrics by inkjet recording, and is particularly useful for printing with reactive dyes such as cotton, linen, viscose, wool, silk, nylon, etc. It is useful for printing mixed woven fabrics or blended nonwoven fabrics made of reactive fibers that can be dyed with disperse dyes and non-reactive fibers that can be dyed with disperse dyes, such as polyester fibers, acetate fibers, polypropylene fibers, vinylon fibers, etc. 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 method of the present invention is to apply the ink composition for inkjet recording as described above to the woven fabric, nonwoven fabric or molded article as described above, and the inkjet recording method used in the method of the present invention is to apply the ink composition □ through a nozzle Any method may be used as long as it can be effectively separated and applied to the woven or non-woven fabric that is the projectile, and a typical example of such methods is 1, for example, IEEE Trans.
actions on Industry App
lications Vol, JA-13, No. 1 (
February/March 1977 issue), Nikkei Electronics No. 30
No. 5 (December 6, 1982 issue).

The methods described above are suitable for the method of the present invention.To explain some of them, there is an electrostatic attraction method.In this method, the number of nozzles and the number of nozzles. A method in which a strong electric field is applied between the ink and the ink, the ink is drawn out one after another from a nozzle, and an information signal is applied to the deflection electrodes while the drawn ink composition flies between the deflection electrodes to record the ink. There is a method of ejecting ink particles in response to an information signal without deflecting the particles, and either method is effective for the method 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, large and small, are sprayed 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 nozzle diameter that is larger than conventional methods.

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 method of the present invention is a method described in Japanese Patent Application Laid-Open No. 54-51837, in which the ink subjected to the action of thermal energy undergoes a rapid volume change, and the acting force due to this state change causes the ink to An inkjet method in which the ink is ejected from a nozzle is also suitable.

Any of the various inkjet recording methods described above can be used in the present invention, and any of these methods can be used to print characters, figures, and other patterns using colored ink compositions on fabrics such as woven fabrics and nonwoven fabrics. However, the inkjet recording ink composition used in the present invention is not a mixture of a disperse dye and a water-soluble dye as in the past, but is made of a single component dye, so the liquid composition of the ink is always constant. Yes, 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.

By the method of the present invention as described above, the ink composition can be deposited on a woven fabric etc. according to the image signal, and the reactive dispersion type dye in the ink composition in this state is simply deposited on the woven fabric. Therefore, 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, H
After treatment by T-steaming method, thermofix method, alkali pad steam method, alkali blotch steam method, alkali shock method, alkali cold fix method, etc., cleaning can be carried out according to conventionally known methods.

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 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. 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 (Ink production example) Dye of structural formula (2) 5 parts Anionic surfactant (dispersant) (Demol N, manufactured by Kao Soap ■) 4 parts Ethylene glycol 15 parts Diethylene glycol 13 parts Water
After dispersing the above 65 parts in an alumina ball mill for about 36 hours, the pH was adjusted to 4.7 with acetic acid, and further dispersion was carried out in an alumina ball mill for 3 hours, followed by a Fluorobor filter FP. -1000 (manufactured by Sumitomo Electric) with particle size of 10I
Coarse particles larger than Lm were removed to obtain an aqueous ink (A) used in the present invention.

Example 2 (Ink production example) Dye of the above structural formula (7) 4 parts anionic surfactant and 0.05 parts anionic surfactant (Demol C7 manufactured by Kao Soap ■, Nikko Chemicals Co., Ltd.) ) 1.5 parts nonionic surfactant (Emulgen 981, manufactured by Kao Soap ■)
0.2 parts 1so-propyl alcohol 0.5 parts propylene glycol
15 parts polyethylene glycol 400 5
Department water
After dispersing the above 75 parts 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 5 g, m using Fluorobor Filter FF-500 (manufactured by Sumitomo Electric ■).
The above coarse particles were removed to obtain the aqueous ink (B) used in the present invention.

Example 3 (Ink production example) 7 parts dye of the above structural formula (14) 2 parts dye of the above structural formula (15) Nonionic surfactant (Emulgen 707, manufactured by Kao Soap ■)
1.5 parts nonionic surfactant (Rheodol T
V-P120, manufactured by Kao Soap ■) 2.0 parts ethyl calpitol 20 parts water
7 parts One aqueous ink (C) used in the present invention was obtained from all the above components in the same manner as in Example 2.

Example 4 (Ink production example) Dye of the above structural formula (9) 6-part 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
60 parts From all the above ingredients, 1 was prepared in the same manner as in Example 1.
Aqueous ink (D) used in the present invention was obtained.

Comparative Example 1 (Ink Production Example) In place of the reactive dispersion dye in Example 1, C1■, 33 parts of Disperse Blue and 492 parts of Active Blue were used. E
) was obtained.

Comparative Example 2 (Ink Production Example) In place of the reactive dispersed dye in Example 2, 542 parts of C1■, Disbirds Red and Active Red 222 were used.
A comparative ink (
F) was obtained.

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

Example 5 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. Furthermore, dyeing was carried out by treatment at 90°C for 20 seconds in an alkaline bath prepared with sodium carbonate and potassium chloride, and then
A print was obtained by washing with a neutral detergent. The results are shown in Table 2.

1 fan r,
82" 4.2 4.2 4.2 4.2
4.2 4.2 Wood L 78 53 8
0 18 80 82 Tree I ICPI
The results of analysis using jA conductive coupled plasma emission spectrometry m are shown.

-35 ko-lk Niki l Ki 2 夾" L A average - 11-j L Okagen 1 k Otsushima ink (A) 100% cotton (Shi! -Se-/T)
OO ink (B) Polyester 85L m5X (Blow 1') o O ink (C) Polyester 50%, klnO% cb0-1-') o.

Ink (D) 100% wool (7 evenings)
OO ratio - bite example ink (E) cotton toot <Georgette)
X X4 Link (F)
11100% (di, -zet) O
X Tree 1 The sharpness of the thin line (width approximately 1 m) of the print was visually determined.

0: Good ×: Bad Tree 2 Dots were lined up in a row at about 1n intervals and printed at 30 cm, and the dispersion of the dots was visually determined.

0: Good ×: Bad Patent applicant: Canon Co., Ltd. (Issuance of procedural amendment) March lr, 1986

Claims (2)

[Claims] (1) A textile printing method in which a recording liquid containing a dye is applied to a fabric by an inkjet method and then dyed, the textile printing method being characterized in that the dye is a reactive dispersion dye. (2) The method according to claim (1), wherein the fabric is a blended woven fabric or blended nonwoven fabric of reactive fibers and non-reactive fibers.