JPH0699872B2 - INKJET DETECTION INK AND INKJET DETECTION METHOD - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dye-proof ink useful for a dye-proof method by an ink jet recording method, and a color dye-proof which is useful for a color dye-proof method for coloring at the same time as the dye-proof. Regarding ink.

(Prior art) Conventionally, a so-called dye-proofing method in which a fabric or an under-treated cloth is printed with a dye-proofing paste, and then dyed, and a dye that does not prevent dyeing on the fabric is added to the paste At the same time, a coloring / resisting method for dyeing the stain-proof part is widely used.

(Problems to be Solved by the Invention) However, conventional general dye-resisting (including color-resisting)
The method is that it is necessary to make a printing plate for dye-proof, and it is expensive to make these plates, for example, a dye-proof plate cylinder or a screen plate, and the cost is not suitable unless a considerable amount is produced. There is. In addition, since the period of fashion of the printed fabric is generally short, the cost of plate making each time is further increased, and it is not possible to quickly respond to these fashions, and there is a serious problem that a large amount of inventory may be held.

Further, since the dye-proof paste used in the conventional dye-proofing method needs to be in the form of a paste having a very high degree of paste in order to be compatible with various dye-proofing machines, various water-soluble binders, various fillers, etc. Therefore, the edges of the dye-proof part are not sharply dyed, and the dye-proof pattern lacks accuracy.
There has been a problem that many complicated post-treatments are required to remove these subcomponents after the dyeing prevention.

As a method for solving such a problem, a color-preventing discharge printing method by an ink jet method has been proposed (Japanese Patent Laid-Open No. Sho 61-135).
61-6365). According to this method, an ink containing a reducing agent and an ink containing a non-reducing decomposable dye are separately applied to a colored cloth at the same place to perform a color preventive discharge printing. Although this method solves the above-mentioned problems to some extent, the reducing ink and the dye ink are accurately combined with each other in that the cloth has elasticity due to moisture and the ink dots formed by the inkjet method are minute. It is difficult to apply it to the same place of the cloth, and therefore, there is a drawback that spots and color unevenness are likely to occur in the protective pattern.

Further, even when the ink dots exactly overlap at the same point, a problem of ink bleeding newly occurs due to the increase in the ink amount due to the overlap.

Therefore, an object of the present invention is to provide a dye-proof ink useful for an ink jet method, which can simultaneously solve the economical problem in the conventional general dye-proof method as described above and the problem that an accurate print cannot be obtained. That is.

Such and other objects of the present invention are achieved by the present invention described below.

DISCLOSURE OF THE INVENTION That is, the present invention is an ink-jet dye-proof ink characterized by containing a dye-proofing agent selected from an organic acid and an oxidizing agent, water, and optionally an organic solvent, and a fabric for the ink. For the process of applying by an inkjet method,
And an inkjet dye-proofing method, which comprises a step of dyeing the cloth to which the ink is applied.

Explaining the present invention in more detail, the dye-proof ink of the present invention is replaced with various printing methods in the conventional dye-proof method,
When the inkjet recording method is adopted, it can be used in place of the conventional dye-proof paste.

The dye-proof ink of the present invention is mainly composed of a solution of a dye-proof agent selected from an organic acid and an oxidizing agent, to which ink jet recording suitability is imparted.

Examples of the dye-proofing agent used in the present invention include organic acids such as citric acid, tartaric acid, oxalic acid, and glycolic acid,
And sodium m-nitrobenzenesulfonate, o- or p
Examples thereof include sodium nitrotoluene sulfonate, salts of m-nitrobenzene sulfonic acid such as calcium and zinc, and oxidizing agents such as m-nitroanthracene sulfonic acid.

Those compounds can be easily obtained from the market by those skilled in the art, and can be appropriately selected and used depending on the type of the cloth to be dyed, the presence or absence of the submersion agent, and the type.

The ink for ink-jet dye-resisting ink of the present invention is used by dissolving or dispersing the above-described dye-resisting agent in a medium at a concentration of about 0.1 to 30% by weight. As the medium for the ink, water alone, preferably a mixed liquid of water and an organic solvent, is used. Examples of the organic solvent used include alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and isobutyl alcohol. Amides such as dimethylformamide and dimethylacetamide; ketones 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 and propylene glycol , Butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol Alkylene glycols containing an alkylene group of 2 to 6 carbon atoms; glycerin, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl)
Lower monoalkyl ethers of polyhydric alcohols such as ether and triethylene glycol monomethyl (or ethyl) ether; lower dialkyl of polyhydric alcohols such as triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether Ethers; N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned.

The above media can be used alone or as a mixture,
The most preferable medium composition is water and at least one organic solvent, and the solvent contains at least one water-soluble high-boiling point organic solvent, for example, a polyhydric alcohol such as ethylene glycol, propylene glycol or glycerin. is there.

The essential components of the ink of the present invention are as described above, but other conventionally known various dispersants, surfactants, viscosity modifiers,
A surface tension adjusting agent, a fluorescent whitening agent and the like can be added as necessary.

For example, viscosity adjusting agents such as polyvinyl alcohol, celluloses and water-soluble resins; surface tension adjusting agents such as cationic, anionic or nonionic surfactants, diethanolamine and triethanolamines; pH by buffer solution
Examples thereof include regulators and fungicides.

Further, in order to prepare a dye-proof ink used in an ink jet recording method of charging the ink, a specific resistance adjusting agent such as lithium chloride, ammonium chloride, or an inorganic salt of sodium chloride is added. When applied to an ink jet method of a type in which the dye-proof ink is ejected by the action of thermal energy, thermal physical property values (for example, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted. .

The dye-proof ink of the present invention as described above has a viscosity of about 30.
By adjusting the surface tension to cps or less and the surface tension in the range of about 35 to 65 dyne / cm (each is 25 ° C.), the most excellent inkjet suitability can be obtained.

The dye-proof ink of the present invention basically comprises the components and properties as described above, and is applied in a pattern to a cloth such as a woven cloth or a dipped-treated cloth by the inkjet recording method as described above, and then dyed. It is useful for forming various blank patterns by the process and post-treatment.

In another embodiment of the present invention, a dye or pigment that is not affected by the dye-proofing agent in the ink is dissolved or dispersed in the white dye-proofing ink shown above to dye-proof the fabric. At the same time, there is provided a dye-proof ink useful for coloring and dyeing, which dyes the dye-proof part in another hue.

Examples of such dye-proof dyes include dye-proof basic dyes that are well known in the conventional color dye-proof technology.
Select from direct dyes, acid dyes, reactive dyes, reactive dispersion dyes, disperse dyes, vat dyes, soluble vat dyes, sulfur dyes, mordant dyes, oxidative dyes, various pigments, etc. according to the type of fabric. Good.

Such a stain-proofing agent-resistant dye can be made into a color-resisting ink by dissolving or dispersing it in the stain-proofing ink of the present invention at a concentration of about 0.1 to 15% by weight.

When the ink of the present invention is a colored dye-proof ink, it is a one-component type, unlike the conventional two-component type color dye-proof, and in the case of this one-component type, the ink used is dye-proofed. Since the agent and the dye or pigment are used in combination, the stability of the ink is particularly important, and in order to improve such stability, the pH of the ink according to the dye or pigment used,
It is preferable to appropriately control various physical properties such as viscosity, surface tension, and concentration. The control of these various physical properties is not uniform depending on the dyestuff to be used, the dye and other ink components, etc., but depending on the type of the components to be used by the various compounds shown in the ink used for white dyestuff, Each time, it may be determined experimentally by finding a factor that enhances stability.

The dye-proof ink of the present invention is suitable for imparting a one-liquid pattern to a cloth or a submersion-treated cloth as described below by an inkjet recording method as described below to perform white-colored or color-proofed dyeing. Such fabrics to which the anti-ink ink of the present invention is applied include natural fibers such as cotton, wool, silk and hemp, regenerated fibers such as cupra and rayon, acrylic, nylon, polyester, vinylon, polypropylene and acetate rayon. A woven or non-woven fabric made of the above synthetic fiber, or a woven or non-woven fabric made from the above-mentioned fibers.

In addition, the under-pickling cloth is an under-pickling cloth made of an alkaline aqueous solution of naphthol AS used for anti-dyeing with a naphthol dye, or an aqueous solution of an acid and a base for efficiently performing anti-dyeing.

As the dye for dyeing the fabric and the under-dip-treated cloth dye-proofed as described above, a basic dye excellent in dye-proof property, which is well known in the conventional dye-proof and coloring dye-proof techniques,
Direct dyes, acid dyes, reactive dyes, reactive dispersion dyes, disperse dyes, vat dyes, soluble vat dyes, sulfur dyes, mordant dyes, oxidative dyes, naphthol dyes, various pigments, etc. According to the above-mentioned method, the cloth may be selected and used, and the dye-proofed cloth may be dyed according to the conventional technique.

The ink jet recording method in which the anti-dye ink of the present invention is applied in a pattern to one of the above-mentioned subbed-treated cloths as a pattern is defined as the ink is effectively separated from the nozzles, and ink is applied to the cloth as a range. Any method may be used as long as it can provide the above-mentioned method. Typical examples of those methods are, for example, IEE Trans Actions on Industry Applications (IEEE Transa
stions on Industry Applications) Vol.IA-13, No.1
(February and March, 1977), Nikkei Electronics April 19, 1976, January 29, 1973 and May 6, 1974. The methods described in these are suitable for the dye-proofing method of the present invention, and some of them will be described as follows.
First, there is an electrostatic suction method.In this method, a strong electric field is applied between the nozzle and an accelerating electrode placed a few mm in front of the nozzle, the ink is made into particles from the nozzle and drawn out one after another, and the drawn ink is deflected. There are a method of recording an information signal by applying it to a deflection electrode while flying between electrodes, and a method of ejecting ink particles corresponding to an information signal without deflecting ink particles. Effective for dyeing method.

The second method is to apply high pressure to the ink with a small pump,
This is a method in which minute ink particles are forcibly ejected by mechanically vibrating the nozzle with a crystal oscillator or the like, and the ejected ink particles are charged at the same time as the ejection according to an information signal. When the charged ink particles pass between the deflection electrode plates, they are deflected according to the charge amount. As another method using this method, there is also a method called a micro dot inkjet method. In this method, ink pressure and excitation conditions are maintained at appropriate values within a certain range, and two types of ink droplets, large and small, are ejected from the nozzle tip. It is generated, and only the medium and small diameter droplets are used for recording. The feature of this method is that a minute droplet group can be obtained even with a nozzle diameter as thick as the conventional one.

A third method is a piezo element method. In this method, a piezo element is used as a pressure means to be applied to ink, instead of a mechanical means such as a pump unlike other methods. In this method, an electric signal is applied to the piezo element to cause mechanical displacement, thereby applying pressure to the ink and ejecting it from the nozzle.

Further, in the method described in Japanese Patent Application Laid-Open No. 54-59936, 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 due to this state change. Can also be used effectively.

By the inkjet method as described above, the dye-resisting ink of the present invention or the one-pack type color dye-resisting ink is applied in a pattern on a cloth or a submersion-treated cloth, and then dried if necessary, and further subjected to ordinary dyeing. When this is done, dyeing of the part where the ink applied in a pattern is present is prevented, and only the part where no ink is present is dyed. Further, in the case of color resisting, at the same time, the dye resistant pigment or pigment contained in the ink is dyed on the dye protected portion to form a pattern of another hue. By subsequently continuing ordinary post-treatments such as washing with water, washing with hot water, soaping, etc., the dyes that have not been dyed on the fibers or their decomposed products are removed, and whitening prevention and coloring prevention are achieved.

According to the present invention as described above, the anti-dyeing ink is applied in a pattern on the cloth or the under-pickled cloth by the ink jet recording method, then dried as required, and further subjected to a normal dyeing treatment to be applied in a pattern. Dyeing of the portion where the ink is present is prevented and only the portion where the ink is absent is dyed. Further, in the case of color resisting, at the same time, the dye resistant pigment or dye contained in the ink is dyed on the dye protected portion, and a pattern of another hue is formed. By subsequently continuing ordinary post-treatments such as washing with water, washing with hot water, soaping, etc., the dyes that have not been dyed on the fibers or their decomposed products are removed, and whitening prevention and coloring prevention are achieved.

According to the present invention as described above, a stain-proofing agent is used as a solution and as a stain-proofing ink imparted with inkjet recording suitability, and such an ink is applied to a cloth or an under-pickled cloth by an inkjet method to prevent whitening prevention. Dyeing or coloring dye-proofing is unnecessary, so it is not necessary to create expensive printing plates and the like as in conventional dye-proofing methods, and various images can be easily and arbitrarily created by a computer connected to an inkjet recording device, Since the image can be used immediately for resist printing, it is possible to always follow the short fashion period of the pattern on the print cloth, and the cost can be matched even if it is not necessarily mass-produced.

Further, unlike the conventional method, it is not necessary to use a high-viscosity stain-proofing paste or a two-component type ink, so various problems based on these high-viscosity stain-proofing paste or a two-component type ink,
In particular, there is no problem that unevenness in the formed pattern, unnecessary spots, bleeding, and the like occur.

Next, the present invention will be described more specifically with reference to examples. In the text, parts or% are based on weight unless otherwise specified.

Example 1 Tartaric acid 5 parts Diethylene glycol 30 parts Water 70 parts After stirring all the above components for 3 hours, a fluoropore filter EP-
The dye-proof ink (A) of the present invention was obtained by filtering with 100 (trade name) (Sumitomo Electric Co., Ltd.).

Comparative Example 1 Sodium hydrosulfite 8 parts (trade name: Hydrosulfite R Conc, manufactured by Ciba Geigy) Polyethylene glycol (molecular weight 1,000) 20 parts Nonionic surfactant 0.2 part (trade name: Emulgen PP-150, manufactured by Kao) Water 80 Parts All the above components were treated in the same manner as in Example 1 to obtain a dye-proof ink (B) for comparison.

Example 2 Sodium m-nitrobenzene sulfonate 10 parts Ethylene glycol 30 parts Zinc sulfate 5 parts Water 55 parts The above all components were treated in the same manner as in Example 1 to obtain a dye-proof ink (C) of the present invention.

Example 3 Direct dye (trade name; Kayacelon) for all components in Example 1
Dark Blue C-BK, made by Nippon Kayaku)
The same treatment as in Example 1 was carried out to obtain the colored dye-resisting ink (D) of the present invention.

In addition, each ink (A to
The properties of D) are shown in Table 1 below.

Examples 4 to 7 and Comparative Example 2 The dye-proof inks (A to D) were used in (1) an ink jet printer (former) utilizing heat energy (nozzle diameter 40).
X 50 μm) and (2) Inkjet printer (Otsu) PJ-1080A (manufactured by Canon Inc., nozzle diameter 65 μmφ) using piezo element is installed, and four nozzles are used to fabric to 100 as shown in Table 2 below. A linear printing of dots was performed.

Further, after the ink was mounted on the printers (A) and (B), the ink was capped and left at 50 ° C. for 1 month, and after the recovery operation, the same printing was performed.

The ejection status of each printer (A and B) immediately after mounting the ink is extremely stable for each ink (A to D).
The 0 printed dots had extremely sharp edges, and showed the degree of identity that could hardly be discerned visually. Further, it was clearly superior in accuracy and reproducibility to the printing method using a conventional plate. However, the ejection condition after leaving was only the ink B was unstable, and the ejection was eccentric.

The printed fabric was dried, then subjected to the dyeing treatment shown in Table 3 below, washed and thoroughly dried. The results of the dye-proof are shown in Table 4 below.

(Effect of the Invention) The present invention provides a dye-proof ink (including a colored dye-proof ink) useful for a dye-proof method by an ink jet recording method using one liquid.

By using the ink of the present invention in an ink jet recording method, not only the economical problem and the problem that an accurate print cannot be obtained in the conventional plate-based dye-proofing method are solved, but also the ink-jet discharge discharge by a two-component ink is used. The problem that spots and color unevenness are likely to occur due to the method and the problem of bleeding are also solved, and it becomes possible to obtain a fine pattern that cannot be obtained by the conventional dye-proofing method without a plate-making process.

Claims (4)

[Claims] 1. An inkjet dye-proof ink comprising a dye-proofing agent selected from an organic acid and an oxidizing agent, water, and optionally an organic solvent. 2. The inkjet dye-proof ink according to claim 1, further comprising a dye which is hardly decomposed with respect to the dye-proofing agent and which does not hinder the dyeing reaction with the fabric. 3. A process of applying an ink containing an anti-staining agent selected from an organic acid and an oxidizing agent, water, and optionally an organic solvent to a cloth by an inkjet method, and dyeing the cloth to which the ink is applied. An ink jet resisting method, which comprises a step of: 4. The ink jet protective ink according to claim (3), wherein the ink also contains a dye that is hardly decomposed with respect to the anti-dyeing agent and does not prevent the dyeing reaction with the fabric. Dyeing method.