JPH081033B2 - Ink Jet Dyeing Method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an ink-jet dye-proofing method, and more particularly, to an ink-jet dye-proofing method capable of forming various designs by changing the dye-proofing rate of a cloth.

(Prior Art) Conventionally, a cloth and a pre-dipped cloth are printed with a dye-proof paste and then developed. The so-called dye-resisting method and the color-disinfecting method in which a dye that does not hinder the dyeing of the cloth in the above-mentioned paste is added to simultaneously dye the dye-resisting area are widely used.

(Problems to be Solved by the Invention) However, the conventional general method for preventing dyeing (including coloring dyeing) requires the production of a printing plate for dyeing. There is a problem that the plate cylinder and the screen plate are expensive to make, and the cost cannot be met unless a considerable amount is produced. 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.

In addition, the anti-contamination paste used in the conventional anti-contamination method needs to be made into a highly viscous paste in order to be compatible with various anti-contamination machines, so various water-soluble binders and various fillers, etc. should be used. It is necessary to use in combination, so the edges of the dye-proof part are not sharply dyed, and the precision of the dye-proof pattern is lacking, and after the dyeing, many complicated steps are required to remove these subcomponents. There was a problem that required processing.

As a method for solving such a problem, a color-preventing discharge printing method by an inkjet method has been proposed (see Japanese Patent Laid-Open No. 61-6365). According to this method, an ink containing a stain-proofing agent and an ink containing a non-reducing decomposable dye are separately applied to a colored cloth and at the same location to perform a color-preventing 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.

Further, in the conventional dye-proofing method, since the dye-proofed portion is uniformly dye-proofed, there is a drawback that the pattern formed is monotonous.

Therefore, an object of the present invention is to simultaneously solve the economical problems in the conventional general dye-proofing method as described above, the problem that an accurate print cannot be obtained, and the problem that the pattern formed is monotonous. It is an object of the present invention to provide a dye-resisting method using an inkjet method.

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 provides an ink containing at least water, an organic solvent, and a dye-proofing agent, having a viscosity at 25 ° C. of 30 cps or less and a surface tension in the range of 35 to 65 dyne / cm by an inkjet method. An inkjet dye-proofing method comprising a step of applying a pattern to a cloth or a cloth treated with a submersion agent and a step of dyeing the cloth with a dye, wherein the application of the ink is carried out under any of the following conditions. This is an inkjet dye-proofing method characterized by being carried out in combination.

The ink ejection energy is changed to change the ink application amount.

Ink is applied using a plurality of nozzles having different nozzle diameters.

A plurality of inks having different concentrations of the stainproofing agent are applied from a plurality of nozzles.

A plurality of inks containing a dye-proofing agent having different dye-proofing power are applied from a plurality of nozzles.

Explaining the present invention further, the main feature of the present invention is that instead of various printing methods in the conventional dye-proofing method, an ink jet method is adopted, and a conventional high-viscosity dye-proofing paste is used as the dye-proofing agent. Organic acids, reducing agents, which do not need to be prepared
A liquid containing a dye-proofing agent such as an oxidizing agent is used as a dye-proof ink, that is, an inkjet ink.

Also, in the case of colored dye-resisting, instead of the conventional two-component type ink-jet discharge-discharging method, a one-component type ink-jet method is adopted, and unlike two types of ink, dyeing to a cloth is performed with a stain-resisting agent. The point is that a colored anti-discoloring ink that uses a dye that does not interfere, that is, a one-component type ink is used.

The second main feature is that the dye-providing ratio of the dye-protected portion is changed by changing the ink application conditions during the dye-blocking or the color dye-proofing.

According to a detailed study by the present inventor, in carrying out dye-resisting or color-resisting by an ink jet method, various advantages were caused by the first characteristic point,
The area to be dye-proofed or color-proofed was uniform in the entire pattern, and the pattern formed was monotonous. The present invention is different from the conventional silk screen method in the case of ink-jet-based dyeing or dye-based dyeing,
The application of the dye-proof ink or the colored dye-proof ink is extremely monotonous, and it is very easy to change the applied amount, the concentration of the dye-proofing agent in the ink, or the type of the dye-proofing agent. By changing the conditions of ink application, it is possible to change the dye-proof ratio of the ink on the fabric where it is applied, and to change the dye-proof ratio as needed. Area not to be)-
It is possible to freely control the dye-proof rate of the fabric, such as medium density (region that has been dye-proofed to some extent) -light color (region that is mostly dye-proofed) -white (region that is all dye-proofed). As a result, the inventors have found that the problem of monotonicity of conventional designs is solved and that various designs are formed.

The ink jet method used in the first step of the present invention and which characterizes the present invention firstly means that the ink can be effectively separated from the nozzle to apply the ink to the cloth as the range. Any method may be used, and typical ones of them are, for example, IEEE Trans actions on Industry Applica- tions.
tions) Vol. IA-13, No. 1 (February and March, 1977), Nikkei Electronics April 19, 1976, January 29, 1973 and May 6, 1974. ing. The methods described in these are suitable for the dye-proofing method of the present invention,
Explaining some of them, first there is an electrostatic suction method. In this method, a strong electric field is applied between the nozzle and an acceleration electrode placed several mm in front of the nozzle, and the ink is made into particles from the nozzle and one after another. A method of recording information by giving an information signal to the deflection electrodes while the drawn ink and the drawn ink fly between the deflection electrodes,
There is a method of ejecting ink particles in response to an information signal without deflecting the ink particles, both of which are effective for the dye-proofing method of the present invention.

The second method is to apply a high pressure to the ink with a small pump and mechanically vibrate the nozzle in a quartz oscillator to forcibly eject minute ink particles.
The ejected ink particles are charged simultaneously with the ejection according to the 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 ink jet method. In this method, ink pressure and vibration 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 Laid-Open No. 54-599365, an ink-jet method in which ink subjected to the action of thermal energy causes a rapid volume change and the action force resulting from this state change ejects the ink from a nozzle Can also be used effectively.

By the ink jet system as described above, a dye-proof ink or a one-component type color dye-proof ink described below is applied to a cloth (this cloth may not have been dyed but may have a dye attached thereto) or Existence of the ink applied in a pattern by applying the ink to the soaked cloth in a pattern while changing the ink application conditions, then drying if necessary, and dyeing with a normal dye for dye protection. Dyeing of the part is prevented according to the ink application conditions, and the part where the ink does not exist and the part where the amount of the dye-proofing agent is small are dyed according to the ink application condition. The dye-resisting portions of the pattern formed in this way are not all white-resisted, but are completely stain-proofed and one part dyed and one part dyed according to the ink application conditions. The pattern consists of. Further, in the case of color resisting, at the same time, a dye resistant to a dye contained in the ink is dyed on the dye-protected portion according to the ink application conditions, and a pattern of another hue is formed. By continuing the usual post-treatments such as washing with water, washing with hot water, soaping, etc., the dyes that have not been dyed on the fiber or their decomposition products are removed, and the dyeing and coloring with different dyeing rates are completed. To do.

The anti-dyeing ink used in the present invention and secondly characterizing the present invention is mainly composed of an aqueous solution of an anti-dyeing agent such as an acid, a reducing agent or an oxidizing agent as used in conventional anti-dyeing agents. Inkjet recording aptitude is given to.

As the stainproofing agent that can be used in the ink used in the present invention, any material can be used as long as it is a material that can prevent dyeing or color development of fibers of conventional dyes for dyeing prevention. Acid, tartaric acid,
Organic acids such as oxalic acid and glycolic acid, acidic substances such as aluminum sulfate and other acidic salts, sodium m-nitrobenzene sulfonate, sodium o- or p-nitrotoluene sulfonate, calcium or zinc m-nitrobenzene sulfonate , Salts such as m-nitroanthracene sulfonic acid, sodium hydrosulfite (Na
₂ S ₂ O ₄ ), mixed sodium salt of anhydrous H ₂ SO ₄ and H ₂ SO ₃ , sodium sulfoxylate-formaldehyde complex, sodium bisulfite-formaldehyde complex, calcium hydrosulfite, zinc sulfoxylate-formaldehyde Secondary agents such as secondary salts, zinc sulfoxylate-formaldehyde primary salts, zinc sulfoxylate-acetaldehyde, cetyltrimethylammonium bromide, octadecylpyridinium bromide, vinylpyrrolidone polymers, stannous chloride, tin acetate, etc. Is.

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 cloth to be dyed and the type of dye for dye protection.

The inkjet dye-proof ink used in the present invention is prepared by dissolving or dispersing the above dye-proofing agent in a medium at a concentration of about 0.1 to 30% by weight. As a medium for ink,
Water alone is used, preferably a mixed solution of water and an organic solvent. Examples of the organic solvent used include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-
Butyl alcohol, tert-butyl alcohol, isobutyl alcohol, etc., C1-C4 alkyl alcohols; dimethylformamide, dimethylacetamide, etc. amides; acetone, diacetone alcohol, etc. ketone or keto alcohols; tetrahydrofuran, dioxane, etc. Ethers; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; alkylene groups such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol Is 2-6
Alkylene glycols containing 1 carbon atom; glycerin; lower monoalkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether; Lower dialkyl ethers of polyhydric alcohols such as triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether; N-methyl-2-pyrrolidone, 1,3-dimethyl-2-
Examples thereof include imidazolidinone.

Although the above media can be used alone or as a mixture, the most preferred media composition is water and at least one organic solvent, and the solvent is at least one water-soluble high-boiling organic solvent such as diethylene glycol or propylene glycol. And polyhydric alcohols such as glycerin.

The essential components of the ink used in the present invention are as described above, but other conventionally known various dispersants, surfactants, viscosity modifiers, surface tension modifiers, optical brighteners, etc. are added as necessary. can do.

For example, viscosity adjusting agents such as polyvinyl alcohol, celluloses and water-soluble resins; various cationic, anionic or nonionic surfactants, indication tension adjusting agents such as diethanolamine and triethanolamine; buffer solutions
Examples thereof include pH adjusters and antifungal agents.

Further, in order to prepare a dye-proof ink used in an ink jet type 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 system 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, thermal expansion coefficient, thermal conductivity, etc.) may be adjusted. .

The dye-proof ink used in the present invention as described above has a viscosity of about 30 cps or less and a surface tension of about 35 to 65 dyne / cm.
The most excellent ink jet aptitude can be obtained by adjusting the temperature range (25 ° C.).

The dye-proof ink used in the present invention basically comprises the components and properties as described above, is applied in a pattern to a cloth by the ink jet method as described above, and then various dye-proof by a dyeing step and a post-treatment. It forms a resist pattern having a different rate.

In another embodiment of the present invention, a dye or a pigment that is not affected by the anti-dye agent in the ink is dissolved or dispersed in the anti-dye ink described above, and the cloth is subjected to ink application conditions changed. It is a useful dye-proofing method for coloring and dyeing, in which the dye-proofing is carried out in a pattern form and the dyed part is dyed in another hue.

As the dye-resistant dye in the ink used in such a method, a dye-resistant basic dye, a direct dye, an acid dye, a reactive dye, which are well known in the conventional color dye-proof technology, Depending on the type of cloth, it may be used in advance from reaction-dispersion dyes, disperse dyes, building materials, soluble vat dyes, azoic dyes, sulfur dyes, oxidation dyes, various pigments and the like.

Such a stain-proofing agent-resistant dye is preferably dissolved or dispersed in the stain-proofing ink used in the present invention at a concentration of about 0.1 to 15% by weight to suitably perform color-staining with different stain-proofing rates. You can

When the method of the present invention is a color resist, it is a one-component type, which is different from the conventional two-component type color dye-resisting method. Since it is used in combination with a dye or pigment having a stainproofing property, 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 dye-proofing agent, dye and other ink components to be used, but depending on the types of the components to be used depending on the various compounds shown in the ink used for the above-mentioned dye-proofing. , Each time, it may be determined experimentally by finding a factor that enhances stability.

The dye-resisting method of the present invention applies the dye-resisting ink described above to a cloth or a submerged-treated cloth as described below in a one-liquid manner and in a pattern by changing the ink applying conditions by the inkjet method described at the beginning. , White according to the ink application conditions
The method is characterized by partial dyeing or color dyeing, and preferable methods for changing the ink application conditions include, for example, (1) changing the ink application amount so that a relatively large portion is applied. A method of being sufficiently dye-proofed, and the dye-proofing rate is reduced as the amount of ink applied is reduced so that dyeing can be partially performed in the subsequent dyeing process. For example, specifically, there are methods such as adjusting the drive application voltage of the printer so as to change the ejection energy, and using a plurality of nozzles having different nozzle diameters.

(2) A method of applying a plurality of inks having different concentrations of a dye-proofing agent to change the dye-proofing rate as in the above (1).

(3) A method of changing the dye-proof rate in the same manner as (1) above using dye-proofing agents having different dye-proofing powers.

(4) A method combining the above methods.

 Etc. are useful.

Such cloth used in the present invention includes cotton, wool,
Natural fibers such as silk and hemp, recycled fibers such as cupra and rayon, woven or non-woven fabrics made of synthetic fibers such as acrylic, nylon, polyester, vinylon, polypropylene and acetate rayon, or woven fabrics made of the above-mentioned fibers Alternatively, it is a non-woven fabric. When azoic dye-proofing is performed according to the present invention, these fabrics are subjected to a submersion treatment with an azoic submersion agent. Among these cloths, particularly preferable are cellulose-based and regenerated cellulose-based cloths. These cellulose-based cloths have good hydrophilicity themselves, and therefore have good absorbability of water-based ink. The delicate pattern can be formed because it is accurately dye protected according to the application conditions. On the other hand, in the case of a cloth having low hydrophilicity, since the absorbability of the water-based ink is poor, the applied ink may bleed or flow to form a delicate pattern. Of course, such a drawback can be solved by making the cloth hydrophilic or changing the components of the ink.

Such a cloth is a basic dye, a direct dye, an acid dye, a reactive dye, a reactive dispersion dye, a disperse dye, which is well known in the conventional dye-proofing and color-dyeing techniques and has excellent anti-dyeing resistance. , Vat dye, soluble vat dye, sulfur dye,
It may be dyed with a mordant dye, an oxidation dye, an azoic dye, various pigments, or the like in a hue different from the hue to be dyed, or in the case of the same hue, with different densities. By doing this, the dye-proof part does not simply become dye-proof,
It becomes a colored dye-proof part, and it has the same effect as coloring dye-proof.
Further, it goes without saying that the whole or a part of it may be similarly dyed after the dye-proof treatment. Further, a dye to be dyed later may be attached to the cloth as described above. In such a case, a treatment for dyeing these dyes is performed after applying the dye-proof ink. For example, it is a preferable method when a reactive dye or an azoic dye is used.

As described above, the method of dyeing the fabric applied with the dye-proof ink under different application conditions is performed by dyeing with a dye for dyeing according to a conventionally known method. Any of the conventionally known anti-dye dyes can be used as the anti-dye dye,
Specifically, for example, basic dyes, direct dyes, acid dyes, reactive dyes, reactive dispersion dyes, disperse dyes, vat dyes,
Examples thereof include soluble vat dyes, sulfur dyes, mordant dyes, oxidation dyes, azoic dyes, and various pigments. Among them, a cloth having an appropriate dye-proof property is selected and used according to the cloth and the dye-proof agent used. Among these dyes, direct dyes, reactive dyes, azoic dyes, vat dyes are particularly preferable, and since the dye-proof ink used is aqueous, the dye-proofing agent in the dye-proof ink is a dye to be dyed later. On the other hand, it has good reactivity and shows excellent dye resistance according to the ink application conditions.

According to the present invention as described above, the dye-proof ink is applied in a pattern on the cloth by changing the ink adhesion conditions by an inkjet method, then dried as necessary, and further dyed with a usual dye for dye protection. By doing so, the dyeing of the part where the ink applied in a pattern is present is prevented according to the ink applying conditions, and only the part where the ink does not exist and the part where the stain-proofing agent is small are dyed. Further, in the case of color resisting, at the same time, a dye or pigment having a dye resistant property contained in the ink is dyed on the dye protected portion, and a pattern of another hue is formed. By continuing the usual post-treatments such as washing with water, washing with water, soaping, etc., the dyes that did not dye on the fibers or their decomposition products are removed, and white to partial dyeing and color dyeing are achieved. To be done.

According to the present invention as described above, a stainproofing agent is used as a solution and as a stainproofing ink imparted with ink jet recording suitability, and such an ink is applied to a cloth or a dipped-treated cloth by an ink jet method. White
Since partial dyeing or color dyeing is performed, it is not necessary to prepare expensive printing plates and the like as in conventional dyeing methods, and various images can be easily and arbitrarily created by a computer connected to an inkjet recording device. Since it can be created and the image can be used immediately for dyeing, it can always follow the short fashion period of the pattern of the print cloth, and the cost is suitable even if it is not always mass-produced.

Further, unlike the conventional method, it is not necessary to use a high-viscosity dye-proof paste or a two-component type ink, so various problems caused by these high-viscosity dye-proof glue or a two-component type ink, especially There is no problem that unevenness in the formed pattern, unnecessary spots, bleeding, or the like occurs.

Further, in the present invention, since the ink-jet method is used in applying the dye-proof ink, it is easy to arbitrarily change the conditions for applying these inks, so that the cloth can be dye-proofed at any dye-proof rate. Since it is possible, various types of dyeing can be performed in the range from complete dyeing to partial dyeing, and as a result, dyes can be effectively used to form a wide variety of dyeing designs. The problem of monotonicity of technology patterns was solved.

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.

Reference Example 1 (Preparation of dye-proof ink used in Examples) Glycerin 12 parts N-methyl-2-pyrrolidone 12 parts Water 76 parts All the above components were stirred for 2 hours to prepare a base ink. Next, to 100 parts of the base ink, the dye-proofing agents and coloring materials shown in Table 1 below were added, and the mixture was stirred for 3 hours.
Inks (AI) used in Examples and Comparative Examples of the present invention were obtained by filtering with EP-100 (trade name; manufactured by Sumitomo Electric Industries, Ltd.).

Table 1 also shows the physical properties of each ink at 25 ° C.

Table 1 Ink A tartaric acid 5 parts (surface tension = 55, viscosity = 2.3) Ink B tartaric acid 3 parts (surface tension = 55, viscosity = 2.1) Ink C tartaric acid 1 part (surface tension = 56, viscosity 2.0) Ink D sodium Hydrosulfite (trade name; Hydrosulfite R Conc, manufactured by Ciba Geigy) 8 parts Difficult-to-reduce deviation color direct dye (trade name; Kayarus Light Yello
w F8G, manufactured by Nippon Kayaku) 3 parts (surface tension = 52, viscosity = 2.9) Ink E Sodium Hydrosulfite (trade name; Hydrosulfite R Conc, manufactured by Ciba Geigy) 0.5 part Difficult-to-reduce decolorizable direct dye (trade name) ; Kayarus Light Yellow
F8G, manufactured by Nippon Kayaku) 3 parts (surface tension = 55, viscosity = 2.1) Ink F m-nitrobenzene sulfonate 10 parts (surface tension = 56, viscosity = 2.5) Ink G m-nitrobenzene sulfonate 5 parts ( Surface tension = 56, viscosity 2.3) Ink H m-nitrobenzene sodium sulfonate 2 parts (surface tension = 56, viscosity = 2.1) Ink I citric acid 3 parts (surface tension = 55, viscosity 2.1) Surface tension (dyne / cm) is KYOWA CBVP SURFA CETE
NS IOMETER A-1 (manufactured by Toa Denpa Kogyo) was measured at 25 ° C, and viscosity (cps) was measured by VISCONIC ELD (manufactured by Tokyo Keiki) 2
It was measured at 5 ° C.

Reference Example 2 (Preparation of Dye-Resistant Ink Used in Comparative Example) In place of the non-reducible decolorizable direct dye contained in the inks (D) and (E) shown in Reference Example 1, an easily reducible decolorizable direct dye (trade name) ; Kayarus Supra Yellow RL, manufactured by Nippon Kayaku)
Inks (J) and (K) used in the comparison of the present invention were obtained by treating in exactly the same manner as in the preparation of the inks (D) and (E) except that the above was used.

Reference Example 3 (Preparation of Shimozuke Cloth) CI Azoic Coupling Component 18 (Trade name; Naphthoid AD, Sumitomo Chemical Co., Ltd.) 1 part Roth oil (50%) 1.5 parts Sodium hydroxide aqueous solution (35%) 1.5 parts Boiling water 15 parts All the above components were mixed, and 81 parts of cold water was further added to obtain a soaking solution.

100% cotton satin cloth in the above dipping solution at a bath ratio of 1:20 at 30 ℃, 1
Soak for 5 minutes in the mangle and dry the fabric about 1.8 times.
The lower pickled cloth (a) used in Examples and Comparative Examples of the present invention was obtained by tightly squeezing it so that the weight becomes about twice.

Reference Example 4 (Preparation of developer) CI Azoic diazo component 13 (Brand name: Fast
Scarlet RC Base, made by Hoechst) 2 parts Hydrochloric acid (32%) 1.8 parts Hot water 2 parts Stir all the above ingredients, add 36 parts cold water and adjust to 10 ° C. Sodium nitrite dissolved in a small amount of water beforehand (0.
68 parts) and diazotize in about 10 minutes.

After filtration, immediately before color development, 1.34 parts of sodium acetate, 0.94 parts of 50% acetic acid aqueous solution, and 954 parts of cold water were added and stirred to obtain a color development liquid (1) used in Examples and Comparative Examples of the present invention.

Example 1 Inkjet printer PJ-using a piezo element
1080A (trade name; made by Canon, hereinafter referred to as printer (Kou).) Of the four nozzles, the inks (A to C) shown in Reference Example 1 were respectively mounted on three nozzles, and the dyeing of Reference Example 3 was performed. On the fabric (a), 300 dots each were printed in 10 rows in a straight line from each nozzle.

After drying, it was treated with the developer (1) of Reference Example 4 at a bath ratio of 1:20 for 20 minutes and squeezed with a mangle. After leaving it for 30 minutes, it was thoroughly washed with water, treated with dilute hydrochloric acid for a short time, and then washed again with water.

(Results) The dye-proof area of the ink (A) was completely white-colored, but as the inks (B) and (C) were used, the dye-proof rate was lowered and intermediate dye-proof was performed. That is, by using a plurality of inks having different organic acid concentrations, it was possible to achieve diversification of the dye-proof pattern.

Further, the straight line dye-resisting portion in the 10th row had extremely sharp edges, and showed the degree of identity that could hardly be discerned visually. It was clearly superior in terms of accuracy and reproducibility compared to the conventional dye-resist method.

Example 2 (resist prevention example) Inkjet printer BJ using thermal energy
-80 (trade name: manufactured by Canon Inc., hereinafter referred to as a printer) is loaded with the ink (B) in Reference Example 1, and the straight line is formed from 10 nozzles to the dyed fabric (a) in Reference Example 3. I printed 100 dots on top. Next, the same printing was performed in parallel using the ink (1) instead of the ink (B).

After drying, the same color development process as in Example 1 was performed. The ink (B) and the ink (I) have the same reducing agent concentration, but the dye-proof rate was higher in the case of the ink (B). That is, by using a plurality of inks having different kinds of organic acids, it was possible to diversify the resist pattern.

In addition, the edges of the linear dye-proof portions were extremely sharp, and were excellent in accuracy and reproducibility.

Example 3 (Example of color resisting) Reference example 1 was applied to 2 of the 4 nozzles of the printer (A).
Each of the inks (D) and (E) shown therein was mounted, and 300 dots each were printed in a straight line from each nozzle on each of the dyed fabric (a) of Reference Example 3 from each nozzle. After drying, the same color development process as in Example 1 was performed.

(Results) The color-resisting portion with the ink (D) was dye-proofed with a vivid yellow color, but the color-resisting portion with the ink (E) was partially developed with the azoic dye and was not completely dye-proofed. It turned orange. That is, by using a plurality of colored dye-proof inks having different reducing agent concentrations, the dye-proof pattern could be diversified.

The shape of the colored dye-proof part was the same as that of Example 1, and the accuracy and reproducibility were good.

Example 4 Reference example 1 was applied to 3 of the 4 nozzles of the printer (A).
Equipped with each of the inks (F ~ H) shown in the inside, 70% cotton
And, for a blended broad cloth of 30% polyester, 300 dots each were printed in 10 rows in a straight line from each nozzle.

After drying, an aqueous solution of vat dye Indanthren Brown RM (trade name; manufactured by Bayer) reduced with loading soda and hydrosulfite was padded and steamed for 10 minutes at 12 ° C for soaping. .

(Results) The dye-proof part of the ink (F) was completely white-proofed, but as the inks (G) and (H) were changed, the dye-proof rate was lowered and the intermediate dye-proofing was carried out. That is, by using a plurality of inks having different oxidizer concentrations, it was possible to achieve diversification of the dye-proof pattern.

Example 5 The ink (B) in Reference Example 1 was mounted on a printer (Otsu), and the dyed fabric (a) of Reference Example 3 was printed linearly from 10 nozzles with 100 dots each. In this case, the voltage applied to the heater for ejecting the ink by the thermal energy was measured and found to be 24V.

Next, the voltage applied to the heater was set to 22 V and 26 V to change the amount of ink applied, and the same printing was performed in parallel.
After drying, the same color development process as in Example 1 was performed.

(Results) Observation of the dye-proof area showed that as the voltage increased, the dots in the dye-proof area became larger and the dye-proof rate became higher. That is, it was possible to diversify the dye-proof pattern by changing the amount of the dye-proof ink applied.

Comparative Example The same treatment as in Example 3 was performed except that the inks (J) and (K) shown in Reference Example 2 were used instead of the inks (D) and (E) in Example 3.

(Results) In this example, similar to Example 3, the color dye-proofing was aimed, but the color dye-proofing was not possible simply by white dyeing because the dye used in the ink was erroneously selected.

(Effect of the Invention) The present invention provides a dye-proofing method (including a color dye-proofing method) by an inkjet recording method using a plurality of application conditions with one liquid.

According to the present invention, not only the economical problem and the problem that accurate printing cannot be obtained in the conventional dye-proofing method by the plate are solved at the same time, but also spots and color unevenness are easily caused by the ink-jet discharge-proofing method using two liquids. Therefore, the problem of bleeding and the problem of bleeding can be solved, and it becomes possible to obtain a fine pattern which cannot be obtained by the conventional dye-proofing method, without a plate-making process.

Further, various ink-proofing can be carried out by changing the ink application conditions, a very various dye-proofing pattern can be formed, and the problem of the monotonicity of the pattern of the prior art was solved.

Claims (5)

[Claims] 1. At least an organic solvent and a dye-proofing agent are contained, the viscosity at 25 ° C. is 30 cps or less, and the surface tension is 35 to 65 d.
An ink jet dye-proofing method comprising a step of applying a pattern of ink in the range of yne / cm to a cloth or a cloth treated with a submersion agent by an ink jet method and a step of dyeing the cloth with a dye. Grant of
An inkjet dye-proofing method, characterized in that the following conditions (1) to (4) are performed individually or in combination. The ink ejection energy is changed to change the ink application amount. Ink is applied using a plurality of nozzles having different nozzle diameters. A plurality of inks having different concentrations of the stainproofing agent are applied from a plurality of nozzles. A plurality of inks containing a dye-proofing agent having different dye-proofing power are applied from a plurality of nozzles. 2. The inkjet dye-proof method according to claim 1, wherein the ink is used in combination with a dye which is hardly decomposable with respect to the dye-proofing agent and does not hinder the dyeing reaction with the cloth. 3. The inkjet dye-proof method according to claim 1, wherein the dye-proof agent is an organic acid. 4. The inkjet dye-proofing method according to claim 1, wherein the dye-proofing agent is a reducing agent. 5. The inkjet dye-proofing method according to claim 1, wherein the dye-proofing agent is an oxidizing agent.