JPS6020514B2 - Resist dyeing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a beam-proofing method for textile products, and more specifically, in a beam-proofing method that uses water-soluble polyvalent metal salts and polyvalent metal hydroxides as resist dyes, dye This article relates to a beam-proofing method that improves the washability of printed materials after fixation.

A physical resist dyeing method using activated carbon, activated clay, glue, etc. as a barrier method for hydrophobic fiber products such as polyester and cellulose acetate, and a method that decomposes the dye using a reducing agent such as stannous chloride. Known methods include an anti-discharge printing method that uses chelates of polyvalent metal compounds and dyes, and a chemical anti-beam method that uses chelates of polyvalent metal compounds and dyes.

However, the former physical resist dyeing method requires a considerably thick glue layer, especially when using disperse dyes, and although it can be applied to hand printing, it is mechanically difficult to apply to roller printing. In addition, automatic screen printing has major drawbacks in practical use, such as the difficulty of continuous operation due to adhesion of the resist paste to the mold, clogging of the screen, etc. In addition, the latter chemical beam-proofing method allows beam-proofing even if the glue layer is made considerably thinner, but the discharge-proof printing method that uses reducing substances such as tin chloride has drawbacks such as halation and discoloration. In addition, the method described in Hakama Kosho 40-120516 using a polyvalent metal compound, for example, provides a somewhat reproducible resisting effect when used in combination with a physical barrier agent in a light-colored barrier barrier using a specific dye; When fixing using high-temperature steam or thermosol methods, which are advantageous in terms of workability in autoscreen printing, the beam-proofing effect of medium-dark colors is completely insufficient, and white resist-dyed products with commercial value or clear coloring are required. In addition to being impossible to obtain a beam-proof product, it is necessary to make the lake layer relatively thick due to its beam-proofing effect, which has the disadvantage of causing mold back adhesion, screen clogging, etc. in automatic screen printing. In order to improve the beam-proofing effect, a resist dyeing method using a combination of Mizuochi polyvalent metal salt and polyvalent metal hydroxide as a beam-proofing agent is also known as the method described in Japanese Patent Publication No. 49-48593, and also the present inventors et al. proposed a combination of water-soluble polyvalent metal salts and polyvalent metal hydroxides at a specific molar ratio, and pH adjustment using an organic carboxylic acid.
Adjusted to 6-8 Samuraibuta 52-221 Pi No. (Tsubaki Kimisho 57
There is an improvement method described in No.-27233). However, an improved method using a water-soluble polyvalent metal salt and a polyvalent metal hydroxide in combination, although the latter method exhibits an excellent resisting effect,
Although it improves the resist dyeing effect, it has the disadvantage that it is extremely difficult to remove metals by dye cleaning after dye fixation. The present inventors have conducted extensive research on a method for removing polyvalent metals through a simple washing process after dye fixation in a beam-proofing method that uses a combination of water-soluble polyvalent metal salts and polyvalent metal hydroxides as beam-proofing agents. result,
The method of the present invention has been arrived at. That is, the present invention provides a method for resist-dying textile products using a water-soluble polyvalent metal salt and a polyvalent metal hydroxide as a beam-proofing agent in combination, in which an organic carboxylic acid is added to a beam-proofing paste, and at the same time the resist dyeing is carried out. It is characterized by adding head nitrates to the paste and/or printing paste. When using the method of the present invention, polyvalent metals can be easily removed by simple cleaning without impairing the beam-proofing effect or the dyeing effect of coloring dyes.

Therefore, by using a large amount of water-soluble polyvalent metal salt and polyvalent metal hydroxide in combination, it has excellent clarity without coloring or dullness caused by polyvalent metals even in the beam protection method where demetallization is extremely difficult. Printed products can be provided. In addition, there is no need for a strong cleaning process using acids, ammonia, or metal ion sequestering agents for cleaning after dye fixation, and simple cleaning is sufficient, which is extremely advantageous in terms of processing costs such as shortening the process and saving water resources, making it suitable for industrialization. offer great advantages. Of course, polyvalent metals can be easily removed even by high-temperature steaming or coloring treatment using a thermosol method, which is more difficult to remove metals. Examples of nitrites used in the method of the present invention include ammonium nitrite, potassium nitrite, sodium nitrite, silver nitrate, cobalt nitrite, barium nitrite, etc., with potassium nitrite and sodium nitrite being particularly preferred. When using a water-soluble polyvalent metal salt and a polyvalent metal hydroxide together as a beam-proofing agent, the solubility of the polyvalent metal compound improves due to the interaction between the two, so it is necessary to increase the concentration of the beam-proofing agent. It is known from Samurai Publication No. 49-48593 that the beam-proofing effect can be improved.

However, the stability of the size solution and the resisting effect of medium-dark colors are still insufficient, and as a result of intensive research into improved methods, the present inventors have found that water-based polyvalent metal salts and polyvalent metal hydroxides and the former 1
By using a solution with a pH of 6 to 8 in which organic carboxylic acid is added to a mixture containing the latter at a ratio of 1.2 to 3.0 mol to mol, the stability of the size solution can be solved, as well as an excellent beam-proofing effect and a sharp handle. Succeeded in obtaining a medium color printed material with excellent clarity and sharpness, and was granted a patent application No.
No. 233). The present invention was created in the 49th century by Samurai Ko.
Anti-staining methods using water-soluble polyvalent salts and polyvalent metal hydroxides in combination as described in Japanese Patent Application No. 57-27233 and Japanese Patent Application No. 57-27233; Hakama Yusho 52-22 is highly effective and difficult to remove polyvalent metals.
When applied to the method described in No. 1, an excellent metal removal effect can be achieved. The reason for the excellent metal removal effect is unknown, but the presence of nitrite ions suppresses the chelation reaction between polyvalent metals and fibers and the formation of water-soluble or water-insoluble polyvalent metal compounds. it is conceivable that. However, such effects are similar to other sodium chlorite, sodium hypophosphite, sodium hypochlorite, m-
This was completely surprising since this could not be achieved using oxidizing agents such as sodium nitrobenzenesulfonate or similar compounds such as sodium nitrate and ammonium nitrate. Examples of the polyvalent metal hydroxide used in the present invention include copper, barium, calcium, nickel, cobalt,
Hydroxides such as aluminum may be used, but barium hydroxide and calcium hydroxide are particularly preferred.

Examples of water-resistant polyvalent metal salts include sulfates and hydrochlorides of copper, aluminum, chromium, etc., and sulfuric acid steel is particularly preferred.

Examples of organic carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, and caproic acid; oxycarboxylic acids such as glycolic acid and hydroxyacetic acid;

Examples include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, and adipic acid, and unsaturated carboxylic acids such as methacrylic acid and acrylic acid, but especially aliphatic monocarboxylic acids having 6 or less carbon atoms. Preferred are formic acid, acetic acid, propionic acid and n-acid. To explain the method of the present invention in more detail, when a textile product is beam-proofed using a water-soluble polyvalent metal salt and a polyvalent metal hydroxide together as a dye resisting agent, a dye is added to the beam-proofing paste and/or the printing paste. It is characterized by the addition of nitrates, but in particular, the addition of nitrites to the printing paste ensures that the fibers do not discolor due to the nitrites themselves, that the resist dyeing effect does not deteriorate, and that the light fastness of the printed product is excellent. It is particularly preferable from the following points.

When water-soluble polyvalent metal salts and polyvalent metal hydroxides are used in combination, it is preferable that the resist dyeing paste has a matrix of usually 6 to 8 from the viewpoint of paste stability, birch dye stability, dyeability, etc. Rather than simply blending both metal compounds so that the pH is 6 to 8, 1.0% of the polyvalent metal hydroxide is added to 1 mole of the water-soluble polyvalent metal salt.
Neutralization to pH 6 to 8, especially 6.5 to 7.5 with an organic monocarboxylic acid in an excess of 2 to 3.0 moles is
It is particularly preferred from the viewpoint of beam-proofing effect, edge sharpness, sharpness in colored beam-proofing, etc. Usually, a small amount of water and/or an organic carboxylic acid is added to a total of 30 to 8 parts by weight of water lacquer polyvalent metal salts and polyvalent metal hydroxides, and mixed thoroughly, and if desired, an amphoteric surfactant or non-alcoholic acid is added. Add 0 to 15 parts by weight of an ionic surfactant, 0.5 to 1 part by weight of nitrites, and further add water to make a total of 10 parts by weight. Mix the mixture to sufficiently melt or disperse the metal compound. After preparing a beam-proofing agent composition, it is mixed with a glue (original glue), an auxiliary agent, etc. to prepare a beam-proofing paste. In this case, it is usually preferable to use 3 parts by weight or more of the organic carboxylic acid. Therefore, the molar ratio and concentration of both metal compounds are adjusted so that the pH becomes 6 to 8 by using 3 parts by weight or more of the organic carboxylic acid. is preferable. Furthermore, nitrites may be added directly during the preparation of the resist dyeing paste, or even when used in the printing paste without being used in the resisting paste, an excellent dyeing and cleaning effect can be exerted. Particularly preferable combinations and compounding ratios (weight) of the metal compounds used as beam preventive agents are 35 to 5 parts of barium hydroxide, 10 to 25 parts of steel sulfate, 30 to 45 parts of calcium hydroxide, 15 to 25 parts of copper sulfate, and water. These include 80 to 5 parts of barium oxide, 10 to 2 parts of chromium chloride, 30 to 5 parts of barium hydroxide, 10 to 2 parts of aluminum chloride, and 5 to 15 parts of sulfuric acid steel.

Further, the compounding ratio (weight) of the nitrites to be added to the beam preventive agent composition or the resist dye lake is preferably 2 to 12 parts per 10 anchors in total of both metal compounds. The prepared resist dye composition is mixed with a usual printing paste to prepare a resist dye paste. Sizing agents for printing include starch-based, cellulose-based, gum-based, water-soluble or water-swelling synthetic polymers such as polyacrylamide,
Examples include polyvinyl alcohol and polypynylacetal, but particularly in automatic screen printing, it is preferable to use a gum type, a combination of a gum type and a cellulose type, or a combination of a gum type and a water-soluble synthetic polymer. The mixing ratio of the resist composition to the resist paste depends on the target material, the dye, the type and amount of the metal compound used, the type of printing machine, and the type of resist beam (colored resist beam or white resist dye, light color or medium-colored resist dye). Although it varies depending on the color of the beam, etc., the amount of beam-protecting agent composition is usually 20 to 6 parts by weight, preferably 30 to 5 parts by weight, per 10 parts by weight of the beam-proofing paste. The content of all metal compounds based on the weight of the beam-protecting paste 10 is usually 10 to 45 parts by weight, preferably 20 to 35 parts by weight. Further, the content of the organic carboxylic acid based on the weight part of the resist paste 10 is preferably 1 part by weight or more, and particularly preferably 2 to 1 part by weight.
Furthermore, the content of nitrites based on the weight of the beam-protecting paste 10 is usually 0. The amount is at least 1 part by weight, preferably 1 to 6 parts by weight. If more than the required amount is used, the facial nitrates themselves will cause discoloration, making them inappropriate. It is preferable to prepare the resist dye according to the above procedure from the viewpoint of uniform dissolution or dispersibility, and when the total concentration of the metal compound is low, it is not necessarily necessary to mix in the above order, but any order may be used. In addition, although it is not particularly necessary, when the pH of the beam-protecting paste varies depending on the glue, stiffener, etc. used, it is preferable to adjust the pH to 6 to 8. Nitrites can be added to the printing paste without being added to the beam-proofing paste, or can be added to both the beam-proofing paste and the printing paste.

When added to a printing paste, it has the advantage that even if it is used in a relatively large amount, it does not discolor the fiber itself and does not adversely affect the sunlight fastness of the printed product. The amount added at that time is usually 0.5 part by weight or more, preferably 2 to 1 part by weight, based on the weight of the printing paste 10. When added to both resist dyeing paste and printing paste, usually 0.00 parts by weight of each paste. It is added in an amount of 1 part by weight or more, preferably about 1 to 5 parts by weight. Textile products to which the present invention is applied include, in particular, products containing hydrophobic fibers such as polyester, polyamide, acetate, products containing hydrophilic fibers or glass fibers treated with hydrophobic synthetic resins, and products containing etherified or esterified hydroxyl groups. Disperse dye-containing textile products, such as hydrophilic fiber-containing products such as cellulose, silk, polyvinyl alcohol, etc., pretreated with polyols or their derivatives, amide compounds, aromatic compounds, alkylene oxide-added nonionic compounds, etc. Preference is given to dyeable textiles or textiles dyeable with disperse dyes such as complexes of ionic dyes and compounds having an opposite charge to said ions, especially polyester textiles.

Textile products include fibers, tows, warped yarns, knitted fabrics, nonwoven fabrics, synthetic papers, Y-tape for rugs, and the like.

Further, examples of the dye that can be used as a beam barrier in the present invention include dyes that have a chemical structure that can be chelated with polyvalent metals, dyes that are dispersed with a dispersant that eliminates the dispersion effect by interacting with polyvalent metals, and the like. Specifically, dyes containing anionic groups that can react with polyvalent metals, disperse dyes, disperse dyes that are dispersed with anionic activators that can react with polyvalent metals,
Examples include a complex between an anionic dye and a cationic compound, a complex between a cationic dye and an anionic compound, and the like.

However, particularly preferred are disperse dyes having a chemical structure that is capable of reacting and chelating, especially with polyvalent metals. Further, as intercalating dyes in color resist dyeing, there may be mentioned dyes which do not react with polyvalent metals or have low reactivity, and particularly preferred are disperse dyes which do not react with polyvalent metals to form a chelate, or which are difficult to chelate with polyvalent metals. The resist dyeing agent of the present invention can be applied not only to hand printing but also to automatic screen printing, roller printing, etc., but it is particularly effective as an excellent resist dye in the wet-on-wet printing method of automatic screen printing. It is possible to exhibit effective and continuous printing properties.

For the color development method after printing, any of the normal pressure or high-pressure steam method, high-temperature steam method, thermosol method, etc. used in normal textile printing can be applied, but in particular, high-temperature steam is used in the case of using dispersed dyes for polyester fibers. The thermosol method is preferred from the viewpoint of operability.

Further, after color development, no special washing step is required, and polyvalent metals can be easily removed by ordinary washing with water, washing with hot water, or reduction washing.

The present invention will be explained below with reference to Examples.

Note that parts and percentages in the examples are parts by weight and percentages by weight. Example 1 A textured yarn fabric made of 100% polyester fiber was patterned using a screen printing machine using resist dyeing pastes ~'C} of the following formulations prepared using resist dye compositions 'a}~{d of the following formulations, respectively. It was stamped on the form.

Resistant composition, beam-proofing paste formulation, beam-proofing agent composition 'a~'c-4
5 parts Motonori (Meipro Gum NP, Meipro Inc.) 4 Ikaribe water 15 parts Total amount 10 cities and then C. 1. Disperse Yellow 8 Part 3, C. 1.
Dispersed 1463 copies, C. 1. 267 parts of Disperse Blue, 10 parts of locust bean glue, 7 parts of water
After printing the printing paste consisting of 7 parts, drying it and heating it in a high temperature steamer at 175q0 for 10 minutes,
Washed with water, hot water, reduced washing, water washed, and dried.

As a result, the comparative example using the printing paste prepared using the resist dye composition [c} had insufficient beam-proofing effect, and it was not possible to obtain a white beam-proofing product with commercial value. .

In addition, in a comparative example using a printing paste prepared using the beam-preventing agent composition a, coloring with copper was not possible unless strong acid washing (10 minutes with oxidized acid and 7 times 10 minutes) was performed after fixing the dye. It could not be removed, and an excellent white beam-proofing product could not be obtained by the above-mentioned ordinary washing with water, hot water washing, and reduction beam cleaning. On the other hand, in the present invention, which uses a printed paste base prepared using a beam-protecting agent composition {b holly to which potassium nitrite is added, an excellent white beam-protecting product can be obtained simply by passing through the above-mentioned washing process. In addition, the printing paste of the present invention [C. 1. By adding Disperse Orange 3 as a coloring dye, it was possible to obtain a colored beam with a clear orange pattern on a black background. Example 2 On a fabric made of 100% polyester fibers, printing paste and {B} prepared using resist dye compositions 'a} and {b' with the following formulations were printed in a pattern using a screen printing machine. Stamped.

Resistant composition Resistant followed by C.I. 1. A printing lake consisting of Disperse Blue 1138%, 8 parts of guar gum paste, and 84 parts of water was overprinted on the entire surface, dried, and then steamed for 6 minutes at 18,040 in a high-temperature steamer, followed by water washing, hot water washing, and reduction washing. , washed with water and dried.

As a result, by the method according to the present invention using a printing paste style, a brightly colored beam-proof product with a rich orange hue on a deep blue background was obtained. On the other hand, in the comparative example using the printing paste 'B-, it was not possible to obtain a clearly colored beam-proof product due to the coloring caused by copper.

Example 3 Using the beam-preventing agent composition 'b' of Example 2, a printing paste and 'B' having the following formulation were prepared, and a 100% cationic dye-beamable polyester fiber (Ceres C, Toyobo Co., Ltd.) was fabricated. A screen printing machine is used to print a pattern pattern on the top of the screen. 1. Dispersiero 8 2.5 parts, C
．． 1. Dispersed 1643 copies, C. 1. Overprint with a printing paste consisting of 1,137 parts of Disperse Blue, 6 parts of Locust Bean Gum-based sizing agent, 3 parts of Turben Oil Emulsion, and 78.5 parts of water, dry, and then use a high-temperature steamer at 170°C for 10 minutes. After steaming, it was washed with water, hot water, reduction washing, water, and dried.

As a result, excellent white resist dyed products were obtained by the method of the present invention.

On the other hand, in the comparative example, it was not possible to obtain an excellent white barrier beam due to the coloring caused by copper. Example 4 Beam-proofing glue of Example 2'
After printing B- in a pattern on a polyester fabric, C. 1
．． A printing paste consisting of Disperse Blue-1138%, 8 parts of guar gum paste, 5 parts of sodium nitrite, and 7 parts of water was overprinted, dried, and then steamed in a high temperature steamer at 180 qo for 6 minutes.

Claims (1)

[Claims] 1. In a method for resist dyeing textile products using a combination of water-soluble polyvalent metal salts and polyvalent metal hydroxides as resist dyes, an organic carboxylic acid is added to the resist dye paste, and the resist dye paste and/or
Or a resist dyeing method characterized by adding nitrites to the printing paste.