JPH0413472B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for resisting alkaline discharge printing of hydrophobic fibers. For more details, use formula (1) [In the formula, X represents a hydrogen atom, a methyl group, a methoxy group, a chlorine atom, a bromine atom, or an iodine atom] This invention relates to an alkaline discharge-proof printing method for hydrophobic fiber materials characterized by using a monoazo dye represented by the following formula. In recent years, in the dyeing process of hydrophobic fibers, especially polyester fibers, in order to increase the added value of dyed products, the use of anti-discharge dyeing methods, which can produce complex patterns, has become increasingly popular. Among these, alkaline anti-discharge printing using an alkaline agent as an anti-discharge agent is widely used due to its advantages such as less corrosion of equipment and lower cost for processing dyeing waste liquid compared to conventional reduction anti-discharge printing using tin or processed tin. It has become like that. Alkaline resist discharge printing requires a dye that becomes colorless with alkali (resist agent or discharge agent) or has a structure that does not show dyeing on hydrophobic fibers. In order for a dyed fabric subjected to anti-discharge printing to have satisfactory practicality, it is necessary to have sufficient fastness. By the way, the anti-discharge printing method involves printing resist dyeing paste on the yarn or cloth to be dyed to prevent the dye from adhering to that area, and then ground-dying it. It is distinguished from the discharge printing method, in which the dye in the printed area is solubilized or decolorized in a colorless form by printing.
Furthermore, there is a coloring resist dyeing method, in which a resist dye or a dye (insert dye) that is resistant to the discharge dye is mixed into resist dyeing paste or discharge dye paste, and the resist discharge dyed area is dyed the color of the insert color dye at the same time as resist discharge printing. It is called the colored discharge printing method, and the method of turning the resist discharge printing area white is called the white resist dyeing method or the white discharge printing method. Currently, the most common alkaline anti-discharge printing method is the anti-discharge method, but the discharge printing method is also increasingly being adopted. In the discharge printing method, the dye once dyed on the fiber is discharged (bleached), so it is required that the dye is more easily bleached or not dyed on the fiber than in the case of resist printing. However, the fact is that there are few dyes that have such excellent discharge printing properties, so there are limits to their use. An object of the present invention is to provide a dye for alkaline resist discharge printing which can provide excellent effects not only in resist dyeing methods but also in discharge printing methods. A monoazo compound obtained by coupling a diazotide of a benzene-based amine to a 1-substituted or unsubstituted 3-cyano-4-methyl-6-hydroxypyrid-2-one makes hydrophobic fibers, especially polyester fibers, durable. Furthermore, it is known that dyes can be dyed in deep yellowish colors, and most of the monoazo dyes of formula (1) used in the present invention are known from Japanese Patent Publication No. 24905/1983. As a result of a comparative study on the alkali-discharge resistance of these pyridone-based azo dyes, the present inventors found that the pyridone-based azo dye represented by formula (1) has significantly superior alkali-discharge resistance compared to other pyridone-based azo dyes. The present invention was completed based on the discovery that this shows the following. As shown in Table 1, it is clear that the dye represented by formula (1) is significantly superior in alkali discharge printing resistance compared to other pyridone-based azo dyes.

【table】

【table】

[Table] <Meaning of judgment grade> ◎...Excellent whiteness〇...Good whiteness with very slight coloring △...Poor whiteness with some coloring ×...Significant coloring Monoazo dyes represented by formula (1) are 2-nitroaniline, 2-nitro-4-methylaniline,
2-nitro-4-methoxyaniline, 2-nitro-4-chloroaniline, 2-nitro-4-bromoaniline, and 2-nitro-4-iodoaniline were diazotized by a known method to form 3-cyano-4-methyl. Obtained by coupling with -6-hydroxypyrid-2-one. In order to carry out discharge-proof printing of hydrophobic fibers using monoazo dyes represented by the formula (1), these dyes are mixed with a suitable dispersant such as a hommarine condensate of naphthalenesulfonic acid or an anionic dispersant such as ligninsulfonic acid, or Add a nonionic activator such as a block copolymer of ethylene oxide and propylene oxide or an ethylene oxide adduct of alkylphenol and a small amount of water, thoroughly wet-mill using a ball mill or sand mill, and then form a paste or dry it. something is put into use. Hydrophobic fibers to which the alkaline anti-discharge printing method of monoazo dye represented by formula (1) can be applied include polyester fibers, polyamide fibers, cellulose diacetate fibers, cellulose triacetate fibers, and the like. Next, a method for carrying out alkaline resist printing or alkaline discharge printing of hydrophobic fibers, particularly polyester fibers, using the monoazo dye of formula (1) will be explained. A resist dyeing paste consisting of an alkaline resist dye and other auxiliary agents is printed in a desired pattern on a fabric that has been applied with the micronized dye of formula (1) by a pad method or a printing method and then subjected to intermediate drying, followed by printing at high temperature and high pressure. Apply steaming or high temperature steaming (alkaline white resist dyeing). Further, a discharge printing paste consisting of an alkaline discharge printing agent and other auxiliary agents is printed in a desired pattern on a fabric that has been ground-dyed with the monoazo dye of formula (1) by a method known per se, followed by high-temperature, high-pressure steaming or high-temperature steaming. Apply teaming (alkaline white discharge printing). In either method, a bleached dyed fabric with a yellow or orange ground color and a pattern with excellent whiteness can be obtained. In this case, the alkaline discharge printing agent may be a base exhibiting a pH value of at least 8 in a 5% aqueous solution, such as alkali and alkaline earth metal hydroxides (sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.), alkali metal hydroxides, etc. Examples include salts with inorganic weak acids (sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.), salts of alkali metals with organic acids (sodium acetate, etc.), alumonia or aliphatic amines (triethylamine, etc.), and these may be used alone or in combination. Two or more types can be used in combination. Further, by mixing an alkali-resistant insert dye into the above-mentioned removal-proof paste, alkali-colored resist dyeing and alkali-colored discharge printing are performed. In either method, a dyed fabric with a pattern of the color of the insertion dye on a yellow or orange background color is obtained. Examples of alkali-resistant insertion dyes that can be used in the above-mentioned colored resist discharge printing include the following. Polyamide fibers, cellulose diacetate fibers, and cellulose triacetate fibers can also be subjected to alkaline discharge printing using the dye of formula (1) in the same manner as in the case of polyester fibers. Next, the present invention will be specifically explained using examples. In addition, all parts indicated as "example middle" are parts by weight. Example 1 3 parts of the compound of formula (2), 4 parts of Demol N (manufactured by Kao Atlas Co., Ltd., an anionic dispersant) and Demol C (manufactured by Kao Atlas Co., Ltd.)
The mixture was crushed with 3 parts in a wet state for 5 hours, and then dried to obtain a finely divided dye. A colored paste having the following composition was prepared using this finely divided dye. This colored paste was overprinted on Tetron cloth, and intermediate drying was performed at 80°C for 3 minutes. Subsequently, an alkaline resistance dyeing paste having the following composition was printed using a polka dot screen, and after intermediate drying was performed again at 80°C for 3 minutes, steaming was performed using superheated steam at 175°C for 7 minutes. Then wash with water, hot water,
After reduction washing and drying, a dyed (resist dyed) cloth with a pure white polka dot pattern on a yellow background was obtained. <Color paste> Micronized dye of Γ formula (2)... 3 parts Γ Faingum MC-8 (manufactured by Daiichi Kogyo Seiyaku) 7% Γ Sorbitose C-8 (manufactured by Skolten) 4.5% Citric acid 0.33% Improver 880 (manufactured by Yokohama Polymer) 3.3% and water (84.9%) base glue...60 parts Γwater...37 parts total 100 parts <Alkaline resist dyeing paste> Sodium Γ carbonate 5 parts Γ Color Fine AD (No. 1) (manufactured by Kogyo Seiyaku) 10 parts ΓFine Gum D-2514 (manufactured by Daiichi Kogyo Seiyaku) 20% and water (80%) 60 parts Γwater 25 partsTotal 100 partsThe compound of formula (2) is as follows. It was synthesized as follows.
7.6 parts of 2-nitro-3-methylaniline was added to a solution consisting of 29.5 parts of concentrated hydrochloric acid and 75 parts of ice water, and a solution of 3.6 parts of sodium nitrite dissolved in 25 parts of water was gradually added dropwise at a temperature below 5°C. After stirring for about 2 hours, excess nitrite ions were removed with sulfamic acid to obtain a transparent diazo liquid. After completely dissolving 7.5 parts of 3-cyano-4-methyl-6-hydroxypyrid(2)-one in a solution of 10 parts of caustic soda dissolved in 150 parts of water at 50 to 55°C, The diazo solution was gradually added dropwise while stirring. The obtained crystals were separated and dried to obtain 14.9 parts (95.3% of the theoretical amount) of a monoazo compound represented by formula (2).
This one has λmax (75% acetone in water) 448nm,
It showed mp290-292℃. Example 2 In the same manner as in Example 1, a finely divided dye of the compound of formula (3) was obtained. Three parts of this dye were added to 3,000 parts of water, and the pH was adjusted to 5 with acetic acid and sodium acetate. 100 parts of Tetoron cloth was immersed in this dye solution and dyed at 130°C for 1 hour. Then, the cloth was washed with water, reduced, and dried to obtain an orange dyed cloth. This dyed fabric was printed with an alkaline discharge printing paste having the following composition using a polka dot screen, and after intermediate drying, steaming was performed at 180° C. for 8 minutes using superheated steam. After washing with water, hot water, reduction washing, and drying, a dyed (discharged) cloth with a pure white polka dot pattern on an orange background was obtained. <Alkaline discharge printing paste> Sodium carbonate 3 parts Sodium hydroxide 2 parts Dicyandiamide 2 parts Original paste consisting of 20% Fine Gum D-2514 and water (80%) 70 parts Color Fine AD 10 parts Dispaint PC (manufactured by NICCA Chemical Co., Ltd.) 5 parts Water 8 parts Total 100 parts The compound of formula (3) was synthesized in substantially the same manner as the compound of formula (2) using 2-nitro-4-methoxyaniline. This one is λmax (75% acetone in water)
It showed 468nm, mp256-257℃. Example 3 A finely divided dye of the compound of formula (4) was obtained in the same manner as in Example 1. Using this dye, a pad solution was prepared with the following composition, and an alkaline resist dye paste was prepared with the following composition. First, soak the Tetron diose cloth in the above-mentioned pad solution, squeeze it to 80% with a mangle, and then
Intermediate drying was performed at 80°C for 3 minutes. Next, the above-mentioned alkaline resist printing paste was printed on this cloth using a floral pattern screen, and after intermediate drying was performed again at 80°C for 3 minutes, high temperature steaming was performed at 175°C for 7 minutes. After washing with water, hot water, reduction washing, and drying, a colored resist-dyed fabric with a red floral pattern on a yellow background was obtained. <Pad solution) Micronized dye of Γ formula (4) 40 parts Γ Snow Algin SSL (manufactured by Tomito Chemical) 1 part Γ citric acid 2 parts Γ Succinol CS-K (manufactured by Nippon Someka) 0.5 part Γ water Balance total 1000 Part <Alkaline resist dyeing paste> ΓSumikaron Brilliant Red S-BF (manufactured by Sumitomo Chemical) (dye that does not decompose with alkaline agents or lose its dyeing ability) 4 parts ΓFain Gum D-2514 20% and water (80%) Base paste consisting of 55 parts Γ Sodium carbonate 5 parts Γ Colorfine AD 10 parts Γ Water 26 parts Total 100 parts The compound of formula (4) is a compound of formula (2) using 2-nitro-4-chloroaniline. It was synthesized in almost the same way. This one is λmax (75% acetone in water)
438nm, mp3 showed over 10℃. Example 4 A finely divided dye of the compound of formula (5) was obtained in the same manner as in Example 1. Using this dye, a yellow dyed cloth was obtained by the dyeing method described in Example 2. Print an alkaline discharge paste with the following composition on this dyed cloth using a floral pattern screen, and after intermediate drying,
Steaming was carried out using superheated steam for 1 minute. After similar post-treatment operations, a colored discharge-printed fabric with a red floral pattern on a yellow background was obtained. <Alkali resist dye paste> Γ Sumikaron Brilliant Red S-BF 4 parts Γ Sodium carbonate 3 parts Γ Sodium hydroxide 2 parts Γ Dicyandiamide 2 parts Γ Fine gum D-2514 Base paste consisting of 20% and water (80%) 70 parts Γ Colorfine AD 10 parts Γ Dispaint 5 parts Γ Water 2 parts Total 100 parts The compound of formula (5) was synthesized in substantially the same manner as the compound of formula (2) using 2-nitro-4-chloroaniline. . This one is λmax (75% acetone in water)
It showed 443nm, mp296-297℃. Example 5 In the same manner as in Example 1, Tetron cloth was subjected to alkali white resist dyeing using the compound of formula (6). A dyed cloth with a pure white polka dot pattern on a yellow background was obtained. The compound of formula (4) was synthesized using 2-nitro-4-iodoaniline in substantially the same manner as the compound of formula (2). This one is λmax (75% acetone in water)
Decomposed at 446nm and 230℃.

Claims (1)

[Claims] 1 Formula (1) [In formula (1), X represents a hydrogen atom, a methyl group, a methoxy group, a chlorine atom, a bromine atom, or an iodine atom.] An alkaline anti-discharge printing method for hydrophobic fiber materials, characterized by using a monoazo dye represented by the following: