JPH0135954B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing cellulose fibers in bright yellow. More specifically, the present invention, in the form of a free acid, has the following general formula:
(1) [In the formula, R ₁ is a cyclohexyl group or alkyl,
a benzyl group optionally substituted with alkoxy, halogen or amino group, or phenethyl group,
R ₂ represents a hydrogen atom, a cyano group, a carbamoyl group or a sulfoalkyl group, R ₃ represents a hydrogen atom or a sulfonic acid group, X ₁ represents a hydrogen atom or a methoxy group, X ₂ represents a hydrogen atom, a chlorine atom, a methyl group,
Represents a methoxy group, carboxyl group or sulfonic acid group; when X ₁ is a hydrogen atom, X ₂ is a hydrogen atom,
It is a chlorine atom, methyl group, methoxy group, carboxyl group or sulfonic acid group, and when X ₁ is a methoxy group, X ₂ is a methyl group or a methoxy group.
Y represents -CH= _CH2 or _{-CH2CH2Z ,} Z represents a halogen atom, _-OSO3H or _{OPO3H2 .} ] This is a method for dyeing cellulose fibers, which is characterized by using the dye shown below. It is known that dyes having a β-sulfatoethylsulfonyl group can be applied as so-called vinylsulfone type reactive dyes for dyeing textile materials.
However, dyeings made with azo-based yellow reactive dyes having a β-sulfatoethylsulfonyl group generally have low chlorine fastness, and fading due to chlorine contained in tap water is often a problem. There has been a strong demand for a yellow reactive dye with excellent strength. Yellow dyes with a monochlorotriazinyl group as another typical reactive group different from the β-sulfatoethylsulfonyl group are also known, but these reactive dyes generally require high dyeing temperatures. However, since it lacks exhaust dyeability, it is only used for textile printing, and the resulting dyed product has the disadvantage of low acid stability, so it is by no means sufficient for practical use. Nakatsuta. For this reason, the present inventors conducted extensive research in search of a yellow vinyl sulfone type reactive dye with particularly excellent chlorine fastness.
It has been found that monoazo dyes having a -sulfatoethylsulfonyl group and a monohalogenotriazinyl group give bright yellow dyeings with excellent chlorine fastness. It has also been found that the dye of the present invention can overcome the drawbacks of reactive dyes having a monochlorotriazinyl group as described above. In the present invention, the cellulose fibers include natural or regenerated cellulose fibers such as cotton, linen, viscose human silk, and viscose cotton. In the case of the exhaust method, the dyeing of the present invention is carried out at a relatively low temperature in a dye bath containing Glauber's salt or common salt in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate, or caustic soda. Dyeing can also be done by a textile printing method. For example, a color paste containing an acid binder such as bicarbonate of soda, soda carbonate, tribasic sodium phosphate, or caustic soda, urea, and a sizing agent, preferably sodium alginate, is printed on the fiber, and after intermediate drying, 100% This is done by steaming or drying at ~200°C. Furthermore, the dyeing according to the invention may be carried out by a continuous method. In addition, the cold butt-up dyeing method, which has recently attracted attention as an energy-saving dyeing method, is used.
Cellulose fibers are immersed in a solution of the dye of the present invention dissolved in water in the presence of an acid binder such as soda carbonate, caustic soda, or tribasic sodium phosphate, and mirabilite or common salt, and then squeezed by a known method to make the fibers. It can also be carried out by leaving it at room temperature for 3 to 48 hours and dyeing. The dye of the present invention can be produced, for example, as follows. After primary condensation of 2,4-diaminobenzenesulfonic acid or 2,4-diaminobenzene-1,5-disulfonic acid and cyanuric chloride, diazotization is performed by a conventional method to obtain the general formula () (In the formula, R ₁ and R ₂ have the above-mentioned meanings.) For example, as R ₁ , a cyclohexyl group, a benzyl group, a p-chloro or a bromobenzyl group, a 2,4-dichlorobenzyl group, etc. halogen-substituted benzyl group, p-methyl,
Ethyl, propyl or butylbenzyl group, m-
methyl or ethylbenzyl groups, alkyl-substituted benzyl groups such as 2,4- or 3,5-dimethylbenzyl groups, p-methoxy, ethoxy, propioxy or butoxybenzyl groups, O- or m-
Alkoxy-substituted benzyl groups such as methoxybenzyl groups, nitro-substituted benzyl groups such as O-, m- or p-nitrobenzyl groups, p-dimethylamino, diethylamino, (N,N-ethylcyanoethyl)amino or bis(2 -methoxyethyl)
amino-substituted benzyl groups, such as aminobenzyl groups,
4-methyl-3-nitrobenzyl group, 2-chloro-4-nitrobenzyl group, 8-diethylamino-
4-methylbenzyl group, α-methyl or ethylbenzyl group, phenethyl group, p-methyl, ethyl,
Methoxy or chlorophenethyl group, phenethyl group such as β-methylphenethyl group, etc., hydrogen atom as R ₂ , sulfoalkyl group such as cyano group, carbamoyl group, sulfomethyl group, sulfoethyl group, α-methyl or ethylsulfomethyl group, etc. It is coupled with a pyridone derivative having typical substituents. Then, the general formula () Aniline compounds represented by ₍ wherein X ₁ , -(vinylsulfonyl)aniline, O-,
m- or p-(β-chloroethylsulfonyl)
Aniline, O-, m- or p-(phosphooxyethylsulfonyl)aniline, 4-methoxy-3-
(β-sulfoxyethylvinyl, β-chloroethyl or β-phosphoxyethylsulfonyl)aniline, 2-methoxy-5-(β-sulfoxyethyl, vinyl, β-chloroethyl or β-phosphoxyethylsulfonyl)aniline, 2 -Methoxy-5-methyl-4-(β-sulfoxyethyl, vinyl, β-chloroethyl or β-phosphooxyethylsulfonyl)aniline, 2,5-dimethoxy-4-(β-sulfoxyethyl, vinyl, β- Chlorethyl or β-phosphoxyethylsulfonyl)aniline, 2-carboxy-5-(β-sulfoxyethyl, vinyl, β-chloroethyl or β-phosphoxyethylsulfonyl)aniline, 2
-chloro-4-(β-sulfoxyethyl, vinyl,
A dye represented by the general formula () can be obtained by secondarily condensing an aniline compound, typical examples of which are β-chloroethyl or β-phosphoxyethylsulfonyl)aniline. Alternatively, cyanuric chloride, 2,4-diaminobenzenesulfonic acid or 2,4-diaminobenzene-1,5-disulfonic acid, and an aniline compound represented by the general formula () are condensed in any order,
General formula () (In the formula, X ₁ , X ₂ , R ₃ , and Y have the above-mentioned meanings.) Obtaining a compound represented by the formula, diazotizing it by a conventional method, and coupling it with a pyridone derivative represented by the general formula () However, dyes of general formula () can be obtained. Alternatively, the general expression () (In the formula, X _{1 and} or phosphoric acid to form the general formula () (Y is -CH ₂ CH ₂ OSO ₃ H or -
_{CH2CH2OPO3H2 means . _} ) may also be used as a dye. The dye of the present invention thus obtained is particularly excellent in chlorine fastness, light fastness, and sweat/sunlight fastness. Especially considering that the use of chlorine bleach in household laundry has recently become widespread, the value of the dye of the present invention, which has excellent chlorine fastness, is high. Its excellent light fastness and sweat/sunlight fastness make it suitable for dyeing external wear such as sportswear. Furthermore, since the dye of the present invention exhibits a high exhaustion rate and fixation rate during exhaust dyeing, it is possible not only to obtain dyed products with high density, but also to have excellent wash-off properties, making it easy to remove unfixed dyes. It has the great advantage of being able to Furthermore, the dye of the present invention has the unique ability to be hardly affected by changes in the dyeing temperature, alkali agent, inorganic salt addition amount, and bath ratio during exhaust dyeing, and allows dyeing to be carried out with extremely high reproducibility. As a dye similar to the present invention, for example,
Publication No. 39-18184 states the following: The yellow reactive dye shown is described. However, the chlorine fastness of these dyes is very low, being grade 1 according to the ISO method, and their practical value is small. On the other hand, the yellow dye of the present invention has an excellent chlorine fastness of 2nd to 3rd grade or 3rd grade according to the ISO method.
Moreover, the light fastness is 5th to 6th grade, and the sweat and sunlight fastness is 4th grade or 4th to 5th grade, which are both excellent. Furthermore, with conventional reactive dyes, there was a phenomenon in which the dyed product was affected by acidic gases in the air and its fastness decreased over time, but the dye of the present invention has solved this problem. There is. That is, the acid stability of the dyed product of the dye of the present invention (the test method is to immerse the dyed fabric in 1% acetic acid for 30 minutes, and then treat it with 125 g/cm ² for 6 hours at a temperature of 37 ± 2°C using a perspirometer. ) is good at grade 4-5 or grade 5,
It has great value from this point of view as well. Next, the method of the present invention will be explained with reference to examples. In the text, parts represent parts by weight. Example 1 Dissolve 0.3 parts of the dye shown in 200 parts of water and add mirabilite.
Add 20 parts, add 10 parts of cotton, and raise the temperature to 50℃.
After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping yielded a yellow dyed product with excellent fastness, especially fastness to chlorine. The above dye is synthesized, for example, as follows. To a solution in which 0.1 part of a nonionic surfactant is dissolved in 100 parts of water, 9.2 parts of cyanuric chloride is added and dispersed at 0 to 10°C. A solution prepared by dissolving 10.5 parts of sodium 2,4-diaminobenzenesulfonate in 100 parts of water is added dropwise to this at 0 to 5°C over 1 hour. After the dropwise addition is complete, add a 20% aqueous sodium carbonate solution to adjust the pH to 7-8. Then sodium nitrite
Add 3.5 parts to dissolve and diazotize by injecting 12.7 parts of concentrated hydrochloric acid at 0 to 5°C. Add this diazo suspension to a suspension of 11.5 parts of 3-cyano-1-cyclohexyl-6-hydroxy-4-methyl-2-pyridone and 100 parts of water, adjusted to pH = 5 to 6 with an aqueous solution of caustic soda. , add another 5 parts of sodium bicarbonate and stir until coupling is complete. Next, 16.9 parts of 1-aminobenzene-3-β-hydroxyethylsulfone sulfate was added, and the pH was adjusted.
The temperature was raised to 40°C while adjusting the temperature to 5-6, and the mixture was stirred at the same temperature for 5 hours. Add 60 parts of sodium chloride to this solution to precipitate crystals, suction, wash, and then hold at 60°C.
Dye (1) was obtained by drying. Example 2 Dissolve 0.3 parts of the dye shown in 200 parts of water and add mirabilite.
Add 20 parts, add 10 parts of cotton, and raise the temperature to 40℃.
Then, after 20 minutes, 3 parts of tribasic sodium phosphate is added. Dye for 1 hour at that temperature. After dyeing,
After washing with water and soaping, a greenish-yellow dyed product with excellent fastness, especially chlorine fastness, was obtained. Example 3 Dissolve 0.3 parts of the dye shown in 200 parts of water and add mirabilite.
Add 20 parts, add 10 parts of cotton, and raise the temperature to 50℃.
After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping yielded a greenish-yellow dyed product with excellent fastness, especially fastness to chlorine. Example 4 When dyeing was carried out using the following dyes (4) to (20) in the same manner as in Example 1 or 2, greenish-yellow to yellow dyed products with excellent chlorine fastness were obtained. (In the formula,

【ceremony

Represents [formula]. ) Example 5 Composition of colored paste 5 parts urea 5 parts sodium alginate (5%) Paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts The colored paste having the above composition is mercerized Print on cotton broadcloth, and after intermediate drying, steam at 100℃ for 5 minutes, wash with hot water, soap, wash with hot water, and dry. In this way, a yellow print with excellent chlorine fastness was obtained. Example 6 30 parts of a dye having the structure of formula (1) are dissolved in 925 parts of hot water and cooled to room temperature (approximately 20°C). Next, 15 parts of a 32.5% aqueous solution of caustic soda and 30 parts of Glauber's salt are added to prepare a liquid composition. A cellulose fabric is dipped in this solution, and the squeezing rate is 65% using a known method.
Aperture and hudge. After the padded cellulose fabric is rolled up, it is sealed with polyethylene film or the like and left at room temperature (approximately 20°C) for 20 hours. The cellulose fabric is then washed in cold water, then in hot water, soaped in a boiling detergent solution, washed in cold water, and dried for finishing. This gave a very deep yellow, spot-free dyeing.

Claims (1)

[Claims] 1 The following general formula () in the form of a free acid: [In the formula, R ₁ is a cyclohexyl group or alkyl,
a benzyl group optionally substituted with alkoxy, halogen or amino group, or phenethyl group,
R ₂ represents a hydrogen atom, a cyano group, a carbamoyl group or a sulfoalkyl group, R ₃ represents a hydrogen atom or a sulfonic acid group, X ₁ represents a hydrogen atom or a methoxy group, X ₂ represents a hydrogen atom, a chlorine atom, a methyl group,
Represents a methoxy group, carboxyl group or sulfonic acid group; when X ₁ is a hydrogen atom, X ₂ is a hydrogen atom,
It is a chlorine atom, methyl group, methoxy group, carboxyl group or sulfonic acid group, and when X ₁ is a methoxy group, X ₂ is a methyl group or a methoxy group.
Y represents -CH= _CH2 or _{-CH2CH2Z ,} Z represents a halogen atom, _-OSO3H or _{OPO3H2 .} ] A method for dyeing cellulose fibers, characterized by using the dye shown below.