JPH0419272B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a formazan compound and a method for dyeing cellulose fibers using the same. More specifically, in the free acid form, formula (1) [In formula (1), X is

[Formula] (R ₁ and R ₂ each independently represent hydrogen, a halogen atom, a nitro group, a carboxyl group, a sulfonic acid group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxyl group);

[Conventional technology]

In general, metal-containing formazan dyes are widely used because they give vivid color tones of dyed products and have excellent fastness, especially fastness to sunlight and sweat. Among formazan-based reactive dyes, those whose reactive group is a cyanuric chloride group have better PH stability in dye baths and color paste stability in printing, and excellent level dyeing properties, compared to those whose reactive group is a vinyl sulfone group. The advantage is that it is easy to obtain dyed products. Although Japanese Patent Publication No. 38-5041 describes dyes similar to the compounds of the present invention, the dyes described in the same publication have the disadvantage of poor fixing and build-up properties. Furthermore, the dye described in JP-A-51-88518 which has a monofluorotriazine group as a reactive group has an optimum dyeing temperature of around 50 DEG C., but has the drawback that level dyeing properties are not sufficient. [Problems to be solved by the invention] Recently, energy saving has been emphasized in the dyeing industry, and for economic reasons, the optimum dyeing temperature (dip dyeing method ) is desired. The present inventors conducted intensive research to find a dye that does not have the above-mentioned drawbacks and also meets the demand for energy saving. As a result, the formazan compound represented by formula (1) has good color fastness and is energy saving. The inventors have discovered that this dye is suitable for the needs of the industry and has high fixation and build-up properties, leading to the present invention. In order to obtain the formazan compound represented by the formula (1) of the present invention, first, the formazan compound represented by the formula (2) is [In formula (2), R and M have the same meanings as above. ] The formazan amino compound represented by is synthesized by the method described below. That is, diazotized 6-acetylamino-2
-aminophenol-4-sulfonic acid with formula (3) (In formula (3), R represents the same meaning as above) Represented by formula (4) obtained from a compound represented by It is coupled to 5-sulfo-2-carboxyphenylhydrazone, then treated with a metallizing agent such as copper acetate, copper chloride, copper sulfate, nickel sulfate, or nickel chloride, and then the acetylamino group is hydrolyzed to form an amino group. By doing so, a formazan amino compound of formula (2) is obtained. Using the formazan amino compound thus obtained, a formazan compound of formula (1) is produced, for example, according to the method described below. Formazan amino compound 1 represented by formula (2)
moles of 2,4,6-trichloro-1,3,5
-Reacted with 1 mole of triazine to form formula (5) (In formula (5), R and M have the same meanings as above.) Obtain the condensate, and then add 1 mole of alcohol or phenol represented by Condense. Formazan amino compound 1 represented by formula (2)
Molar formula (6) It is condensed with 1 mol of a compound represented by formula (6), in which X has the same meaning as above. A conventional separation method such as an acid precipitation method or a salting out method is applied to separate the target product thus obtained from the reaction solution. Next, R and X in formula (1) will be explained using a specific example. R is hydrogen, sulfonic acid group, hydroxyl group, bromine, chloro, fluorine, methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, methoxy group, ethoxy group, propoxy group, butyroxy group, Carboxyl group, etc. Specific examples of X include phenoxy group, (2-, 3-, or 4-chloro) phenoxy group, (2-, 3-, or 4-methyl) phenoxy group, (2- , 3-, or 4-sulfo) phenoxy group, (2-, 3-, or 4-carboxy) phenoxy group, (2-, 3-, or 4-
methoxy) phenoxy group, (2-, 3-, or 4
-hydroxy) phenoxy group, (2-, 3-, or 4-ethoxy) phenoxy group, (2-, 3-,
or 4-bromo)phenoxy group, (2-,3-,
or 4-fluoro)phenoxy group, (2-,3-,
or 4-ethyl) phenoxy group, cyclohexanoxy group,

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] Methoxy group, ethoxy group, propoxy group,
HOCH ₂ CH ₂ O−, HOOCCH ₂ O−,
HO ₃ SH ₂ CH ₂ CO−, H ₃ CH ₂ COH ₂ CH ₂ CO−,
H ₃ COH ₂ CH ₂ CO−, H ₃ COH ₂ CH ₂ CH ₂ CO−,

【formula】

【formula】

〔Effect of the invention〕

The formazan compound (dye) of the present invention has high dye stability when prepared as a printing paste or padding bath, and there is little concentration fluctuation in dyed products due to changes in steam heat or dry heat treatment conditions in printing methods and padding dyeing methods. High fixation rate similar to the dyeing method,
Indicates build-up ability. The dyed product obtained is lightfast,
It has excellent fastness to sweat, light, water, and chlorine water, and exhibits a purple to blue hue. In addition, when subjected to a textile printing method, the white area staining property is good. [Example] Next, the present invention will be explained in detail with reference to Examples. In the examples, parts represent parts by weight, and sulfonic acid groups and carboxyl groups in each formula are represented in the form of free acids. Example 1 Add 4.92 parts of 3-acetylamino-5-amino-4-hydroxybenzenesulfonic acid to 20 parts of water and 30 parts of ice.
Part, 10% Liponox NA (manufactured by Lion Yushi Co., Ltd.,
Dispersant) Add to a solution consisting of 0.5 part while stirring,
Next, the mixture was completely dissolved in a 48% liquid caustic soda solution at a pH value of 6 to 7. Thereafter, 5.0 parts of concentrated hydrochloric acid was added to precipitate crystals, which were suspended at the same time, and an aqueous solution of 1.4 parts of sodium sulfite dissolved in 10 parts of water was added dropwise to this suspension for 1 hour while maintaining the temperature below 10°C. A diazotization reaction was performed. Next, in this diazotization reaction solution, 2
-benzylidenehydrazino-4-sulfobenzoic acid
Completely dissolve 6.4 parts in 30 parts of water with a pH value of 6 to 8, and add 5.3 parts of copper sulfate pentahydrate to a solution with a pH value of 6 to 10℃ below 10℃.
The mixture was stirred and reacted for 3 hours while maintaining the temperature of 8. Add 30 parts of 48% liquid caustic soda solution to this reaction solution,
The mixture was heated to 90 to 95°C and treated (hydrolyzed) at the same temperature for 4 hours to obtain a reaction solution containing the following formazan amino compound. On the other hand, add 3.7 parts of cyanuric chloride to 20 parts of water, 40 parts of ice,
Cyanuric chloride was suspended in a solution of 0.5 parts of 10% Liponox NA aqueous solution and stirred for 30 minutes. To this suspension was added 2.15 parts of o-cresol in 40 parts of water, and a solution of caustic soda was added. PH value 9~
The solution prepared as No. 10 was poured over 30 minutes while maintaining the pH value of 6 to 8 and the temperature of 10° C. or less. then 10
Adjust the pH value to 6 to 8 with a 10% soda ash aqueous solution at around ℃.
The mixture was stirred for 5 hours while maintaining the temperature. This reaction solution was added to the reaction solution containing the formazan amino compound at PH.
The mixture was poured at a temperature of 30 to 40°C while maintaining a value of 6 to 8, and the reaction was allowed to proceed at the same temperature for 2 hours. Then, the mixture was salted out with sodium chloride at the same temperature, and the crystals were filtered off. It was dried under reduced pressure at 30°C to obtain 24.5 parts of the compound of formula (9). (λmax624nm 20% pyridine aqueous solution) Example 2 A dye bath was prepared using 2 parts of the compound of formula (9) obtained in Example 1, 80 parts of sodium chloride, and 898 parts of water.
Dip 50 parts of cotton stockinette into this dye bath and dye at 50℃ for 30 minutes.
After treating for 1 minute, 20 parts of sodium carbonate was added, followed by treatment at the same temperature for 60 minutes to carry out dyeing.
Then, after washing with water, an aqueous solution containing 2 parts of anionic activator
Using 1000 parts, soaping was carried out at 95 to 100°C for 10 minutes, followed by washing with water and drying to obtain a clear blue dyed product with good level dyeing properties. This item is light resistant,
It had excellent wet and chlorine water fastness. Examples 3 to 37 Compounds were synthesized according to Example 1, and cotton was dyed according to Example 2. Table 1 shows the structural formula of the synthesized compound, the hue when dyed on cotton, and the λmax of the compound in a 20% aqueous pyridine solution.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Example 47 30 parts of the compound of formula (9) described in Example 1, 100 parts of urea
Cotton gearbagsin was padded in a pad bath consisting of 20 parts of anhydrous sodium carbonate, 2 parts of sodium alginate, and 848 parts of water, squeezed to a squeezing rate of 70%, and then dried at 100°C for 2 minutes. Dry heat treatment was performed. Next, the dyed product was washed with water and soaped in the same manner as in Example 2, washed with water, and dried to obtain a blue dyed product with excellent fastness. Example 48 1000 parts of colored paste having the following composition was prepared using the compound of formula (10).

[X represents 10, 30 and 60, Polymin Lnew is a reduction inhibitor manufactured by Nippon Kayaku. ]

The colored paste was printed on mercerized cotton broadcloth, dried at 100°C for 3 minutes, steamed in saturated steam at 100°C for 5 minutes, and then washed with water. Next, after washing with warm water at 60° C. for 5 minutes, soaping was performed for 15 minutes using 1000 parts of a boiling bath containing 2 parts of an anionic surfactant, followed by washing with water. By drying the print, a bright blue print with excellent build-up properties was obtained. [Comparative Test] A comparative test of fixing properties of the compound of the present invention and known dyes was carried out by the following method. 50 parts of unsilced cotton stockinette was immersed in a dye bath prepared from 1 part of the compound or dye, 80 parts of anhydrous sodium sulfate, and 899 parts of water, and treated at 50°C for 30 minutes. Staining was carried out for 60 minutes at temperature. The dyed product was washed with water and hot water, then soaped in the same manner as in Example 2, washed with water, and dried. The following table shows a concentration comparison using the compound of Example 1 of the present invention as a standard.

【table】

[Table] As is clear from the table, it is recognized that the compounds of the present invention have extremely high visual density of dyed products and extremely excellent fixing properties compared to dyes having structures similar to the compounds of the present invention.

Claims (1)

[Claims] 1 Formula (1) in the form of free acid [In formula (1), X is [Formula] group (R ₁ and R ₂ are each independently hydrogen, halogen atom,
Represents a nitro group, carboxyl group, sulfonic acid group, methyl group, ethyl group, methoxy group, ethoxy group, or hydroxyl group. ); [Formula] Alkoxy group having 1 to 3 carbon atoms which may be substituted with a carboxyl group, hydroxyl group or sulfonic acid group; 3 carbon atoms
-6 alkoxyalkoxy group; naphthol group having 1 to 3 sulfonic acid groups; represents a benzyloxy group which may be substituted with a sulfonic acid group,
R is hydrogen, a sulfonic acid group, a hydroxyl group, bromo, chloro, fluorine, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carboxyl group,
M represents copper or nickel, respectively. ] A formazan compound represented by 2 Formula (1) in free acid form [In formula ( _{1 )} , ); [Formula] Alkoxy group having 1 to 3 carbon atoms which may be substituted with a carboxyl group, hydroxyl group or sulfonic acid group; 3 to 6 carbon atoms
an alkoxyalkoxy group; a naphthol group having 1 to 3 sulfonic acid groups; a benzyloxy group which may be substituted with a sulfonic acid group; R is hydrogen, a sulfonic acid group, a hydroxyl group, bromo, chloro,
Fluorine, alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
4 represents an alkoxy group or a carboxyl group, and M represents copper or nickel, respectively. ] A dyeing method for cellulose fibers characterized by using a formazan compound represented by the following.