JPH0450946B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a formazan compound and a method for dyeing cellulose fibers using the same. ``Prior art'' Metal-containing formazan dyes have the advantage that the color tone of the dyed products produced by them is clear and their fastness is excellent, especially in sunlight and sweat. Compared to those whose reactive group is a vinyl sulfone group,
Cellulose is a metal-containing formazan reactive dye that has the advantages of good dye bath pH stability, good color paste stability during printing, and the ability to easily obtain dyed products with excellent level dyeing properties. It is preferably used for dyeing fibers. Tokuko Showa 36-13834,
There are various patents for monohalogen-triazine reactive dyes having substituents with etherified hydroxylation on the triazine nucleus, as typified by Japanese Patent Publication No. 38-3933. There are no examples of reactive dyes having a structure linked via two or more ether bonds. On the other hand, JP-A No. 48-94730 describes a formazan compound using a diamino compound as a linking compound, but the dye described therein has poor color value and build-up properties when dyeing medium-dark colors, and has poor light fastness. It has the disadvantage of insufficient fastness. ``Problems to be Solved by the Invention'' It is desired to develop a metal-containing formazan-based reactive dye that has good color value, good build-up properties, and excellent light fastness. "Means for Solving the Problems" The present inventors have conducted intensive research to develop a metal-containing formazan compound that does not have the above-mentioned drawbacks, and as a result, have arrived at the present invention. The present invention provides the formula (1) in the free acid form. [In formula (1), X is

[Formula] (R ₁ represents hydrogen, a halogen group, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, or an alkoxy group having 1 to 4 carbon atoms);

[Formula] (R ₂ and R ₃ are each independently hydrogen and chlorine, Q is O, S, SO ₂ ,
CH ₂ , C (represents CH ₃ ) ₂ ); -O- (CH ₂ CH ₂ )
represents n-O- (n represents 1 or 2), R
is hydrogen, a sulfonic acid group, a hydroxyl group, chloro, fluorine, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carboxyl group, and M is copper or nickel, respectively. The method involves producing a dye and using it to dye cellulose fibers. 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 A formazanamino compound represented by [Formula (2), R and M have the same meanings as above] is synthesized by the method described below. That is, diazotized 6-acetylamino-2-
Aminophenol-4-sulfonic acid is expressed by formula (3) (In formula (3), R represents the same meaning as above) Represented by formula (4) obtained from a compound represented by Formula (2) is obtained by coupling to 5-sulfo-2-carboxyphenylhydrazines, then reacting with copper sulfate, nickel sulfate, copper chloride, nickel chloride, etc., and then hydrolyzing the acetylamino group.
of formazan amino compound is obtained. Using the formazan amino compound thus obtained,
For example, the formazan compound of formula (1) is synthesized according to the method described below. The formazan amino compound represented by formula (2) is reacted with 1 mole of 2,4,6-trichloro-1,3,5-triazine to form formula (5). A condensate represented by formula (6) was obtained, and then reacted with 1 mol of a dihydroxy compound represented by XH H (X represents the same meaning as above). An intermediate product represented by is obtained, and then reacted with 1 mol of a compound represented by the above formula (5). Alternatively, formula (6) and 2,4,6-trichloro-
By reacting with 1 mol of 1,3,5-triazine, formula (7) An intermediate product represented by the above may be obtained, and this may be reacted with 1 mol of a formazan amino compound represented by the formula (2). Formula (8) obtained by reacting 2 moles of 2,4,6-trichloro-1,3,5-triazine with 1 mole of a dihydroxy compound represented by XH H (X represents the same meaning as above) Two moles of the formazan amino compound represented by formula (2) are condensed with the compound represented by formula (2). 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 with specific examples. As R, hydrogen, sulfonic acid group, hydroxyl group, chloro, methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, methoxy group, ethoxy group, propoxy group, butyloxy group, carboxyl group, etc. Regarding X,

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-O-(CH ₂ CH ₂ ) ₂ 0 and the like. The formazan compound of the present invention is suitable for dyeing natural and regenerated cellulose fibers as well as blended fibers containing these fibers and fibers other than cellulose fibers, and the dyeing methods include printing, dip dyeing, and padding dyeing using conventional reactive dyes. The methods used for this can be applied. First, in the textile printing method, the base paste is usually sodium alginate, emulsion paste, etc., and dyes, acid binders, urea, etc. are added to this to prepare a color paste, which is printed on the fibers, and if necessary, intermediate drying is performed. After the ivy is removed, it is treated with steam or dry heat to fix the dye. In this case, a color paste that does not contain an acid binder is printed on the fiber impregnated with an acid binder solution, or a color paste that does not contain an acid binder is printed, and then a solution containing an acid binder is applied. The dye may be fixed by treatment using the same method as described above. Next, when applying the compound (dye) of the present invention under relatively high bath ratio conditions such as dyeing, the compound (dye) of the present invention may be heated for several minutes or several times in the presence of an inorganic salt such as sodium chloride or sodium sulfate, if necessary. After sufficient dyeing, an acid binder is added, and dyeing is further carried out for several minutes to tens of minutes under heating if necessary. In this case, a method in which an acid binder is added from the beginning of dyeing can also be used. When the compound (dye) of the present invention is applied under relatively small bath ratio conditions such as the pudding dyeing method, the dye, acid binder, penetrant, urea as a solubilizing agent, and alginic acid as a migration preventive agent are used. Cellulose fibers or cellulose-containing fibers are padded in a pad bath prepared from soda or the like, squeezed, and then treated with steam or dry heat to fix the compound (dye). Examples of the acid binder used in the above dyeing method include sodium hydrogen carbonate, sodium metaphosphate, trisodium phosphate, sodium ortho- or metasilicate, sodium carbonate, and sodium hydroxide. "Effects of the Invention" The dyed products obtained by the printing method, padding dyeing method, dipping dyeing method, etc. using the formazan compound of the present invention have good washability, water fastness, and chlorine water fastness. It has excellent build-up properties, light fastness, and sweat fastness, and exhibits a purple to blue hue. "Examples" Next, the present invention will be explained in detail by examples.
The present invention is not limited to these. In the examples, parts represent parts by weight, and the sulfonic acid group carboxyl group in each formula is represented in the form of a free acid. Example 1 Add 12.8 parts of a formazan amino compound with the following structure to water.
150 parts, 50 parts of ice, 10% Liponox NA (dispersant,
It was added under stirring to a solution consisting of 0.5 part of an aqueous solution (manufactured by Lion Oil and Fat) and dissolved. Next, add 3.8 parts of cyanuric chloride and
% soda ash aqueous solution for 1 hour while maintaining the pH value at 6 to 8. Next, 1.1 parts of hydroquinone was added to this reaction solution in 50 parts of water, and the pH value was adjusted to 8 to 9 with a caustic soda solution.The pH value was 6 to 8.
The mixture was injected over 30 minutes while maintaining the same temperature. The mixture was heated to 45-55℃ with a 10% soda ash aqueous solution while maintaining the pH value at 6-8.
Allowed time to react. Salting out was carried out with sodium chloride at the same temperature, and the precipitated crystals were filtered out and dried under reduced pressure at 40°C. 23.0 parts of the compound of formula (9) was obtained. λmax 628nm (20% pyridine aqueous solution) Example 2 (dying method) 2 parts of the compound represented by formula (9), sodium chloride
Prepare a dye bath using 80 parts and 898 parts of water.
After 50 parts of cotton stockinette was soaked and treated at 80°C for 30 minutes, 20 parts of sodium carbonate was added and dyed at the same temperature for an additional 60 minutes. Next, anionic activator 2
A vivid blue dyed product was obtained by soaping at 95-100°C for 10 minutes using 1000 parts of an aqueous solution containing 1,000 parts, washing with water, and drying. This item is light resistant,
It had excellent sweat fastness to light. Examples 3 to 28 Compounds were synthesized by a method similar to Example 1,
I dyed cotton. Table 1 shows the structural formula of the synthesized compound, the hue when dyed on cotton, and 20% of the compound.
λmax in pyridine aqueous solution is shown. These compounds (dyes) showed a high color value on cotton, and the dyed products had excellent light fastness and sweat fastness.

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[Table] Example 36 (Patzding staining method) 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 intermediately dried at 100°C, and then dried at 170°C for 2 minutes. Perform dry heat treatment. 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 light fastness and sweat fastness. Example 37 (Printing method) Using the compound of formula (10), prepare 1000 parts of colored paste as shown in the following table.

[Table] is a reduction inhibitor manufactured by Nippon Kayaku. 〓
Print the above color paste on mercerized cotton broadcloth,
It was dried at 100°C for 3 minutes, steamed in saturated steam at 100°C, and then washed with water. The steam heat treatment time is 5 minutes.
I went for 10 minutes, then 20 minutes. 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. Furthermore, the difference in density of the dyed product due to the difference in steaming time was extremely small. In addition, the printed material had excellent light fastness and sweat fastness. (Comparative Test) A comparative test of color value, build-up property, and light fastness between the compound of the present invention and a known dye was conducted by the following method. Compound or dye 0.5 parts and 1.5 parts (1% of dyed material)
and 3%), 80 parts of anhydrous sodium sulfate and 914.5 parts of water
50 parts of unsilced cotton stockinette were immersed in dye baths prepared at 30 parts and 913.5 parts, respectively.
After treatment at .degree. C. for 30 minutes, 5 parts of anhydrous sodium carbonate was added, followed by staining at the same temperature for 60 minutes. Thereafter, each dyed product was washed with water and hot water, and then soaped in the same manner as in Example 2, washed with water, and dried.
Light fastness is measured using dyed material at a dye concentration of 2%.
Test method based on JIS standards (JIS L 0842-1971)
It was carried out according to the following. The judgment value is based on the blue scale (JIS
Judgment was made based on L0841-1974). Concentration comparisons using the compound of the present invention as a standard are shown in the table.

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[Table] As is clear from the table, it is recognized that the compounds of the present invention are superior in color value and build-up properties as compared to known dyes, and are also superior in light fastness.

Claims (1)

[Claims] 1 Formula (1) in the form of free acid [In formula (1), X is [Formula] (R ₁ represents hydrogen, a halogen group, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms);
[Formula] (R ₂ and R ₃ are each independently hydrogen and chlorine, Q is O, S, SO ₂ ,
CH ₂ , C (represents CH ₃ ) ₂ ); -O (CH ₂ CH ₂ ) nO
- (n represents 1 or 2), R is hydrogen,
A formazan compound represented by a sulfonic acid group, a hydroxyl group, chloro, fluorine, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carboxyl group, and M represents copper or nickel, respectively. 2 Formula (1) in free acid form [In formula (1), X is [Formula] (R ₁ represents hydrogen, a halogen group, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms);
[Formula] (R ₂ and R ₃ are each independently hydrogen and chlorine, Q is O, S, SO ₂ ,
CH ₂ , C (represents CH ₃ ) ₂ ); -O- (CH ₂ CH ₂ )
represents n-O- (n represents 1 or 2), R
represents hydrogen, a sulfonic acid group, a hydroxyl group, chloro, fluorine, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carboxyl group, and M represents copper or nickel, respectively. A dyeing method for cellulose fibers that uses a compound.