JPS6067562A - Formazan compound and dyeing of cellulosic fiber using the same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I {n is 1 or 2; when n is 2, the group of formula II is -Z1 [Z1 is amino, morpholino, (substituted) anilino or group of formula III (R is H, sulfonic acid, OH, Cl, F, etc.; M is Cu or Ni), etc.]; when n is 2, the group of formula II is formula IV (Z2 is -HNC2H4NH-, group of formula V, etc.), group of formula VI (R4 and R5 are methyl, sulfonic acid group, etc.), etc.}. EXAMPLE:The compound of formula VII. USE:A dye for dyeing or printing a cellulosic fiber in blue color. PREPARATION:The objective compound can be produced by (1) reacting the formazan amino compound of formula VIII with 1mol of 2,4,6-trichloro-1,3,5-triazine, and (2) condensing the resultant product of formula IV with 1mol of ammonia or amine of formula Z1-H.

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 form of a free acid, formula (1) [In formula (1), n represents 1 or 2, and when n-1, Z is -21 (21 is an amino group; a morpholino group; -7] a sulfonic acid group) , carboxyl group, methyl group, C1-4 alkoxy group, hydroxyl group, anilino group optionally substituted with chlorine or fluorine; monomer optionally substituted with carboxyl group, HO3S〇- group, hydroxyl group or sulfonic acid group or dialkylamino group; N-alkyl-N-phenylamino group; naphthylamino group having 1 to 3 sulfonic acid groups; benzylamino group having 1 sulfonic acid group or in the form of a free acid of formula (2) (Represents a group represented by formula (2), R and M have the meanings given below), and when n = 2, each independently represents hydrogen, chloro, methyl group, sulfonic acid group or carboxyl group. ) represents a group, a sulfonic acid group or a carboxyl group;
M represents an alkoxy group or a carboxyl group, and M represents copper or nickel, respectively. ] The present invention relates to a formazan compound represented by the following and a method for dyeing cell-based fibers using the same.

In general, metal-containing formazan dyes provide dyed products with vivid color tones and excellent fastness, particularly fastness to sunlight and fastness to rubbing. On the other hand, among formazan-based reactive dyes, those whose reactive group is a cyanuric chloride group have better pH stability in dye baths, better stability of dark colored paste for printing, and better level dyeing properties than those whose reactive group is a vinyl sulfone group. It has the advantage of being easy to change. A metal-containing formazan-based reactive dye having a cyanuric chloride group as a reactive group that has such characteristics is preferably used for dyeing cellulose fibers.

Tokuko Showa 38-5041. JP-A No. 48-94730 describes metal-containing formazan reactive dyes having a cyanuric chloride group, but the dyes described therein have the property of causing undesirable aggregation for dyeing in the dye bath;
The drawback is that the color value and build-up properties are not good when dyeing dark colors.

The present inventors have conducted extensive research to find a dye that does not have the above-mentioned drawbacks, and as a result, the formazan compound represented by formula (1) can be dyed in medium to deep colors without causing aggregation in the dye bath. The present invention was achieved by discovering that each of these materials exhibits color value and build-up properties.

In order to obtain the formazan compound represented by formula (1) of the present invention, first, formula (3) [In formula (3), R and M represent the same meanings as above. ] The formazan amino compound represented by is synthesized by the method described in 9- below.

That is, diazotized 6-acetylamino-2- (formula (4
), R has the same meaning as above. ) 5-sulfo-2- represented by formula (5) obtained from the compound represented by
The formazan amino compound of formula (3) is obtained by coupling to carboxyphenylhydrazones, then reacting with steel sulfate, nickel sulfate, copper chloride, nickel chloride, etc., and then hydrolyzing the acetylamino group to form an amino group. It will be done.

Using the formazan amino compound thus obtained, a formazan compound of formula (1) is synthesized, for example, according to the method described below.

10 Formazan amino compound 10 represented by formula (3)
-2.4.6-)lichloro-1,3,5-)riazine 1
mol to obtain a condensate represented by formula (6), and then Z, -H(Z.

have the same meanings as above).

(2) A formazan amino compound represented by formula (3) is condensed with 1 mol of a compound represented by formula (7) (Z+ in formula (7) has the same meaning as above).

■1.Formazan amino compound shown by formula (3)2.
4.6-)lichloro-1,3,5-)riazine is condensed with H, and then diamines (Z
2 represents the same meaning as above. ) 1 mol is obtained, and then reacted with 1 mol of the compound represented by formula (6).

Or formula (8) and 2.4.6-)lichloro-1,3,
1 mole of 5-triazine may be reacted to obtain an intermediate product represented by formula (9), and this may be reacted with 1 mole of a formazan amino compound represented by formula (3).

Normal separation methods such as acid precipitation method and salting out method are applied.

Next, in equation (1), 几, Z (if n=1, 2 = 21
゜n=2 (Z=Z2) will be explained using a specific example.

R is hydrogen, sulfonic acid group, hydroxyl group, chloro, fluorine, methyl group, ethyl group, propyl group, n-butyl group,
L-butyl group, methoxy group, ethoxy group, propoxy group, butyloxy group, carboxyl group, etc., and n for Z
Z□ in the case of = 1 is an amino group, a morpholino group, -NHCH,.

or 4-sulfophenyl)amino group, N-(o.

m, or p)) luidino group, N-(2-, 3+, or 4
-, carboxyphenyl)amino group, N-(mono, di, or trisulfonaphthyl)amino 13-, etc. Similarly, when n=2, examples of Z2 include 14- 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.Dyeing methods include printing, dip dyeing, and padding dyeing. Methods used for dyeing with dyes can be applied.

First, in the printing method, alginic acid is usually used)
Using emulsion glue as the base glue, dye, acid binder, etc.
A colored paste is prepared by adding urea, etc., and this is printed on the fibers. After intermediate drying if necessary, the dye is fixed by steaming or dry heat treatment. In this case, the fibers impregnated with an acid binder solution are printed with a colored paste that does not contain an acid binder, or the colored paste that does not contain an acid binder is printed and then treated with a solution containing an acid binder. After that, the dye may be fixed by treatment in the same manner as described above.

Next, when applying the compound (dye) of the present invention under relatively large bath ratio conditions such as dyeing, it is necessary to apply the compound (dye) at 20 to 130°C in the presence of an inorganic salt such as sodium chloride or sodium sulfate.
After dyeing for 0 to 60 minutes, add acid binder and dye for further 30 to 60 minutes.
Staining is carried out at 100°C for 20-60 minutes. In this case, it is also possible to use a method in which an acid binder is added from the beginning of dyeing.

When the compound (dye) of the present invention is applied under relatively small bath ratio conditions such as padding dyeing method, dye, acid binder, penetrant, urea as a solubilizer, and sodium alginate as a migration preventive agent are used. The fibers are padded in a pad bath prepared from the above methods, squeezed, and then treated with steam or dry heat to fix the 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.

The formazan compound (dye) of the present invention has a high stability of the dye when prepared as a printing paste or pad bath.
In the padding dyeing method, there is little variation in the density of the dyed product due to changes in steam or dry heat treatment conditions, and it exhibits the same high fixation rate and build-up properties as the normal dip dyeing method. The dyed product obtained has excellent fastness to light, washing, water, and chlorine water, and exhibits a purple to blue hue. It also has good hot water stain resistance when subjected to textile printing. Furthermore, even if two types of the compounds of the present invention are used as a mixture, the same effect as when used alone can be obtained.

Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples.

The middle part of the example represents parts by weight, and the sulfonic acid group in each formula is represented in free form.

Example 1 3.8 parts of cyanuric chloride were added under stirring to a solution consisting of 20 parts of water, 40 parts of ice, and 0.5 part of a 10% Liponox NA (dispersant manufactured by Lion ■) aqueous solution.

After stirring for 30 minutes (suspension), 3.46 parts of ortanilic acid was dissolved in 40 parts of water and 18-seed solution was added over 30 minutes while maintaining the temperature below 10°C. After that, 1 at around 10℃
The mixture was stirred and reacted for 6 hours while maintaining the p and I-I values at 6 to 8 using a 0% aqueous soda ash solution. This reaction solution was added to a solution in which 12.8 parts of a formazan amino compound having the following structure was dissolved in 150 parts of water.

The mixture was heated to a temperature of 45 to 55° C. and reacted for 2 hours while maintaining the pH value at 6 to 8 with a 10% soda ash aqueous solution. Then, the mixture was salted out with sodium chloride at the same temperature, and the crystals were filtered off. It was dried at 60°C to obtain 24.0 parts of the compound of the formula (1). (λmax 610 nm, water) Example 2 2 parts of the compound of the formula (1), 80 parts of sodium chloride, 1000 parts of water After immersing 50 parts of cotton stockinette in the dye bath and treating at 80°C for 30 minutes, 20 parts of sodium carbonate was added and
Treat at the same temperature for a minute and perform staining. Then, after washing with water, 95-1
By performing saw pinking at 00°C for 10 minutes, washing with water, and drying, a vivid blue dyed product can be obtained. This product had excellent light fastness, wet fastness, and chlorine water fastness. Further, no aggregation of the dye was observed during dyeing.

Examples 3 to 39 According to Examples 1 and 2, compounds were synthesized and cotton was dyed. Table 1 shows the structural formula of the synthesized compound, the hue when dyed on cotton, and the λmax of the compound in water.

21- Example 40゜12.8 parts of a formazan amino compound having the following structure were added to 15 parts of water.
0 parts, ice 50 parts, 10% Liponox NA aqueous solution 0.5
Each part was added to the solution under stirring and dissolved.

Next, add 3.8 parts of cyanuric chloride and 10%
The reaction was carried out for 1 hour while maintaining the pH value at 6 to 8 with an aqueous soda ash solution. Next, a solution of 1.85 parts of 2.2'-disulfo-4,4'-diaminodiphenylethane dissolved in 50 parts of water was added to the reaction solution.

The mixture was heated to 45-55° C. and reacted for 4 hours while maintaining the pH value at 6-8 with a 10% aqueous soda ash solution. - Salting out with sodium chloride at the same temperature, filtering out the precipitated crystals, and drying at 60°C. Compound 23 of the formula (11)
．． 0 copies were returned. (λmax 600 fim, water)
2 parts of the compound represented by formula (11), 4 parts of sodium chloride
Prepare a dyebath using 0 parts and 1000 parts of water, and soak 50 parts of cotton stockinette in the dye bath and treat at 80°C for 30 minutes, then add 20 parts of sodium carbonate and leave at the same temperature for another 60 minutes. Perform staining with

Next, saw pinking was carried out in the same manner as in Example 2, and by washing with water and drying, a bright blue dyed product was obtained. This product had excellent light fastness, wet fastness, and fastness to chlorine water.

Examples 42 to 63 A cylindrical compound was synthesized in the same manner as in Example 40, and cotton was dyed.

Table 2 shows the structural formula of the synthesized compound, the hue when dyed on cotton, and the λmax of the compound in water.

29- Table 2 30- -33 Example 66゜1.5 parts of a mixture consisting of 1.0 part of the compound represented by formula (12) and 0.5 parts of the compound represented by formula (13), 50 parts of sodium chloride , make a dye bath from 100 parts of water,
Soak 50 parts of cotton stockinette in a dye bath of
After treatment for 15 minutes, 15 parts of trisodium phosphate are added and dyeing is subsequently carried out for 60 minutes at the same temperature. Next, it was soaped in the same manner as in Example 2, washed with water, and dried to obtain a blue dyed product. Note that (12) and (1) above
When the mixture consisting of 3) was synthesized as a mixture during synthesis as described below and subjected to dyeing, a dyed product substantially similar to that described above was obtained. That is, 34-12.8 parts of a formazan amino compound having the following structure are mixed with 15 parts of water.
0 parts, ice 50 parts, 10% Liponox NA aqueous solution 0.5
Each part was added to the solution under stirring and allowed to dissolve.

After stirring for 30 minutes, 0.9 part of cyanuric chloride was added, and the mixture was reacted for 1 hour at a temperature below 10° C. while maintaining the pH value at about 7 with a 10° C. aqueous soda ash solution. Next, the temperature was raised to 50°C, and
The reaction was allowed to proceed for 1 hour at a temperature of ˜55° C. while maintaining the pH value between 6 and 8 with a 10% aqueous soda ash solution. Next, add 1 water
1.8 parts of cyanuric chloride was added to a solution consisting of 0 parts, 30 parts of ice, and 0.5 parts of Ripar OH (dispersant manufactured by Lion Oil ■) with stirring, and after stirring for 1 hour, 1.2 parts of 29% ammonia water was added.
The 9-fold condensate was added to the reaction solution and reacted for 1 hour at about 20 DEG C. and a pH value of 8-9. Add this mixture to 50-55
The temperature was raised to °C and the reaction was carried out for 2 hours at a pH value of approximately 7. The mixture was then salted out at the same temperature), and the obtained crystals were filtered and dried at 60'C.

22.0 parts of a mixture containing O compounds of formula (12) and formula (13) in a ratio of about 1:1 was obtained.

Examples 67-70 According to the method described in Example 66, a mixture of compounds was prepared and cotton was dyed.

Table 3 shows the structural formula of each component of the mixture, the hue when dyed on cotton, and the λmax (in water) of the mixture.

Table 3 38- Example 71゜ Cotton gabardine was padded with 1000 parts of a pad bath consisting of 30 parts of the compound of the formula (1) described in Example 1 and 970 parts of water, and intermediate drying was performed by squeezing to a squeezing rate of 60%. Fixation was carried out using a Zucker dye tester at 80° C. for 60 minutes in a treatment bath consisting of 20 parts of trisodium phosphate, 200 parts of anhydrous sodium sulfate, and 780 parts of water.

Next, it was soaped in the same manner as in Example 2, washed with water, and dried to obtain a blue dyed product.

Using the compound of formula (14) (compound obtained in Example 9), 1000 parts of a brown paste was prepared according to the table below.

The colored paste was printed on mercerized cotton broadcloth, dried at 60°C for 10 minutes, steamed in saturated steam at 100°C, and then washed with water. The steam heat treatment time was changed to 5 minutes, 10 minutes, and 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, and then washing with water was performed. 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.

39- Comparative Test A comparative test of the dyeing power of the compound of the present invention and known dyes was carried out by the following method.

0.5 parts of compound or dye, 80 parts of anhydrous sodium sulfate,
50 parts of non-mercerized cotton knitted fabric was immersed in a dye bath prepared with 899.5 parts of water and treated at 80°C for 30 minutes, then 20 parts of anhydrous sodium carbonate was added and dyed at the same temperature for 60 minutes. Ta.

Thereafter, the dyed product was washed with water and hot water, followed by soaping in the same manner as in Example 2, washed with water, and dried.

The table shows a visual density comparison using the compound of the present invention as a standard.

41-140-42- As is clear from the table, the dyeing density of the compounds of the present invention is extremely high compared to known dyes and dyes having structures similar to the compounds of the present invention.

Patent applicant: Nippon Kayaku Co., Ltd.

Claims (2)

[Claims] (1) Formula (1) in the form of a free acid] When =1, 4 is -Z1 (Zt is an amino group: a morpholino group:
Sulfonic acid group, carboxyl group, methyl group, CI"-4
alkoxy group, hydroxyl group, anilino group optionally substituted with chloro or fluorine; carboxyl group, Ho, 80-
a mono- or dialkylamino group which may be substituted with a group, a hydroxyl group or a sulfonic acid group; an N-alkyl-N-phenylamino group; a naphthylamino group having 1 to 3 sulfonic acid groups; one sulfonic acid group represents a group represented by formula (2) in the form of a benzylamino group or a free acid having Table S, 802, CH-C
R represents hydrogen, sulfonic acid group, hydroxyl group, chloro,
Fluorine, C1-4 argyl group, 01-4 alkoxy group or carboxyl group, and M each represent copper or nickel. ] A formazan compound represented by (2) Formula (1) in the form of free acid [In formula (1), n represents 1 or 2, and when n = 1, 4 is -2, (2, is an amino group: morpholy-: ) group; sulfone Acid group, carboxyl group, methyl group, 01
~4 alkoxy group, hydroxyl group, anilino group optionally substituted with chloro or fluorine; carboxyl group, HO3S
〇- group, a hydroxyl group or a dialkylamino group which may be substituted with a hydroxyl group or a sulfonic acid group; N-alkyl-N-phenylamino group: a naphthylamino group having 1 to 3 sulfonic acid groups; 1 represents a group represented by formula (2) (in formula (2), R and M have the meanings given below) in the form of a benzylamino group or free acid having a sulfonic acid group, and n = 2 , R2 are each independently hydrogen, chloro, methyl group, sulfonic acid group or carboxyl group, methyl group, sulfonic acid group or carboxy (Q haO, S , SO2
, CH=CH, NH, CH2, CI (2CH2 or C0
NH), R is hydrogen, sulfonic acid group, hydroxyl group, chloro, fluorine, C1-4 alkyl group, C! ~
In the alkoxy group or carboxyl group of 4, M represents copper or nickel, respectively. ] A method for dyeing cellulose-based fibers, characterized by using a formazan compound represented by: