JPS6220563A - Trisazo compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (M is H or alkali metal; R<0> is H or COOH; R<1> is H, lower alkyl, COOH, sulfonic acid group, etc.; R<2> is H, lower alkyl, acetylamino, etc.; R<3> is lower alkyl or lower alkoxy; R<4> is H, lower alkyl, acetylamino, etc.; P is CCl3, CF3, CHCl2 or CH2Cl; Q is H or halogen; W is halogen; m is 1-3; n is 0 or 1; rings A and B are benzene ring or naphthalene ring). EXAMPLE:The compound of formula II. USE:A dye for dying cellulosic fiber an nitrogen-containing fiber in deep blue color. Suitable for the dying of blended fiber of cellulose and polyester in one- step one-bath process. PREPARATION:The compounds of formula III-V are subjected to diazotization and coupling reactions twice to obtain a disazo compound and the diazonium salt of the disazo compound is coupled with a compound obtained by the condensation reaction of the compound of formula VI with the compound of formula VII.

Description

Detailed Description of the Invention (a) Purpose of the Invention (a) Field of Industrial Application The present invention relates to a novel trisazo compound used as a dye for cellulose fibers, nitrogen-containing fibers, and especially cellulose fibers. be.

(B) Conventional technology Conventionally, when dyeing cellulose fibers, reactive dyes are used, and acid binders such as sodium carbonate, potassium carbonate, and sodium hydroxide, as well as sodium chloride and sulfuric acid are used.
In the presence of an electrolyte such as IJum, at a pH of 10 or more, at a temperature of 1
A method is adopted in which the test is carried out under conditions of 00°C or lower.

However, in recent years there has been an increase in demand for blended fabrics of cellulose fibers and other fibers, especially polyester fibers.
In order to dye cellulose/polyester mixed fibers (hereinafter sometimes simply referred to as C/P fibers), it is necessary to apply dyes and dyeing conditions to cellulose fibers and dyes and dyeing conditions to polyester fibers, respectively. Ta. That is, the dye and dyeing conditions for dyeing polyester fiber are the same as those for cellulose fiber.
This was because the dogs had different voices. That is, to dye polyester fibers, disperse dyes are used and the temperature is about 13°C.
This is because it was necessary to dye at 0°C.

For example, if the C/P fibers mentioned above were to be dyed in the same process, two different dyes would be used in combination, a reactive dye and a disperse dye, which would pose several problems. Ta. For example, in order to dye the reactive dye sufficiently on the cellulose fiber side, an acid binder is used to dye the cellulose fiber side.
Although it is necessary to make the acid binder more than ilo, the presence of the acid binder accelerates the decomposition of the disperse dye, resulting in insufficient dyeing of the disperse dye to the polyester fiber. On the other hand, in order to dye the disperse dye on the polyester fiber side, high temperature conditions (usually 130
℃), but the high temperature under the above-mentioned conditions accelerates the hydrolysis of the reactive dye, and the dyeing of the cellulose fibers is significantly inhibited. Therefore, such C/
When dyeing P fibers, a two-bath method is generally used in which one fiber, cellulose or polyester, is dyed and then the other fiber is dyed in a separate bath.

(c) Problems to be Solved by the Invention The present invention seeks to provide a trisazo compound that can dye cellulose fibers under the same conditions as when dyeing polyester fibers with disperse dyes and under other dyeing conditions. It is something to do.

(b) Structure of the Invention (a) Means for Solving Problems The present invention is based on the general formula [wherein M represents a hydrogen atom or an alkali metal, and R
'represents a hydrogen atom or a carboxyl group, R1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a carboxyl group or a sulfonic acid group, 1R2 represents a hydrogen atom,
Represents a lower alkyl group, lower alkoxy group, acetylamino group or sulfonic acid group, R represents a lower alkyl group or lower alkoxy group, R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or an acetylamino group °, P represents a CCt group, a CF group, a CHCl group, or a CF2Cl group, Q represents a hydrogen atom or a halodan atom, W represents a halodan atom, m represents an integer of 1 to 3, and n represents 0 or 1. , and 3JA and B represent a benzene ring or a naphthalene ring. ] This is a trisazo compound represented by the following.

In the trisazo compound (hereinafter simply referred to as "trisazo compound") represented by the general formula (1) of the present invention,
Examples of the alkali metal represented by M include lithium sodium and potassium, and lower alkyl groups represented by R+R2, R5, R4 and R5 have 1 to 1 carbon atoms.
4 alkyl groups are mentioned, R1, R2, R3 and R
The lower alkoxy group represented by 4 has 1 to 4 carbon atoms.
Examples of the alkoxy group represented by Q and W include a fluorine atom and a chlorine atom.

The trisazo compound represented by the general formula (1) can be produced, for example, as follows.

That is, the following general formulas (II), (III),
Using each compound represented by (IV) (in each formula, RaRaRtRaRt m, 1JIh and B are the same as defined above), normal diazotization and coupling were performed twice, and the following general formula (V) In the formula, RtReRt
R, Re m and rings A and B are as defined above. ].

On the other hand, both compounds represented by the following formulas (M) and (■) (in each formula, naPaQ and W are the same as defined above, and HaL represents a halogen atom) are subjected to a condensation reaction in an aqueous medium, and the following A compound represented by the general formula (■) (where n g P a Q e and W are the same as defined above) is produced.

Then, the above (V) is added to the compound represented by the general formula (Vl).
A trisazo compound of the general formula (1) can be produced by coupling the diazo compound with a diazotized diazonium compound in a water-acetic acid medium.

The trisazo compound of the present invention thus produced can itself be used as a dye.

Examples of fibers that can be dyed with the trisazo compound of the present invention include cellulose fibers such as cotton, viscose rayon, cuproammonium rayon, and hemp. Furthermore, it can also be applied to dyeing nitrogen-containing fibers such as I-lyamide, wool, and silk. In addition, cellulose fibers in mixed fibers such as polyester, triacetate, polyacrylonitrile, polyamide, wool, silk, etc. containing cellulose fibers can of course be dyed well.

In the fiber dyeing method using the trisazo compound of the present invention, dyes necessary for dyeing non-cellulose fibers, such as Co1our Indsx (3rd edition)
Dyeing can be done by adding disperse dyes etc. listed in the dye bath at the same time.

When dyeing cellulose fibers using the trisazo compound of the present invention, for example, the trisazo compound represented by the above general formula (1) and the dye bath during dyeing may be adjusted to
Buffers necessary to maintain the temperature at 0.5 to 1 O (for example, acids such as carbonic acid, phosphoric acid, acetic acid, citric acid, and sodium salts or potassium salts of these acids, singly or in mixtures, usually 0.5 to 10
5.0 g/l) and, if necessary, an electrolyte (sodium chloride or sodium sulfate, etc., usually 1 to 150 g/l).
Prepare a dyebath containing about 1/l), add cellulose fibers to this dyebath, and dye at a temperature of 100 to 150°C for 30 to 5
Good dyeing can be achieved by heating for 0 minutes.

In addition, in order to dye blended fabrics, blended knitted fabrics, etc. produced by adding other fibers such as polyester fibers to cellulose fibers, one method is to use a trisazo compound represented by the above general formula (1) of the present invention, Co1our Index above
By adding the above-mentioned disperse dye to the above dye bath, cellulose fibers and polyester fibers can be simultaneously dyed using a one-bath, one-stage method.

In addition, when dyeing the above-mentioned blended fabrics, blended knitted fabrics, etc., one-bath two-stage dyeing is used, in which one fiber is dyed and then the other fiber is dyed in the same bath. Alternatively, the dyeing method using the trisazo compound of the present invention and the dyeing method for fibers other than cellulose fibers may be combined to dye cellulose fibers and other fibers from separate baths. It is also possible to adopt a two-bath method.

EXAMPLES Hereinafter, the method of the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.

(b)) Examples Example 1 2-naphthylamine-3,6,8-)disulfonic acid 38
, 39 to 2-methoxy-5-methylanili 713.7g
A monoazo compound produced by diazotization and coupling using a conventional method, and further! A disazo compound represented by the following structural formula was prepared by diazotization and coupling with 1c2-methoxy-5-methylaniline 13.79 in a conventional manner.9.

On the other hand, 1-amino-8-hydroxynaphthalene-3,6
-Disulfonic acid 31.977 and 2-trichloromethyl-
4,6-dichloro-5-chloropyrimidine 25.6gt
Condensation was carried out at −0°C to produce a compound represented by the following structural formula 8%, and a diazo solution obtained by diazotizing the above disazo compound with a water-acetic acid system was added to the reaction solution, and KOH was added. After coupling with IH7, salting out with potassium chloride yields a trisazo compound 90 of the following structural formula (shown in free acid form). I got '59.

This triazotized Tanimo 0.2.9, Glauber's salt 16 p, -
Dye bath button prepared by adding Na2HPO4-12H200.4 g and KH2PO40, III as a buffer to 200 d of water, unsilved cotton knitted fabric 10.9'i
The temperature was raised to 120°C over 30 minutes, and then heated to 60°C at the same temperature.
After dyeing for minutes, wash with water, nooping, wash with water, and dry.
A greenish-dark blue dyeing was obtained.The dyeing strength of this compound was very good, the dyeing obtained was extremely dense, and the light fastness, chlorine fastness and sweat-sunlight fastness were all excellent. was also good.

Example 2 Aniline-2,5-disulfonic acid 25.3. A monoazo compound produced by diazotizing and coupling p with 2-methoxy-5-methylaniline 13.79 in a conventional manner,
Furthermore, 2-methoxy-5-acetylaminoaniline 18
．． 0. A disazo compound represented by the following structural formula was produced by diazotization and coupling with lit in a conventional manner.

On the other hand, 2-amino-5-hydroxynaphthalene-7-sulfonic acid 23.99.2-trichloromethyl-4,6-
A compound represented by the following structural formula, which is a condensate with 25.6 g of dichloro-5-chloropyrimidine, was produced.

47.9 of this compound and 59.2 g of the previously produced disazo compound were diazotized and PH
After the coupling reaction in step 7, the reaction solution was spray-dried to obtain trisazo compound 87.59 represented by the following structural formula (shown in free acid form).

0.2 g of this trisazo compound, Glauber's Salt 16J9. 10g of unmercerized cotton knitted fabric was added to a dye bath prepared by adding Na2HPO4''12H20o, 5.9 and KH2PO40,02/ as buffering agents to 20011L of water, and the temperature was raised to 130℃ over 30 minutes. After dyeing at temperature for 30 minutes, washing with water, soaping, washing with water, and drying were performed to obtain a dark blue dyed product.This dyeing bath was used before and after dyeing.
It was 8. Furthermore, the dyed product obtained was extremely rich and had good light fastness, chlorine fastness, and sweat-sunlight fastness.

Example 3 2-methoxy-5-methylaniline used in Example 2 (13.7/l) was replaced with 1-naphthylamine-7-sulfonic acid (22.3/l). A trisazo compound 92.39 represented by the following structural formula was prepared in the same manner as in Example 2 using pt-s. ．． Glauber's salt 12g, Na as a buffering agent
2HPO4'12120 0.4 fi and KI (2
To a dye bath prepared by adding 40.1 g of PO to 20011 il of water, blended fabric 1 of I-liester/cotton = 50:50 was added.
0.9, the temperature was raised to 130° C. over 30 minutes, dyed at the same temperature for 60 minutes, washed with water, sown pink, washed with water, and dried to obtain a dark blue dyed product with good same color property.

The dye bath had a pH of 8 before and after dyeing.

Furthermore, the dyeing property was very good, and the dyed product obtained was extremely rich, and the light fastness, chlorine fastness, and sweat-sunlight fastness were all good.

Examples 4 to 31 According to the method described in Example 2, each trisazo compound listed in Table 1 was produced. Using each of the obtained compounds, cotton cloth was dyed according to the method described in Example 2, and the results are shown in Table 1.

(c) Effects of the invention The trisazo compound of the invention can exhibit the following effects.

(i) It is excellent as a dye for cellulose fibers and nitrogen-containing fibers, especially the former type of fibers.

(11) In particular, since cellulose fibers can be easily dyed under - and other dyeing conditions when dyeing polyester fibers with disperse dyes, mixed fibers of cellulose and polyester can be dyed using a one-bath, one-stage method. It is excellent as a dye for cellulose fibers.

Patent applicant: Mitsubishi Chemical Industries, Ltd. ・'1・11

Claims (3)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) [In the formula, M represents a hydrogen atom or an alkali metal, and R
^0 represents a hydrogen atom or a carboxyl group, and R^1
represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a carboxyl group or a sulfonic acid group, R^2 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an acetylamino group or a sulfonic acid group, R^3 represents a Represents a lower alkyl group or lower alkoxy group, R^4 represents a hydrogen atom, lower alkyl group, lower alkoxy group or acetylamino group, P represents a CCl_3 group, a CF_3 group,
represents a CHCl_2 group or a CH_2Cl group, Q represents a hydrogen atom or a halogen atom, W represents a halogen atom, m represents an integer of 1 to 3, n represents 0 or 1, and Ring A and Ring B represents a benzene ring or a naphthalene ring. ] A trisazo compound represented by (2) The trisazo compound according to claim 1, wherein in the general formula (I), ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼. (3) In the general formula (I), ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ is ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R^6 represents a lower alkyl group). A trisazo compound according to scope 1 or 2.