JPS6220562A - Trisazo compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [D is group of formula II (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.; m is 1-3; n is 0 or 1; rings A and B are benzene ring or naphthalene ring); X is F, Cl, group of formula III (R<5> and R<6> are H, methyl, sulfonic acid group, etc.; R<7> is H, methyl or ethyl), etc.; Y is H, halogen, lower alkyl, lower alkoxy, -COOM or -SO3M; Z is H, methyl, -COOM or -SO3M]. EXAMPLE:The compound of formula IV. USE:A dye for dying cellulosic fiber and nitrogen-containing fiber in deep blue color. PREPARATION:The compounds of formula V-VII are subjected to diazotization and coupling reactions twice to obtain a disazo compound, which is diazotized and then coupled with the compound of formula VIII.

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. It is something.

(b) Conventional technology Conventionally, when dyeing cellulose fibers, reactive dyes are used in the presence of acid binders such as sodium carbonate, potassium carbonate, and sodium hydroxide, and electrolytes such as sodium chloride and sodium sulfate. At a pH of 10 or higher and a temperature of 100
A method is adopted in which the process is carried out at temperatures below ℃.

However, in recent years, the demand for blended fabrics of cellulose fibers and other fibers, especially polyester fibers, has increased, and in order to dye such cellulose/polyester blended fibers (hereinafter sometimes simply referred to as C/P fibers). It was necessary to apply dyes and dyeing conditions to cellulose fibers and dyes and dyeing conditions to polyester fibers, respectively. This is because the dyes and dyeing conditions for dyeing lyester fibers are significantly different from those for cellulose fibers. In other words, to dye polyester fibers, disperse dyes are used and the temperature is about 130°C.
This is because it was necessary to dye at ℃.

For example, if we were to dye the C/P fibers mentioned above in the same process, we would have to dye them using two different dyes, a combination of a reactive dye and a disperse dye, and potash. there were. For example, in order to dye the reactive dye sufficiently on the cellulose fiber side, use an acid binder to dye -10
Although the above conditions are necessary, the presence of the acid binder promotes 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 disperse dyes on the polyester fiber side, high temperature conditions (usually 130°C) are required, but the high temperature under the above-mentioned high voice accelerates the hydrolysis of reactive dyes and causes damage to cellulose fibers. Dyeing will be significantly inhibited. Therefore, when dyeing such C/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. It will become.

(c) Problems to be Solved by the Invention The present invention solves the problem by using a disperse dye. The object of the present invention is to provide a trisazo compound capable of dyeing cellulose fibers under the dyeing conditions used for dyeing IJ ester fibers.

(b) Structure of the Invention (a) Means for Solving the Problems The present invention is based on the general formula [wherein, D represents a hydrogen atom or an alkali metal, and R
Is it a hydrogen atom or Cal? represents a xyl group, R1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a car-ζ xyl group, or a sulfonic acid group, R2 represents a hydrogen atom,
represents a lower alkyl group, a lower alkoxy group, an acetylamino group or a sulfonic acid group, R represents a lower alkyl group, a lower alkoxy group, R4 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an acetylamino group,
m represents an integer of 1 or more and 3 or less, n FiO or 1
and Ring A and Ring B each represent a benzene ring or a naphthalene ring. ); represents a hydrogen atom or an alkali metal), or represents an alkali metal, and L is 0
or 1. ), Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -C00M
group or -803M group (M represents a hydrogen atom or an alkali metal), 2 is a hydrogen atom, a methyl group, -
COOM or -8o3M (M represents a hydrogen atom or an alkali metal). ] It is a triazo compound represented by

Δ A trisazo compound (hereinafter sometimes referred to as a single 1c trisazo compound) represented by the general formula (1) of the present invention.

), examples of the alkali metal represented by M include lithium, sodium, potassium, etc., and R, R,
Examples of the lower alkyl group and lower alkoxy group represented by R, R and Y include alkyl groups and alkoxy groups having 1 to 4 carbon atoms. In particular, a methyl group or a methoxy group is preferred. Further, examples of the halogen atom represented by Y include the following. Further, as Y, -80,H group or 1000H group is particularly preferable.

The trisazo compound represented by the general formula (1) is:
For example, it can be manufactured as follows.

That is, the following general formulas (II), (III), (IV
)Z (II) (III) (
Using each compound represented by F/) (wherein Ro, R1, R2, R3, R4, m and rings A and B are the same as defined above), conventional diazotization and force,
76 ring twice and the following general formula (V) (wherein, RN
RXRN R% m and Ring A and Ring B are as defined above. ) is the disazo compound shown by

Then, a diazonium compound obtained by diazotizing this disazo compound (V) in a water-acetic acid medium is prepared using the following general formula (■
) (where n, X%Y and 2 are the same as defined above.

) By bringing the compound shown by and the force, S, S A triazo compound represented by the general formula (1) is obtained by Δ I can do that.

In addition, in order to produce the compound represented by the general formula (M), a compound represented by the following general formula (■) (wherein, Xl represents a chlorine atom or a fluorine atom) and the following general formula ( (2) condensation with a compound represented by (wherein n is the same as defined above);
A compound represented by the following general formula is obtained.

(In the formula, n and Xl are the same as defined above.) Then, this compound (■) and the following general formula (X) (in the formula, 2
is the same as the above definition. ) are condensed at a molar ratio of 1:1 to obtain a compound represented by the following general formula (N).

(In the formula, n, By condensing the compound with the following general formula (X[[)
A compound represented by can be produced.

H...(X[ll) (In the formula, 'x', y, z and n are the same as defined above.) Then, in the general formula (1), X is (where R5, R6, R' , M and L companies are the same as defined above.) To obtain the compound A, the general formula (
It can be easily obtained by condensing 1 molar ratio of the compound represented by Xllll) and 2 molar ratio of the general formula with P)(6) in hot water at 80° to 90°C.

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 polyamide, wool, and silk. Furthermore, 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 disperse dyes described in Co1our Index (3rd edition), are added to the dye bath at the same time. In addition, it can be dyed.

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 pH of the dye bath during dyeing may be used.
5 to 10 (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 sulfuric acid), usually 1 to 15 g/l.
0 g/l), add cellulose fibers to the dye bath, and incubate at a temperature of 100 to 150℃ for 30 minutes.
Good dyeing can be achieved by heating for ~50 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, a trisazo compound represented by the above general formula CI) of the present invention and the above-mentioned Co1our Index
By adding the listed disperse dye to the above dye bath, cellulose fibers and polyester fibers can be dyed simultaneously by a one-bath, one-stage method.

In addition, when dyeing blended fabrics, blended knitted fabrics, etc., as described above, the conventional one-bath two-step method of dyeing one fiber and then dyeing the other fiber in the same bath is used. Furthermore, a two-bath method in which the dyeing method using the trisazo compound of the present invention and the dyeing method for fibers other than cellulose fibers are combined to dye cellulose fibers and other fibers from separate baths. It is also possible to adopt

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.

Middle) Examples Example 1 2-naphthylamine-3,6,8-)disulfonic acid 38
．． 39 to 2-methoxy-5-methylaniline 13,'#
A monoazo compound produced by diazotization and coupling with 2-methoxy-5-methylanili:yL3.7II in a conventional manner is further diazotized and coupled with 2-methoxy-5-methylanili:yL3.7II to obtain a disazo compound represented by the following structural formula. Manufactured.

On the other hand, 1-amino-8-hydroxynaphthalene-3,6
-Disulfonic acid 31.9. p and cyanuric heptadide 13.5
．． After condensing 9 at 0° C. or lower, 10.8 g of p-phenylenediamine was further condensed. Add to this 13.5 g of cyanuric fluoride and 17.3 g of 3-aminobenzenesulfonic acid.
A condensation product of is added to produce a compound represented by the following structure, and a diazo solution obtained by diazotizing the above disazo compound with a water-acetic acid system is added to the reaction solution, followed by coupling.
By salting out with potassium chloride, a trisazo compound having the structural formula and visible light absorption analysis value below was produced.

Trisazo compound shown by the above structural formula 012y1 16 g of Glauber's salt, Na2HPO4' 12 H2 as a buffering agent
Add O0,49 and KH2PO40,111 to 200 g of water (P) (Put 10 y of unmercerized cotton stockinette into the dye bath prepared in step 7, raise the temperature to 120°C over 30 minutes, and dye at the same temperature for 60 minutes. After washing with water, soaping, washing with water, and drying, a greenish navy dyed product was obtained.The degree of dyeing of this dye is very good, and the dyed product obtained is extremely thick, has good light fastness, and chlorine resistance. Both fastness and sweat-sunlight fastness were good.

Example 2 A monoazo compound produced by diazotizing and coupling 25.3,9 aniline-2,5-disulfonic acid with 13.7 g of 2-methoxy-5-methylaniline in a conventional manner,
Furthermore, 2-methoxy-5-acetylaminoaniline 18
．． 0. A nosazo compound represented by the following structural formula was produced by diazotization and coupling with @ in a conventional manner.

On the other hand, 23.9 g of 2-amino-5-hydroxynaphthalene-7-sulfonic acid, cyanuric chloride 18,5I and
．． 4-Cyaminobenzene-2-sulfonic acid 18.8.
9 was condensed. Next, 18.5 cyanuric chloride was added to this.
A condensate of g and 17.3 fl of 2-aminobenzenesulfonic acid was added at 20°C to produce a compound represented by the following structural formula, and further heated at 90°C and pH 6.
-aminobenzeneoxyethylsulfone sulfate 5
Compound 74 condensed with 6.29 and represented by the following structural formula
17 were produced.

After performing diazotization and coupling using this compound and the previously produced nosazo compound, the reaction solution was spray-dried to obtain a compound having the following structural formula and analytical values. Built.

10 Il of unmercerized cotton stockinette was added to a dye bath prepared by adding 0.2 g of this trisazo compound, 16 g of Glauber's salt, 200.5 g of NIL 2 HPO4.12I (200.5 g) and KH2PO4 0.0211 as a buffer to 200 Ill of water, and dyed for 30 minutes. The temperature was raised to 130°C, dyed at the same temperature for 30 minutes, washed with water, soaped, washed with water, and dried to obtain a dark blue dyed product.This dyeing bath had a -8
Met. The dyed product obtained is extremely dense and has good light fastness.
Both chlorine fastness and sweat-sunlight fastness were good.

Example 3 A compound having the following structural formula and analytical values was produced according to the method described in Example 1.

This trisazo compound 0.2. ! i! , 0.2 g of monoazo dye shown by the structural formula below, 12 g of Glauber's salt, Na2HPO4.12 H2O0,49 and KH as buffering agents.
Add 2PO40,1,9 to 200 ml of water to make a dye bath made by FA? 10 blended fabrics of ester/cotton = 50:50
P was added and the temperature was raised to 130℃ over 30 minutes, and at the same temperature it was heated to 130℃.
After dyeing for 0 minutes, washing with water, soaping, washing with water, and drying were performed to obtain a dark blue dyed product with good same color property. This dye bath was P)I8 before and after dyeing. In addition, the dyeing property is very good, and the dyed product obtained is extremely thick and light fastness.
Both chlorine fastness and sweat-sunlight fastness were good.

Examples 4 to 23 Each trisazo compound listed in Table 1 was produced according to the method described in Example 1. Using each compound obtained,
The results of dyeing cotton cloth according to the method described in Example 1 are shown in Table 1.

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

(1) 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.

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, D is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, M represents a hydrogen atom or an alkali metal, 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 lower Represents an alkyl group or lower alkoxy group, R^4 is a hydrogen atom,
It represents a lower alkyl group, a lower alkoxy group, or an acetylamino group, m represents an integer of 1 or more and 3 or less, n represents 0 or 1, and Ring A and Ring B each represent a benzene ring or a naphthalene ring. ), where X is a fluorine atom, a chlorine atom, ▲a mathematical formula, a chemical formula, a table, etc. ^7 represents a hydrogen atom, methyl group, or ethyl group, M represents a hydrogen atom or an alkali metal), or ▲ Numerical formula, chemical formula, table, etc. ▼ (M represents a hydrogen atom or an alkali metal, l represents 0 or 1),
Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a -COOM group or a -SO_3M group (M represents a hydrogen atom or an alkali metal), and Z
is a hydrogen atom, a methyl group, -COOM or -SO_3M
(M represents a hydrogen atom or an alkali metal.) ] A trisazo compound represented by