JPS6281455A - Trisazo compound - Google Patents

Abstract

NEW MATERIAL:Trisazo compounds of formula I, wherein M is H, an alkali metal; R<3> is a lower alkyl, a lower alkoxy, sulfo group; R<1> is H, R<3>; R<2>, R<4> are each R<1>, an acetylamino; R<5> is H, a lower alkyl; X is a group of formula II (wherein l is 0, 1); Y is X, Cl, F, a residue of an arom. or aliph. amine, OH which may be etherified; m is 1-3; n is 0, 1; rings A, B and C may be each a naphthalene ring. EXAMPLE:Compd. of formula III. USE:Dyes which have excellent dyeability and fastness to light and dye cellulosic fibers, nitrogen-contg. fibers, etc. to (reddish or greenish) dark blue. PREPARATION:Compds. of formulas IV-VI are subjected to diazotization and coupling reactions twice to obtain a disazo compd. of formula VII. A diazonium compd. obtd. by diazotizing said disazo compd. in a water/acetic acid medium is coupled with a compd. of formula XI derived from a compd. of formula X obtd. by condensing compds. of formulas VIII, IX in an aq. medium.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel trisazo compound used as a dye for cellulosic fibers and nitrogen-containing fibers.

Conventional technology Traditionally, when dyeing cellulose fibers, reactive dyes are used and dyed in the presence of acid binders such as carbonate, potassium carbonate, sodium hydroxide, and electrolytes such as sodium chloride and sodium sulfate. In this method, a method is adopted in which the pH is 70 or higher and the temperature is 100° C. or lower.

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 mixed fibers (hereinafter 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 polyester fibers are significantly different from those for cellulose fibers. That is, in order to dye polyester fibers, it was necessary to use a disperse dye and dye at a temperature of approximately 73θ°C.

For example, if we were to dye the above C/P fiber string in the same process, we would have to dye it using two different dyes, a combination of a reactive dye and a disperse dye. There was a problem.

In other words, in order to sufficiently dye the reactive dye on the cellulose fiber side, it is necessary to use an acid binder to adjust the pH to 1) 7θ or higher, and the presence of an acid binder promotes the decomposition of the disperse dye. The dyeing of the disperse dye on the polyester fiber becomes insufficient. On the other hand, in order to dye disperse dyes onto polyester fibers, high temperature conditions (normal/3θ°C) are required, but at high temperatures under the above-mentioned high pH conditions, hydrolysis of reactive dyes is promoted and the dyes are transferred to cellulose fibers. The dyeing will be significantly inhibited. Therefore, when dyeing such C/P fibers, a two-bath method is generally used, in which one fiber of cellulose or polyester is dyed, and then the other fiber is dyed in a separate bath. It is.

Problems to be Solved by the Invention The object of the present invention is to provide a polyester fiber hardware using a disperse dye.

Means for Solving the Problems The present invention has the following features: general formula (1) % formula % (1) (wherein M represents a hydrogen atom or an alkali metal; R
1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a sulfonic acid group; HR and R4 represent a hydrogen atom;
Represents a lower alkyl group, lower alkoxy group, acetylamino group or sulfonic acid group, R3 is a lower alkyl group,
It represents a lower alkoxy group or a sulfonic acid group, R5 represents a hydrogen atom or a lower alkyl group, and t of X is θ or /. ), Y represents x1 a chlorine atom, a fluorine atom, an aromatic amino residue, an aliphatic amino residue, or a hydroxyl group that may be etherified, and m represents /, . 2 or 3, n represents O or /, and a benzene ring, and A, B, and C may represent a naphthalene ring).

In the trisazo compound represented by the general formula (1) of the present invention, examples of the alkali metal represented by M include sodium, potassium, and the like.

Examples of the lower alkyl group and lower alkoxy group represented by R1, R2, R3, R4 and R11 include alkyl groups and alkoxy groups having from 1 to 2 carbon atoms, with methyl and methoxy groups being particularly preferred.

The aliphatic amino group represented by Y is an amino group, 0
1%04 monoalkylamino group s "1-C4 dialkylamino group, monoethanolamine group, jetanolamino group, -NHO1H4SO3Na group, -NHOH
100ONa group, -NH021H4SO2C, H401
Aromatic amino groups include anilino group, N-methylaniline,
Examples include N-ethylaniline or anilino groups substituted with chlorine atoms, nitro groups, carboxyl groups, sulfonic acid groups, lower alkyl groups, or lower alkoxy groups, and examples of hydroxyl groups that may be etherified include 10H. group, an alkoxy group of 01 to 04, or a phenyloxy group substituted with a chloro atom, a nitro group, a carboxyl group, a sulfonic acid group, a lower alkyl group, or a lower alkoxy group.

The trisazo compound represented by the general formula (1) can be produced as follows. For example, the following general formula (
II), CI, 0V) (II) (I[[)
(IV) (wherein R1, R3, R3, R4,
(m and benzene rings A1B and C are the same as defined above) A compound represented by the following is once subjected to conventional diazotization and coupling to form a disazo compound represented by the following general formula (V).

On the other hand, the following general formula ('M), [■] ゛tn (in the formula, 2 represents a chlorine atom or a fluorine atom, n,
R' is the same as defined above. ) is condensed in an aqueous medium to produce a compound represented by the following general formula [■] (where n%2 and R11 are the same as defined above).

Next, a compound represented by the general formula (wherein n%R5, X and Y are the same as defined above) is produced by the method (1), (2) or (2) below.

(where t and M are the same as defined above): are condensed in hot water of 100 to 0°C.

■ In the front leg general formula CI), Y is a chlorine atom.
Condensation is carried out in -4 to C hot water.

■ When Y represents an amino residue or an optionally etherified hydroxyl group in the forepaw general formula (1): The compound/sole ratio represented by the above general formula [■] and Y'H (
Here, Y' represents an amino residue or a hydroxyl group even if it is etherified. ) is condensed with a compound represented by 1 molar ratio.

Next, the di-azo form of the above (V) is coupled to the compound represented by the general formula (■) with a diazonium compound diazotized in a water-acetic acid medium to obtain the compound represented by the general formula [I]. Trisazo compounds can be produced.

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 polyamide fibers such as wool, silk, etc.

In addition, polyester containing cellulose fiber, triacetate, polyacrylonitrile, polyamide, wool,
Of course, the cellulosic fibers in mixed fibers such as silk can 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. ~
10 (usually a single or a mixture of acids such as carbonic acid, phosphoric acid, acetic acid, citric acid, and sodium salts or potassium salts of these acids)
Prepare a dye bath to which the dyestuff is added, and if necessary, add an electrolyte (sodium chloride or sodium sulfate, etc., usually to the extent of /~/!θy/), and put the cellulose fibers into the dye bath. , temperature 10θ~/, j at 90℃ O% j
Good staining can be achieved by heating for θ minutes.

In addition, in order to dye blended fabrics, blended knitted fabrics, etc. produced by mixing cellulose fibers with other fibers such as polyester fibers, the trisazo compound represented by the above general formula (1) of the present invention, Oo'1our above
By adding the disperse dye described in Ex.

In addition, when dyeing blended fabrics, blended knitted fabrics, etc., as described above, a one-bath two-step method is used in which one of the fibers is dyed first, and then the other fiber is dyed in the same bath. Furthermore, the dyeing method using the trisazo compound of the present invention and the dyeing method for dyeing 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 explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example/ Cornaphthylamine-z, t, r-trisulfone '11
3F, :1t, 2-methoxy-! -Methylaniline/
The monoazo compound produced by diazotization and coupling with J, 7f in a conventional manner is further co-methoxy-j-
Methylaniline/? ,7? A disazo compound represented by the following formula was prepared by diazotization and coupling using a conventional method. On the other hand, /-amino-? -Hydroxynaphthalene-31g-Disulfonic acid 3/, Rir and [cyanuric acid/
? ,! After condensing 2 at 0°C or lower, deraminobenzenesulfonic acid/7,39 was condensed at 20°C to first produce a compound represented by the following formula %, and then nicotinic acid 7r,
Add Of and sodium hydroxide≦t? The mixture was stirred at θ°C for 10 hours to replace chlorine atoms with nicotinic acid. A diazo solution obtained by diazotizing the above disazo compound with a water-acetic acid system was added to the reaction solution, and the coupling was carried out at 0-j °C, followed by salting out with potassium chloride to obtain the following structural formula (free acid form). ), and the analytical value λ based on visible light absorption below
Trisazo compound with max 7.6? I got it.

A trisazo compound θ, 2t represented by the above structural formula.

Glauber's Salt / , <1. Na2HPO4@/ as a buffering agent
2H20o, 'i t and Kn, po4 θ, /f
7.2 by adding 10 tons of unmercerized cotton knitted fabric to a dye bath adjusted to pH 7 by adding
The temperature was raised to θ°C, dyed at the same temperature for 10 minutes, washed with water, soaped, washed with water, and dried to obtain a greenish dark blue dyed product.

The degree of dyeing of this dye was very good, and the dyed product obtained was extremely dense, and the light fastness, chlorine fastness, and sweat-sunlight fastness were all good.

Examples coaniline-λ,j-disulfonic acid, 2j, JPwo,i!
A monoazo compound produced by diazotization and coupling with -methoxy-j-methylaniline/3,7t in a conventional manner is further diazotized and coupled with methoxy-j-methylaniline/? , Of was diazotized and coupled in a conventional manner to produce a disazo compound represented by the following formula %. On the other hand, co-amino-j-hydroxynaphthalene-2-sulfonic acid, 2
3.9? , cyanuric chloride 7? ,! After condensing F at below 0°C, add 3g of nicotinic acid? and sodium hydroxide/
Add 29? Stir at θ°C for 70 hours to replace the chlorine atom with nicotinic acid to produce a compound represented by the following formula, add the above disazo solution to the reaction solution, and cup at pH 7,j with Q-j 'C. After ringing, the reaction solution was spray dried to obtain a trisazo compound ♂ which is represented by the following structural formula (shown in the form of free acid) and has the following visible light absorption analysis value λmax.
? , 3t was obtained.

(λmax: srsnm (water)) 0.2 f of the trisazo compound represented by the above structural formula.

Glauber's salt/Na1HPO4/2TI as At1 buffering agent
20θ,! ? and KHri PO40,0,2f with water-2
Add unmercerized cotton stockinette/θt to the prepared dye bath and mix for 30 minutes until the temperature reaches /3°C.
After dyeing at the same temperature for 3θ minutes, washing with water, soaping, washing with water, and drying were performed to obtain a dark blue dyed product.
The resulting dyed product, which was kept at pHr throughout, was extremely dense and dense, and had good light fastness, chlorine fastness, and sweat-sunlight fastness.

Example 3 The trisazo compound prepared in Example 0. ．． 21 and monoazo dye 0.2f shown by the structural formula, mirabilite/, 2P1 buffer as Na1HPO4/-2HHO004t t
Polyester/cotton=jθ:jθ
A blended fabric/θt was added and mixed at a temperature of 730°C for 30 minutes. After dyeing at the same temperature for θ minutes, washing with water, soaping, washing with water, and drying were performed to obtain a dark blue dyed product with good isochromaticity. . This staining bath had pFI +1' before and after staining.

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.

Example 3g

Claims (1)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼…………[I] (In the formula, M represents a hydrogen atom or an alkali metal, and R
^1 is a hydrogen atom, a lower alkyl group, a lower alkoxy group,
or represents a sulfonic acid group, R^2 and R^4 represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, an acetylamino group, or a sulfonic acid group, and R^3 represents a lower alkyl group, a lower alkoxy group, or a sulfonic acid group. represents a group, R^5 represents a hydrogen atom or a lower alkyl group,
X represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (M is the same as the above definition, l is 0 or 1), and Y
represents X, a chlorine atom, a fluorine atom, an aromatic amino residue, an aliphatic amino residue, or a hydroxyl group which may be etherified, m represents 1, 2 or 3, and n represents 0 or 1 and benzene rings A, B and C may represent naphthalene rings).