JPS60215060A - Trisazo compound and trisazo dye - Google Patents

Abstract

NEW MATERIAL:A trisazo compound of formula I (where M is H or an alkali metal; R<1> is H, a lower alkyl, a lower alkoxy or a sulfonic acid group; R<2> and R<4> are each H, a lower alkyl, a lower alkoxy, acetylamino, etc.; R<3> is a lower alkyl, a lower alkoxy or a sulfonic acid group; R<5> and R<6> are each H, methyl, methoxy, etc.; Z is chlorine, fluorine, methoxy, etc.; m is 2-3; n is 0 or 1). USE:A trisazo dye which enables dying of cellulosic fibers such as cotton or hemp under the same pH and dying conditions as those for dying polyester fibers with a disperse dye. PREPARATION:A disazo compound of formula V obtained by reacting compounds of formulas II, III, and IV is diazotized, and the diazonium compound is coupled with a compound of formula VI to give the trisazo compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel trisazo compounds and trisazo dyes.

Traditionally, when dyeing cellulose fibers, reactive dyes are used and dyes are dyed at pH 10 in the presence of acid binders such as carbonate, potassium carbonate, and liquefied sodium, and electrolytes such as sodium chloride and sodium sulfate. In the above, a method is adopted in which the temperature is below 100°C.

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 ψ fibers), it is necessary to It was necessary to apply dyes and dyeing conditions and dyes and dyeing conditions to polyester fibers separately. 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 about 730°C.

For example, if the above o and 'p fibers were to be dyed in the same process, two different dyes would be used in combination of a reactive dye and a disperse dye. There was a problem.

For example, in order to dye reactive dyes sufficiently on the cellulose fiber side, it is necessary to use an acid binder to increase ppl (ppl) to 10 or more.The presence of an acid binder promotes the decomposition of disperse dyes, The dyeing on the polyester fiber side becomes insufficient. On the other hand, in order to dye disperse dyes on the polyester fiber side, high temperature conditions (normal/JO℃) are required, but at high temperatures under the above-mentioned high-pitched conditions, hydrolysis of reactive dyes is promoted, and cellulose fibers are Dyeing on the sides will be significantly inhibited. Therefore, when dyeing such 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. be.

The object of the present invention is to provide a trisazo compound capable of dyeing cellulose fibers under the conditions of dyeing polyester fibers (with disperse dyes).

That is, the present invention is based on the general formula (1) % formula % (1) (where M represents a hydrogen atom or an alkali metal, and R
' represents a hydrogen atom, a lower alkyl group, a lower alamino group, or a sulfonic acid group, R8 represents a lower alkyl group, a lower alkoxy group, or a sulfonic acid group, and R5 and R6 represent a hydrogen atom, a methyl group, a methoxy group, or a sulfonic acid group. 2 represents a chlorine atom, a fluorine atom, an aliphatic or aromatic amino residue, a methoxy group or a phenoxy group, m represents co or 3, n represents o4 or /, and a benzene ring The trisazo compounds and trisazo dyes represented by the following formulas (B, B and C may represent 7 talenes) are used.

In the trisano compound represented by the general formula [1] of the present invention, the alkali metal represented by M includes sodium, potassium, etc., and the lower alkyl group and lower alkoxy group represented by B(, RζR3 and R4) Examples include an alkyl group and an alkoxy group having 1 to - carbon atoms.

The aliphatic or aromatic 7-mino residue represented by 2 includes amino, 0 carbonate to 4-alkyla 5-no, ethanolamino, β-sialethylamino, β-sulfoethylamino, glycine residue, anilino and sulfo, Examples include anilino groups substituted with chloro, lower alkyl, lower alkoxy, nitro, carboxy, and the like.

For example, the general formula [■), [11), (IV) [...
) [, ll1) [R1] (wherein, R1, R1, Ra, R4, m and benzene rings A, B and O are the same as defined above) by performing usual diazotization and coupling. This is repeated to obtain a disazo compound represented by the following general formula (V).

On the other hand, the following formulas [■], [■], [■] [■] [■] [■] (wherein, R', R'', Z and n are the same as the above definitions)
In an aqueous medium, the compound represented by is condensed in any order to obtain the following general formula CK) (wherein R11, R6, 2 and n are the same as defined above)
A compound represented by is produced.

Next, the disazo compound of the above-mentioned (V) is coupled to the compound of the general formula [] with a didizonium compound cyasifated in a water-acetic acid medium to obtain the trisazo compound of the general formula [I]. can be manufactured.

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, cellulose fibers in mixed fibers such as polyester, triacetate, polyacrylonitrile, polyamide, wool, silk, etc. containing cellulose fibers can of course be dyed well.

Fibers using the tri-3azo compound of the present invention (3rd edition)
Dyeing can be carried out by simultaneously adding disperse dyes such as those described in 710 to the dye bath.

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
Buffers necessary to maintain toV (for example, carbonic acid, phosphorous acid, acetic acid, citric acid, etc., and sodium salts or potassium salts of these acids, singly or in mixtures, usually 0.j~!
, 01) and an electrolyte (sodium chloride or sodium sulfate, etc., usually 1~/, tO) depending on the 51fC.
t/A) to adjust a nine-dye bath, add cellulose fibers to this dye bath, and dye at a temperature of 30-1 at a temperature of 10θ to 120℃.
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, a trisazo compound represented by the above general formula CI] of the present invention and the above 0010ur Thdex
By adding the listed disperse dye to the above dye bath, it is possible to simultaneously dye sucrose-based fibers and polyester fibers by a one-bath, one-stage method.

In addition, when dyeing blended fabrics, blended knitted fabrics, etc., as mentioned above, a one-bath two-step method is used, in which one fiber is dyed and then the other fiber is dyed in the same bath. Furthermore, a two-bath method may be used 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 the law.

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.

Example 1 Structural formula below in free acid form.

(λ WB 1 and 1! , H2
Add unmercerized cotton stockinette to a dye bath prepared by adding PO40,/f to 200 t ILl of water to a temperature of 7.
The temperature was raised to 12θ°C over 0 minutes, dyed at the same temperature for 60 minutes, washed with water, sown pink, 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.

In addition, the trisazo compound used in this example, conaphthylamine-3,lsJ-)disulfonic acid JLJt
Cometoxie! - A monoazo compound produced by diazotization and coupling with methylaniline/3.7t in a conventional manner is further cometoxylated! -Methylaniline lJ
, 7f by a conventional method to produce a dinuazo compound represented by the following formula. On the other hand, l-amino-r-hydroxynaphthalene-J, J-disulfonic acid 3
After condensing Yarif and cyanuric chloride/l'', !i at 5°C or lower, 2 L/l of 3-(β-hydroxyethyl)sulfonylaniline sulfate was condensed at 3Q to 33°C to form a compound of the following formula. The trisazo compound was prepared by diazotizing the dinuazo compound in the reaction solution with a water-acetic acid system, removing the diazo solution, cambling, and salting out with potassium chloride.

Example λ A trisazo compound represented by the following structural formula in the form of a free acid 0.22, mirabilite/J1% as a buffer (Mallu) 04·/2B40 0 , r
f k and KH2PO40,0ko2 water 200rtt
unmercerized cotton Melya Iio to the prepared dyebath in addition to
';t was added, the temperature was raised to /30°C over 30 minutes, 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 was -g before and after dyeing. The dyed product obtained was extremely dense and had good light fastness, chlorine fastness, and sweat-sunlight fastness.

In addition, the trisazo compound used in this example was non-naphtheramine, i-dinulfonic acid jO,3t/-
The monotuno compound produced by diazotization and coupling with sulftylamine-7-nulfonic acid-,2,Jt in a conventional manner is further diazotized with 2-methquine-5-acytylaminoaniline lza,Of in a conventional manner. A dinuazo compound represented by the following formula was prepared by compounding and campling. On the other hand, 23. Ri f, cyanuric chloride ir, tit o! Hey? −(
A compound of the following formula, which is a condensation product of β-hydroxyethyl)nuruhoelaniline sulfate, zr, and it, is produced, and after diazotization and coupling with the dinuazo compound produced earlier, the reaction solution is sprayed. The trinuazo compound of this example was prepared by drying.

Example 3 A trinuazo compound represented by the following structural formula % (% ()) in the form of free acid Sonoazo dye represented by O, Cof, Glauber's Salt/21, NazH as a buffering agent
PO4/λTl, OO, 4A f and KEI, QO
, / f to 200 m of water to prepare a dye bath with polyester/cotton writhing! θ:! A blended fabric 101 of θ was added and the temperature was raised to 30°C over 30 minutes. After dyeing at the same temperature for 60 minutes, washing with water, sowing pink, washing with water, and drying were carried out to obtain a dark blue dyed product with good same color property. . This dyeing bath was pnr before and after dyeing. Furthermore, the dyeing property was very good, and the dyed product obtained was extremely dense, and the light fastness, chlorine fastness, and sweat-sunlight fastness were all good.

The trinuazo compound used in this example is λ-methoxy!, which was used in Example 2. -Acetylaminoaniline ir, ott-Kome F xy J-Methylaniline/J, produced in the same manner as in Example 7 except that 7f was replaced.

Example 4 A cotton cloth was dyed with a trinuazo compound represented by the following general formula in the same manner as in Example 1,
The results are shown in Table 1.

Claims (2)

[Claims] (1) General formula [■] ・・・・・・・・・[■] (In the formula, M represents a hydrogen atom or an alkali metal, and R
1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or an L sulfonic acid group, R2 and R4 are a hydrogen atom,
Represents a lower alkyl group, lower alkoxy group, a+thylamino group or sulfonic acid group, R3 is a lower alkyl group,
represents a lower alkoxy group or a sulfonic acid group, R5 and R6 represent a hydrogen atom, a methyl group, a methoxy group, or a sulfonic acid group, and 2 represents a chlorine atom, a fluorine atom, an aliphatic or aromatic amino residue, a methoxy group, or A trisazo compound represented by a phenoxy group, m represents co or 3, n represents θ or l, and benzene 3j1A, B and 0 may represent a 7talene term). (2) General formula [I] ...... [Summer] (In the formula, M represents a hydrogen atom or an alkali metal, and R
1 represents a hydrogen atom, a lower alkyl group, a koxy group or a sulfonic acid group at the lower atom, R2 and R4 are a hydrogen atom,
Represents a lower alkyl group, lower alkoxy group, a7tylamino group or sulfonic acid group, R8 is a lower alkyl group,
Represents a lower alkoxy group or a sulfonic acid group, R'
R@ represents a hydrogen atom, methyl group, methoxy group or sulfonic acid group, 2 represents a chlorine atom, fluorine atom, aliphatic or aromatic amino residue, methoxy group or phenoxy group, m represents co or 3, n represents O or 1, and benzene rings A, B and 0 may represent a 7 talene ring).