JPS63189469A - Water-soluble disazo dyestuff - Google Patents

Abstract

NEW MATERIAL:A compd. of formula I in the form of a free acid {R<1> is H, halogen, cyano, carbamoyl, etc.; R<2> is H, (sulfonic acid-substd.)alkyl or lower alkoxy-lower alkyl; R<3> is H, methyl or carboxyl; R<4> is H, methyl or sulfonic acid; A is divalent aromatic or aliphatic residue; Z<1> and Z<2> are a group of formula II or halogen, provided that at least one of them is the group of formula II [R<5> is H or (substd.)lower alkyl; X is (substd.)phenylene or naphthylene; V is -SO2CH=CH2 or -SO2C2H4W (W is a group eliminable by the action of an alkali)]}. EXAMPLE:The compd. of formula III. USE:A dyestuff for dyeing cellulosic fibers and nitrogen-contg. fibers in yellowish colors. The cellulosic fibers can be dyed in an excellent reacting and fixing rate of the dyestuff under conditions for dyeing polyester fibers. PREPARATION:2mol. of a compd. of formula IV (Z is halogen) is condensed with 1mol. of a compd. of formula: H2N-A-NH2 to give a disazo compd., which is then reacted with 1-3mol. of a compd. of formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a yellow water-soluble disazo dye having a novel structure. The invention relates to a disazo dye which has excellent reactive fixation properties, particularly to cellulose and nitrogen-containing fibers.

BACKGROUND OF THE INVENTION Water-soluble reactive dyes are usually used as dyes for dyeing cellulose or nitrogen-containing fibers, and dyes having various structures have been proposed.

Generally, when dyeing the above-mentioned fibers by dyeing using such dyes, the temperature of the dye bath is relatively low, for example, about 60 to 70°C.

In recent years, with the diversification of fiber materials, for example, mixed fibers of cellulose fibers and polyester fibers have been used. Conventionally, the dyeing method for such mixed fibers has been to dye 120% by using a disperse dye in advance. A so-called two-stage method is employed in which polyester fibers are dyed at a high temperature of about 140'C to 140'C, and then cellulose fibers are dyed using a reactive dye at a low temperature of about 60 to 70'C. However, recently, a method has been proposed in which cellulose and polyester fibers are dyed simultaneously in a high-temperature dye bath of 120 to 140'C in one bath using a combination of a reactive dye and a disperse dye. Regarding this, a reactive dye consisting of a pyridone compound represented by the following structural formula [A] is known. (Refer to JP-A-58-186682) [A] Problems to be Solved by the Invention However, it has been difficult to dye cellulose fibers using known reactive dyes in a high-temperature dye bath as described above. When this was done, the rate of reaction and fixation of the dye to the fibers was low, and good dyed cabbage could not be obtained.

For example, when a reactive dye consisting of a pyridone compound represented by the above structural formula [A1] is used as a dye to improve such problems, a high temperature dye bath (for example, 13
When dyeing with 0'C), although a certain degree of effect can be obtained, there is a problem that the dyeing rate and build-up property are still insufficient.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water-soluble dye that exhibits an even better reaction fixation rate for cellulose fibers even under the dyeing conditions of polyester fibers. be.

Means for Solving the Problems The above-mentioned object of the present invention is to obtain a free acid having the following general formula [] (wherein R1 is a hydrogen atom, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, a sulfonic acid group, or represents a sulfomethyl group, R2 represents a hydrogen atom, an alkyl group optionally substituted with a sulfonic acid group, or a lower alkoxy lower alkyl group, R3 represents a hydrogen atom, a methyl group, or a carboxyl group, and R4 represents a hydrogen atom ,
represents a methyl group or a sulfonic acid group, A represents an aromatic or aliphatic divalent residue, Zl and Z2 each represent a group -N-X-V or a halogen atom, and R5 is a hydrogen atom or a substituted represents a lower alkyl group which may have a substituent @ group, This is achieved by using a water-soluble disazo dye represented by the following formula:

The present invention will be explained in detail below.

In the disazo dye represented by the general formula [I] of the present invention, the halogen atom represented by R1 is usually
Examples include fluorine atom, chlorine atom, and bromine atom, with chlorine atom or bromine atom being particularly preferred.

Examples of the alkyl group represented by R2 include linear or branched alkyl groups having 1 to 8 carbon atoms such as methyl group, ethyl group, isopropyl group, n-butyl group, n-octyl group, and 2-ethylhexyl group. can be given. Note that this alkyl group may be substituted with a sulfonic acid group,
A specific example in this case is 02 H4S O3Hl
o 3 H6S O3H is defeated. Examples of the lower alkoxy lower alkyl group include an alkyl group having 1 to 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, such as a methoxyethyl group, an ethoxyethyl group, a propoxypropyl group, and a butoxyethyl group. can give.

Examples of the divalent residue represented by A include ethylene group, 1,3-propylene group, 1,4-butylene group, hexamethylene group, 1,4-cyclohexylene group, -C2H4
Included are aliphatic groups such as 0C2H4-, or phenylene, naphthylene, or stilbene groups which may be substituted with methyl, ethoxy, carboxyl, sulfonic acid, chlorine, or the like.

Further, in the present invention, it is particularly desirable that at least one of Zl and Z2 necessarily be a group -NX-V. When Zl or Z2 represents a halogen atom, it is usually a chlorine atom, a fluorine atom or a bromine atom.

The lower alkyl group which may have a substituent represented by R5 is, for example, a C1 to C4 linear or branched unsubstituted alkyl group, 2-hydroxyethyl, 2-hydroxyethyl,
-cyanoethyl, cyanomethyl, 2-chloroethyl, 3
-1% water such as -ethoxypropyl, an alkyl group substituted with a cyano group, a halogen atom, or an alkoxy group.

The phenylene group or naphthylene group which may have a substituent represented by Examples include a phenylene group or a naphthylene group substituted with one or two substituents selected from a lower alkoxy group such as an ethoxy group, a halogen atom such as a chlorine atom or a bromine atom, and a sulfonic acid group.

Specific examples of the group represented by the general formula -N-X- composed of R5 and X include the following.

Examples of the group represented by -W which is eliminated by the action of an alkali include a sulfurized ester group, a thioTtfL acid ester group, a phosphate ester group, an acetate ester group, and a halogen atom. Ester groups are preferred.

The disazo compound of the present invention exists in the form of a free acid or in the form of a salt thereof, and the salts are usually alkali metal salts and alkaline earth metal salts, with lithium salts, sodium salts, and potassium salts being particularly preferred.・.

The disazo compound represented by the general formula [I] can be produced as follows. For example, the following compound [l
11 (wherein, Z represents a halogen atom, R1, R2, R3
and R4 are the same as defined above) Compound 2
By condensing the molar proportion and the 1 molar proportion of the compound represented by the following general formula [I[1]% formula % [[] (wherein A is the same as the above definition), the following general formula [IV] (formula (wherein, R1, R2, R3, R4, A and Z are the same as defined above) A disazo compound represented by the following general formula [Vl HN-X-V[Vl (wherein, (R5, X and V are the same as defined above) A disazo dye represented by the general formula [I] can be produced. In addition, depending on the usage ratio of the compound represented by the front claw general formula [Vl], 71 and Z of the front claw general formula [I]
It is determined how much of 2 becomes the group -N-X-V, and in some cases, it is recovered as a mixture of two types of pigments that satisfy the general formula [E].

The disazo dye of the present invention can be widely used as a dye for dyeing fibers and cloth, a dye for coloring paper and synthetic resins, and a dye for inkjet printers. Excellent aptitude.

When using the disazo dye of the present invention as a dye, target fibers include cellulose fibers such as cotton, viscose rayon, cuproammonium rayon, and hemp, as well as nitrogen-containing fibers such as polyamide, wool, and silk. Cellulose fibers are particularly preferred. These fibers can also be made of, for example, polyester, triacetate,
Mixed fibers such as polyacrylonitrile may also be used.

In the fiber dyeing method using the disazo dye of the present invention, dyes necessary for dyeing non-cellulose fibers, such as disperse dyes described in the Cofor 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 disazo dye of the present invention, for example, the disazo dye represented by the above general formula [1] and the dye bath 1) H5 to 10 (particularly preferably 8 to 9) Buffers necessary to maintain the temperature (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 5.0 g/ fJ), and if necessary, an electrolyte (sodium chloride or sodium sulfate, etc., usually about 1 to 1503/f1, particularly preferably 40 to 8
0y/, Q) is added, cellulose fibers are added to the dye bath, and the temperature is 100 to 150'C for 30 to 30 minutes.
Good dyeing can be achieved by heating for 60 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, a disazo dye represented by the above general formula [I] of the present invention may be used. By adding a disperse dye described in Color Inde In this case, l)H of the dyebath is preferably maintained at 7-9.

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 disazo dye of this defense and the dyeing method for fibers other than cellulose iron cloth may be combined to dye cellulose fibers and their related fibers from separate baths. It is also possible to adopt a two-bath method.

In addition, during dyeing, the disazo dye of the present invention has a vinyl sulfone-based reactive group in its structure, for example, S O
2C2H40S O3H is hydrolyzed to -8O2CH
=CH2 and reacts with the fiber.

EXAMPLES Hereinafter, 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 1 Production Example 2 moles of a heptanoazo compound represented by the following structural formula in the form of a free acid and 1 mole of p-phenylenediamine were mixed in an aqueous solvent at a temperature of 30 to 40'C under conditions of pH 7. Condensation was carried out below to produce a disazo compound represented by the following structural formula. Furthermore, 2 molar proportions of 3-(β-hydroxyethyl)sulfonylaniline sulfate were added to the mixture containing this disazo compound, and the mixture was reacted at a temperature of 90°C and pH 5 for 7 hours, and then salted out with potassium chloride. A disazo dye mixture (component A: 9% by weight, component B = 91% by weight) represented by the following structural formula was produced.

[8] λmax: 419 nm (water) Dyeing example> Using 0.27 of the disazo dye obtained as above as a dye, this, 16 g of Glauber's salt, and Na2H as a buffering agent.
PO412H200,5g and KH2PO40,02
Mercerized cotton stockinette 109 was added to 200 d of water to adjust the pH to 7.
After raising the temperature to 0°C and dyeing at the same temperature for 60 minutes, washing with water, sowing pink, washing with water, and drying were performed to obtain a yellow dyed product.

The dyeing rate of this dye in this dyeing test was very good at 80%, and the dyed product obtained was extremely rich.
The light fastness was also good at 4-5.

Example 2 Production Example 2 molar proportions of a monoazo compound represented by the following structural formula and 1 molar proportion of ethylenediamine were mixed in an aqueous solvent at a temperature of 30 to 40°C.
Condensation was performed under H7,5 conditions to produce a disazo compound represented by the following structural formula. Furthermore, 3.0 molar ratio of 3-(β-hydroxyethyl)sulfonylaniline tL acid ester/L was added to the mixture containing this disazo compound, and the mixture was reacted at a temperature of 90'C and a pH of 5 for 12 hours. Thereafter, salting out with sodium chloride was carried out to crush the disazo dye represented by the following structural formula.

λmax: 418 nm (water) Dyeing example> Using 0.29 ml of the disazo dye obtained as above as a dye, it was prepared by adding this, 16 g of Glauber's salt, and 0.40 d of sodium bicarbonate as a buffer to 200 d of water. Put 10g of unmercerized cotton stockinette into the dye bath, raise the temperature to 130'C over 30 minutes, dye it at the same temperature for 30 minutes, then wash with water, saw pink, wash with water, dry, and dye yellow. I got something. The pH of this dyeing bath was 8.4 before and after dyeing.

The dyeing rate of this dye in this dyeing test was as good as 76%, and the dyed product obtained was an extremely rich yellow color.
The light fastness was also good at grade 4-5.

Example 3 0.2 g of the disazo dye mixture produced in Example 1 and a known quinophthalone dye for polyester represented by the following structural formula 0
．． Using a mixed dye consisting of 29 and 12tj of mirabilite
, sodium bicarbonate, 0.43 rum as a buffer, water 2
10y of polyester/cotton = 50:50 blended fabric was added to the dye bath prepared by adding 00Idl, heated to 130'C over 30 minutes, dyed at the same temperature for 60 minutes, and then washed with water. , so-pink, washing with water, and drying to obtain a yellow dyed product with good same color property. The pH of this dyeing bath was 8.2 before and after dyeing.

The dyeing properties of each dye in this dyeing test were very good, and the dyed product obtained was extremely rich, and its light fastness was grade 4-5.

Example 4 Disazo dyes of the present invention shown in Table 1 (shown in free acid form)
was synthesized according to the method of Example 1 or Example 2, and polyester/cotton = 50:50 in the same manner as Example 3.
When the blended fabrics were dyed, good dyed products were obtained in each case. Moreover, the light fastness of these samples was 4-5@, which was good.

Effects of the Invention The disazo dye of the present invention is a novel compound having at least one vinyl sulfone reactive group, and is useful as a yellow dye. In particular, when this compound is used for dyeing fibers containing cellulose or nitrogen-containing fibers, it has the effect of not only having good various fastnesses but also having excellent dyeability.

This effect can also be obtained under high temperature dyeing conditions of, for example, 120 to 140'C, which have been conventionally employed as dyeing conditions for polyester. Therefore, the disazo dye of the present invention is particularly suitable as a raw dye for simultaneous dyeing of mixed fibers of polyester and cellulose or nitrogen-containing fibers in a step-by-step bath using a water-insoluble disperse dye, for example.

Claims (1)

[Claims] (1) In the form of free acid, the following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] {In the formula, R^1 is a hydrogen atom, a halogen atom, a cyano group,
represents a carbamoyl group, carboxyl group, sulfonic acid group, or sulfomethyl group, R^2 represents a hydrogen atom, an alkyl group optionally substituted with a sulfonic acid group, or a lower alkoxy lower alkyl group, R^3 represents hydrogen represents an atom, methyl group or carboxyl group, R^4 represents a hydrogen atom, methyl group or sulfonic acid group, A represents an aromatic or aliphatic divalent residue, Z^1 and Z^
2 represents a group -N-X-V or a halogen atom, and at least one of them represents a group -N-X-V [However, R^
5 represents a hydrogen atom or a lower alkyl group that may have a substituent, X represents a phenylene group or a naphthylene group that may have a substituent, and V represents a group -SO_2CH=CH_
2 or a group -SO_2C_2H_4W (where W represents a group that is eliminated by the action of an alkali)]} A water-soluble disazo dye represented by the following.