JPH0619046B2 - Disazo compound and dye composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Purpose of the Invention (a) Field of Industrial Application The present invention relates to a novel disazo compound used as a dye for cellulosic fibers and nitrogen-containing fibers, and a dye composition using the same. It is about.

(B) Conventional technology Conventionally, when dyeing cellulose fibers, reactive dyes have been 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. In addition, a method is used in which the pH is 10 or more and the temperature is 100 ° C or less.

However, in recent years, there has been an increase in demand for blended fabrics of cellulose fibers and other fibers, especially polyester fibers, and for dyeing such cellulose / polyester mixed fibers (hereinafter sometimes simply referred to as C / P fibers). It was necessary to apply the dye and dyeing conditions for the cellulose fibers and the dye and dyeing conditions for the polyester fibers, respectively. This is because the dyes and dyeing conditions for dyeing polyester fibers are very different from those for cellulose fibers. That is, it was necessary to use a disperse dye and dye at a temperature of about 130 ° C. to dye the polyester fiber.

For example, if the above C / P fiber is dyed in the same process, two different dyes are used in combination with a reactive dye and a disperse dye, which causes some problems. It was That is, in order to sufficiently dye the reactive dye on the cellulose fiber side, the pH is adjusted to 10 with an acid binder.
Although it is necessary to set the above, 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
However, under high pH as described above, the high temperature promotes hydrolysis of the reactive dye, and dyeing to the cellulose fiber is significantly inhibited. Therefore, when dyeing such C / P fibers, a two-bath method in which one fiber of cellulose or polyester is dyed and then the other fiber is dyed in a separate bath is generally performed. Of.

(C) Problems to be Solved by the Invention The present invention is directed to a disazo compound capable of dyeing a cellulose fiber under a dyeing condition of a polyester fiber with a disperse dye and other dyeing conditions, and a dye containing the same. It is intended to provide a composition.

(b) Structure of the Invention (a) Means for Solving the Problems The above problems could be solved by the disazo compound of the present invention having a specific molecular structure. That is, the present invention has the general formula [I] [In the formula, M represents a hydrogen atom or an alkali metal, and D
z represents a benzene or naphthalene type diazo component residue, R ¹ represents a hydrogen atom or a lower alkyl group,
R ² represents a hydrogen atom or an optionally substituted lower alkyl group, A represents a divalent aromatic or aliphatic residue, and when R ² is a hydrogen atom, X has a substituent. In the case where R ² is a lower alkyl group which may be substituted, X represents an optionally substituted phenylene group or a naphthylene group, and Y represents —S
Represents an O ₂ CH═CH ₂ group or a —SO ₂ C ₂ H ₄ W group (wherein W represents a group capable of leaving by the action of an alkali), and m is 0.
Or represents 1. ] It is related with the disazo compound shown by these, and the dye composition containing it.

In the disazo compound represented by the general formula [I] of the present invention, examples of the alkali metal represented by M include lithium, sodium and potassium, and examples of the diazo component residue represented by Dz include a sulfonic acid group and a carboxyl group. An acid group, a C ₁ -C ₄ lower alkyl group, a lower alkoxy group,
Examples thereof include a phenyl group or a naphthyl group substituted with a halogen atom such as a chlorine atom and a bromine atom.

The lower alkyl group represented by R ¹ and R ² is C ₁
To C ₄ alkyl groups.

Further, as the substituent of R ^2, a cyano group, a hydroxyl group,
Examples thereof include a lower alkoxy group, a halogen atom and a lower alkylcarboxy group.

The divalent residue represented by A includes an ethynylene group, 1,
Aliphatic group such as 3-propylene group, 1,4-butylene group, hexamethylene group or methyl group, methoxy group, carboxyl group, sulfonic acid group, phenylene group substituted or not substituted with chlorine atom, naphthylene group And other aromatic groups.

X is particularly preferably a lower alkyl group such as a methyl group or an ethyl group, a lower alkoxy group such as a methoxy group or an ethoxy group,
Examples thereof include a phenylene group and a naphthylene group which may be substituted with 1 or 2 substituents selected from the group consisting of halogen atoms such as chlorine atom and bromine atom, sulfonic acid group and the like.

As a concrete example represented by Etc.

Examples of the group represented by W that is eliminated by the action of an alkali include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group, and a halogen atom.

The disazo compound represented by the general formula [I] shown above can be produced as follows.

For example, the general formula [II] (In the formula, M, Dz, R ¹ and m are the same as the above definition) 2 mole ratio of the dye and the following formula [III] H ₂ NA-NH ₂ ... [III] (wherein A is the above definition) The same as the above) 1 mol ratio is condensed to form the following formula [IV] (In the formula, M, Dz, R ¹ and m are the same as defined above).

Then, the diazoazo compound represented by the general formula [IV] is added to the following general formula [V] The disazo compound of the general formula [I] shown above can be produced by condensing 1 mole ratio of the compound represented by the formula (R ² , X and Y are the same as defined above) at 90 ° C.

The disazo compound of the present invention produced in this manner,
As described above, it can be used as a dye capable of dyeing cellulose fibers under the pH and other dyeing conditions when dyeing polyester fibers with a disperse dye.

Fibers that can be dyed with the disazo compound of the present invention include cellulosic fibers such as cotton, viscose rayon, cupra ammonium rayon, and hemp.
Further, it can be applied to dye nitrogen-containing fibers such as polyamide, wool and silk. Further, the cellulosic fiber in the mixed fiber of polyester, triacetate, polyacrylonitrile, polyamide, wool, silk, etc. containing cellulosic fiber can be dyed well, of course.

In the method for dyeing fibers using the disazo compound of the present invention, dyes necessary for dyeing fibers other than cellulosics, for example, disperse dyes described in Color Index (Third Edition) are simultaneously added to the dyebath. Can be dyed.

Cellulosic fibers using the disazo compound of the present invention,
When dyeing a nitrogen-containing fiber or the like, for example, the disazo compound represented by the general formula [I] is added in an amount of 0.01 to 50 g / about,
And buffers necessary to keep the dyebath at a pH of 5-10 during dyeing (eg acids such as carbonic acid, phosphoric acid, acetic acid, citric acid, boric acid and the sodium or potassium salts of these acids, either alone or in mixtures. ) Is usually added in an amount of 0.5 to 5.0 g, and if necessary, an electrolyte (sodium chloride or sodium sulfate) is added in an amount of 1 to 150 g / preferably 40 to 80 g / g. Good dyeing can be performed by adding cellulosic fibers and nitrogen-containing fibers and heating at a temperature of 100 to 150 ° C. for 30 to 50 minutes.

Further, in order to dye a blended fabric, a blended knitted fabric, etc., which is produced by mixing other fibers such as a polyester fiber with a cellulosic fiber, in the above composition, the above Color is further added.
0.01 to 50 g / dispersed dye listed in Index, a surfactant (for example, anionic surfactant such as sulfosuccinic acid-based agent,
Nonylphenol-based nonionic surfactant, etc.) 0.5-
Cellulose fibers and polyester fibers can be dyed at the same time by the one-bath one-step method by preparing a dyeing bath by adding about 3 g / about.

Further, in the case of dyeing a mixed-spun fabric, a mixed-woven knitted fabric, or the like as described above, a one-bath two-step method in which one fiber is dyed as is conventionally used and then the other fiber is dyed in the same bath In addition, a two-bath for dyeing the cellulosic fiber and the other fiber from separate baths by combining the dyeing method with the disazo compound of the present invention and the dyeing method for fibers other than the cellulosic fiber It is also possible to adopt the law.

Therefore, the dye composition containing the disazo compound of the present invention as a dye, in addition to the dye component, other components necessary for the dye, such as water as a medium, buffers as described above, electrolytes, surfactants, etc. It contains a dyeing aid. If necessary, other dyes such as disperse dyes listed in Color Index may be added.

The dye composition of the present invention may be one that can be used as it is for a dye, or one that is a thick liquid or paste that can be used by dissolving it in water during dyeing. In the case of a composition which can be used for dyeing as it is, as described above, the disazo compound represented by the general formula [I] is contained in an amount of 0.01 to 50 g / about, a buffering agent of 0.5 to 5.0 g /, and an electrolyte of 1 to 150 g /
An aqueous solution containing about a degree is general. In the case of a concentrated liquid or paste, the disazo compound can be contained up to about 200 g /.

(B) Examples, etc. Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 below 2 mol ratio of the monoazo dye represented by and 1 mol ratio of p-phenylenediamine are condensed in an aqueous medium at 30 to 40 ° C. A disazo compound represented by the following formula is produced, and 3- (β
-Hydroxyethyl) sulfonyl N-methylaniline sulfuric acid ester (2 mol ratio) was added, condensed at 90 ° C, salted out with potassium chloride, and the following structural formula (shown in the form of free acid) and the analytical value by visible light absorption were obtained. A disazo compound having the above was obtained.

Next, 0.2 g of the above-mentioned disazo compound, 16 g of Glauber's salt, 0.4 g of Na ₂ HPO ₄ 12H ₂ O and 0.1 g of KH ₂ PO ₄ as a buffer were added to 200 m of water.
In addition to 1, add 10 g of unmercerized cotton knitted fabric to a dyebath adjusted to pH = 7, raise the temperature to 120 ° C over 30 minutes, and dye at the same temperature for 60 minutes, then wash with water, soaping, wash with water, and dry Then, an orange dyed product was obtained. The dyeing degree of this dye was very good, and the obtained dyed product had an extremely thick orange color, and the light fastness, chlorine fastness, and sweat-sunlight fastness were all good.

Example 2 Dyeing was carried out according to Example 1 except that 10 g of unmercerized cotton knitted fabric was changed to 10 g of wool muslin in Example 1.

As a result, wool muslin was dyed in a very dark orange color.

Example 3 below 2 mol ratio of monoazo dye represented by and 1 mol ratio of ethylenediamine are condensed in an aqueous medium at 30 to 40 ° C. The disazo compound represented by
(Β-Hydroxyethyl) sulfonyl N-ethylaniline Sulfate 2 mol ratio was added and condensed at 90 ° C., then spray dried to have the following structural formula (in the form of free acid) and an analytical value by visible light absorption. A disazo compound was obtained.

Next, 0.2 g of the above disazo compound, 16 g of Glauber's salt, 0.5 g of Na ₂ HPO ₄ 12H ₂ O and 0.02 g of KH ₂ PO ₄ as buffering agents were added to 200 ml of water.
Add 10 g of unmercerized cotton knitted fabric to the dyeing bath prepared in addition to 30 ℃, raise the temperature to 130 ℃ for 30 minutes, dye at the same temperature for 30 minutes, and then wash with water, soap, wash with water and dry to give a scarlet dyeing. I got a thing. The pH of this dyebath was 8 before and after dyeing. The obtained dyed product was extremely thick and had good fastness to light, fastness to chlorine, and fastness to sweat and sunlight.

Example 4 The following structural formula in the form of free acid 0.2 g of a disazo compound represented by 0.2 g of anthraquinone dye represented by the formula, 12 g of phosphine, 0.4 g of Na ₂ HPO ₄ 12H ₂ O and 0.1 g of KH ₂ PO ₄ as a buffer agent in water 20
Polyester / cotton = 50: 5 in a dye bath prepared by adding 0 ml
10 g of the blended fabric of 0 was added, the temperature was raised to 130 ° C. over 30 minutes, the dyeing was carried out at the same temperature for 60 minutes, followed by washing with water, soaping, washing with water and drying to obtain a red dyed product with good color uniformity. . The dyebath had a pH of 8 before and after dyeing. Further, the dyeing property was very good, and the obtained dyed product was extremely dense and had good light fastness, chlorine fastness, and sweat-sunlight fastness.

The disazo compound used in this example was produced according to Example 1.

Examples 5 to 24 By the method according to the method described in Example 1, the above general formula [I]
Various disazo compounds (shown in the form of the free acid) described in Table 1 below were prepared. The analytical values of the obtained compounds and the results of dyeing cotton cloth are shown in Table 1.

Example 25 A thick dye composition was obtained by mixing the following components.

Disazo compound of Example 1 10 g Na ₂ HPO ₄ 12H ₂ O 10 g KH ₂ PO ₄ 3 g Water 200 ml When the above composition is used, a dye bath can be prepared by diluting with water 10,000 ml.

Example 26 The following components were blended to obtain a thick dye composition.

Disazo compound of Example 3 1 g Na ₂ HPO ₄ 12H ₂ O 2.5 g KH ₂ PO ₄ 0.1 g Glauber's salt 25 g Water 200 ml When the above composition is used, a dye bath can be prepared by diluting it with 800 ml of water.

(c) Effects of the Invention As described above and as shown in the examples, the present invention provides a novel disazo compound, and by using it as a dye, when dyeing polyester fibers with a disperse dye Cellulose fibers can be satisfactorily dyed even under pH and other dyeing conditions, and therefore, there is no need to separately use a separate bath when dyeing cellulose / polyester mixed fibers.

Claims (17)

[Claims] 1. A general formula [I] [In the formula, M represents a hydrogen atom or an alkali metal, and D
z represents a benzene or naphthalene type diazo component residue, R ¹ represents a hydrogen atom or a lower alkyl group,
R ² represents a hydrogen atom or an optionally substituted lower alkyl group, A represents a divalent aromatic or aliphatic residue, and when R ² is a hydrogen atom, X has a substituent. In the case where R ² is a lower alkyl group which may be substituted, X represents a phenylene group or a naphthylene group which may have a substituent, and Y represents —SO ₂
CH = CH ₂ group or -SO ₂ C ₂ H ₄ W group (wherein W represents a group capable of leaving by the action of an alkali), and m represents 0 or 1. ] The disazo compound shown by these. 2. Dz is sulfonic acid group, carboxylic acid group, C
The disazo compound according to claim _{1, which is} a lower alkyl group of _{1 to 4,} a lower alkoxy group of C _{1 to 4} or a phenyl group or a naphthyl group substituted with a halogen atom. 3. The disazo compound according to claim 1, wherein R ² is a lower alkyl group or a lower alkyl group substituted with a cyano group, a hydroxyl group, a lower alkoxy group, a halogen atom or a lower alkylcarboxyl group. 4. The disazo compound according to claim 3, wherein X is a phenylene group, a naphthylene group, a lower alkyl group, a lower alkoxy group, a phenylene group substituted with a halogen atom or a sulfonic acid group, and a naphthylene group. 5. The method according to claim 1, wherein R ² is a hydrogen atom, and X is a naphthylene group or a naphthylene group substituted with a lower alkyl group, a lower alkoxy group, a halogen atom or a sulfonic acid group. Disazo compound. 6. The disazo compound according to claim 1, wherein W is a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group or a halogen atom. 7. A is an ethylene group, a 1,3-propylene group,
1,4-butylene group, hexamethylene group, phenylene group,
The disazo compound according to claim 1, which is a naphthylene group, a methyl group, a methoxy group, a carboxyl group, a sulfonic acid group, or a phenylene group substituted with a chlorine atom, or a naphthylene group. 8. The following general formula [I] [In the formula, M represents a hydrogen atom or an alkali metal, and D
z represents a benzene or naphthalene type diazo component residue, R ¹ represents a hydrogen atom or a lower alkyl group,
R ² represents a hydrogen atom or an optionally substituted lower alkyl group, A represents an aromatic or aliphatic divalent residue, and when R ² is a hydrogen atom, X has a substituent. In the case where R ² is a lower alkyl group which may be substituted, X represents a phenylene group or a naphthylene group which may have a substituent, and Y represents —S
Represents an O ₂ CH═CH ₂ group or a —SO ₂ C ₂ H ₄ W group (wherein W represents a group capable of leaving by the action of an alkali), and m is 0.
Or represents 1. ] The dye composition containing the disazo compound shown by these. 9. Dz is sulfonic acid group, carboxylic acid group, C
_1-4 lower alkyl group, a lower alkoxy group or a dye composition in the range 8 claim of claims is a phenyl group or a naphthyl group substituted by a halogen atom C _1-4. 10. R ² is a lower alkyl group or a cyano group,
The dye composition according to claim 8, which is a lower alkyl group substituted with a hydroxyl group, a lower alkoxy group, a halogen atom or a lower alkylcarboxyl group. 11. The dye composition according to claim 10, wherein X is a phenylene group, a naphthylene group, a lower alkyl group, a lower alkoxy group, a phenylene group substituted with a halogen atom or a sulfonic acid group, and a naphthylene group. . 12. The dye composition according to claim 8, wherein R ² is a hydrogen atom and X is a naphthylene group or a naphthylene group substituted with a lower alkyl group, a lower alkoxy group, a halogen atom or a sulfonic acid group. . 13. The dye composition according to claim 8, wherein W is a sulfate group, a thiosulfate group, a phosphate group, an acetate group or a halogen atom. 14. The dye composition according to claim 8, which is a composition containing water and a dyeing aid. 15. The dye composition according to claim 14, wherein the dyeing aid is a buffer, an electrolyte and a surfactant. 16. The buffer according to claim 15, which is carbonic acid, phosphoric acid, acetic acid, citric acid, boric acid or a salt thereof.
The dye composition according to the item. 17. The dye composition according to claim 15, wherein the electrolyte is sodium chloride or sodium sulfate.