JPH0655905B2 - 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 increasing demand for a mixed fabric 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 ° C)
However, under the above high pH, the high temperature accelerates the hydrolysis of the reactive dye, and the dyeing on the cellulose fiber is significantly inhibited. Therefore, when dyeing such C / P fibers, the two-bath method in which one fiber of cellulose or polyester is dyed and the other fiber is dyed in another bath is generally performed. Of.

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

(b) Structure of the Invention (a) Means for Solving Problems The above problems can 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 R
¹ represents a hydrogen atom, a carboxyl group, a lower alkyl group, a lower alkoxy group, an acylamino group, a carbamoylamino group or a halogen atom, R ² represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, and R ³ represents Represents a hydrogen atom or a lower alkyl group which may have a substituent, and when R ³ is a hydrogen atom, X represents a naphthylene group which may have a substituent, and R ³ has a substituent. In the case of a lower alkyl group which may be substituted, X represents a phenylene group or a naphthylene group which may have a substituent, and Y is a -SO 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 represents 2 or 3. ] It is related with the disazo compound shown by these, and the dye composition containing it as a dye component.

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, potassium and the like, and a lower alkyl group represented by R ¹ , R ² and R ³ , or Examples of the lower alkoxy group include C ₁ -C ₄ alkyl groups and alkoxy groups.

Examples of the halogen atom represented by R ¹ and R ² include a chlorine atom, a fluorine atom and a bromine atom.

The acylamino group represented by R ¹ is Alternatively, —NHSO ₂ R ⁴ group (wherein R ⁴ represents a C _{1 to} C ₃ alkyl group or a phenyl group) can be mentioned.

Examples of the group substituting the lower alkyl group for R ³ include a cyano group, a hydroxyl group, a lower alkoxy group, a halogen atom and a lower alkylcarboxy group.

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 which 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, a halogen atom and the like.

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

For example, the general formula [II] (Wherein M, R ¹ , R ² and m are the same as defined above) and 1 mole ratio of the dye represented by the following formula [III] (In the formula, M, R ¹ , R ² and m are the same as defined above) 1 mole ratio of the dye is condensed to give the following formula [IV] (Wherein M, R ¹ , R ² and m are the same as defined above).

Next, the disazo body 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 ³ , X and Y are the same as defined above).

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.
Disperse dye listed in Index is 0.01 to 50 g /, and surfactants (eg, sulfosuccinic acid anionic surfactant, nonylphenol nonionic surfactant, etc.) 0.53 g /
By adding a degree and the like to prepare a dyeing bath, it is possible to dye the cellulose fiber and the polyester fiber at the same time by the one-bath one-step method.

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 used as it is for dyeing, or may be 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 directly used for dyeing, 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 buffer 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 and the like Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples and the like.

Example 1 below 1 mole ratio of the monoazo dye represented by 1 to 40 mole ratio of monoazo dye represented by
Condensation at ℃ The disazo compound represented by
(Β-Hydroxyethyl) sulfonyl N-methylaniline sulfate 1 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 visible light. A disazo compound having an analytical value by absorption 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 buffers were added to 200 ml of water to adjust the pH to 7, and the unmercered cotton knitted fabric was added.
Add 10g, heat up to 120 ℃ over 30 minutes,
After dyeing for a minute, washing with water, soaping, washing with water and drying were carried out to obtain a yellow dyed product. 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.

For comparison, a conventional reactive dye comprising a disazo compound having the following structural formula (described in JP-A-58-164651) was dyed under the same conditions as described above, and the reaction dyeing rate of each was measured. .

The results are shown below.

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 deep yellow color.

Example 3 below 1 mole ratio of monoazo dye represented by 1 to 40 mole ratio of monoazo dye represented by
Condensation at ℃ The disazo compound represented by
(Β-Hydroxyethyl) sulfonyl N-methylaniline sulfate 1 mol ratio was added, condensed at 90 ° C., spray-dried, and the following structural formula (shown in the form of free acid).
And a disazo compound having an analytical value by visible light absorption 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 unmercured cotton knitted fabric to the dyebath prepared in addition to 30 minutes, raise the temperature to 130 ° C, dye at the same temperature for 30 minutes, then wash with water, soap, wash with water and dry to give a reddish yellow color. A dyed product of This dyebath has a pH of 8 before and after dyeing.
Met. The resulting dyed product is extremely dense and has light fastness,
The chlorine fastness and sweat-sunlight fastness were all good.

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 quinophthalone dye, 12 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 buffers in 200 m of water
polyester / cotton = 50: 50 in the dyebath prepared in addition to l
10 g of the mixed spinning cloth of the above was added, the temperature was raised to 130 ° C. over 30 minutes, and after dyeing at the same temperature for 60 minutes, washing with water, soaping, washing with water and drying were carried out to obtain a yellow 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 17 By the method according to the method described in Example 1, the above general formula [I]
Various disazo compounds (shown in the form of free acid) shown 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 18 The following components were blended to obtain a thick dye composition.

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

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 The above composition may be used to prepare a dyebath by diluting it with 800 ml of water. it can.

(c) Effects of the Invention As described above and as shown in Examples, the present invention provides a novel disazo compound, and by using it as a dye, it is possible to dye 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 (14)

[Claims] 1. A general formula [I] [In the formula, M represents a hydrogen atom or an alkali metal, and R
¹ represents a hydrogen atom, a carboxyl group, a lower alkyl group, a lower alkoxy group, an acylamino group, a carbamoylamino group or a halogen atom, R ² represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, and R ³ represents Represents a hydrogen atom or a lower alkyl group which may have a substituent, and when R ³ is a hydrogen atom, X represents a naphthylene group which may have a substituent, and R ³ has a substituent. In the case of a lower alkyl group which may be substituted, X represents a phenylene group or a naphthylene group which may have a substituent, and Y is a -SO 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 represents 2 or 3. ] The disazo compound shown by these. 2. The disazo compound according to claim 1, wherein R ³ is a lower alkyl group substituted with a cyano group, a hydroxyl group, a lower alkoxy group, a halogen atom or a lower alkylcarboxy group. 3. X is a lower alkyl group, a lower alkoxy group,
The disazo compound according to claim 2, which is a phenylene group or a naphthylene group which is or is not substituted with one or two substituents selected from the group consisting of a halogen atom and a sulfonic acid group. 4. R ³ is a hydrogen atom, and X is substituted or substituted with one or two substituents selected from the group consisting of a lower alkyl group, a lower alkoxy group, a halogen atom and a sulfonic acid group. The disazo compound according to claim 1, which is a naphthylene group which is not present. 5. The disazo compound according to claim 1, wherein W is a sulfuric acid ester group, a thiosulfuric acid ester group, a phosphoric acid ester acid, an acetic acid ester group or a halogen atom. 6. The following general formula [I] [In the formula, M represents a hydrogen atom or an alkali metal, and R
¹ represents a hydrogen atom, a carboxyl group, a lower alkyl group, a lower alkoxy group, an acylamino group, a carbamoylamino group or a halogen atom, R ² represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, and R ³ represents Represents a hydrogen atom or a lower alkyl group which may have a substituent, and when R ³ is a hydrogen atom, X represents a naphthylene group which may have a substituent, and R ³ has a substituent. In the case of a lower alkyl group which may be substituted, X represents a phenylene group or a naphthylene group which may have a substituent, and Y is a -SO 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 represents 2 or 3. ] The dye composition containing the disazo compound shown by these. 7. The dye composition according to claim 6, wherein R ³ is a lower alkyl group substituted with a cyano group, a hydroxyl group, a lower alkoxy group, a halogen atom or a lower alkylcarboxyl group. 8. X is a lower alkyl group, a lower alkoxy group,
The dye composition according to claim 7, which is a phenylene group or a naphthylene group which is substituted or unsubstituted with one or two substituents selected from the group consisting of a halogen atom and a sulfonic acid group. 9. R ³ is a hydrogen atom, and X is substituted or substituted with one or two substituents selected from the group consisting of a lower alkyl group, a lower alkoxy group, a halogen atom and a sulfonic acid group. 7. The dye composition according to claim 6, which is a naphthylene group which is not present. 10. The dye composition according to claim 6, wherein W is a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group or a halogen atom. 11. The dye composition according to claim 6, which is a composition containing water and a dyeing aid. 12. The dye composition according to claim 11, wherein the dyeing aid is a buffer, an electrolyte and a surfactant. 13. The buffer according to claim 12, which is carbonic acid, phosphoric acid, acetic acid, citric acid, boric acid or a salt thereof.
The dye composition according to the item. 14. The dye composition according to claim 12, wherein the electrolyte is sodium chloride or sodium sulfate.