JPH0635555B2 - Trisazo compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel trisazo compound used as a dye for cellulosic fibers and nitrogen-containing fibers.

2. Description of the Related Art Conventionally, when dyeing cellulose fibers, a reactive dye is used, and a pH of 10 is used in the presence of an acid binder such as sodium carbonate, potassium carbonate and sodium hydroxide and an electrolyte such as sodium chloride and sodium sulfate. Above, temperature 10
The method performed under the condition of 0 ° C. or lower is adopted.

However, in recent years, there has been an increasing demand for blended fabrics of cellulose fibers and other fibers, particularly polyester fibers, and in order to dye such cellulose / polyester mixed fibers (hereinafter simply referred to as C / P fibers), It was necessary to apply the dye and dye conditions for cellulose fibers and the dye and dye conditions for 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, in order to dye the polyester fiber, it is necessary to use a disperse dye and dye at a temperature of about 130 ° C.

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, it is necessary to adjust the pH to 10 or more by the acid binder, and the presence of the acid binder accelerates the decomposition of the disperse dye and the polyester fiber of the disperse dye. The dyeing on the fabric will be insufficient. On the other hand, in order to dye the disperse dye on the polyester fiber side, high temperature conditions (usually 130 ° C.) are required, but under the high temperature at the above-mentioned high pH, hydrolysis of the reactive dye is promoted to form cellulose fibers. Dyeing will be significantly hindered. Therefore, when such C / P fibers are dyed, a 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. It becomes.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a trisazo compound capable of dyeing cellulose fibers under pH and dyeing conditions when dyeing polyester fibers with a disperse dye. .

Means for Solving the Problems 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 lower alkyl group, a lower alkoxy group or 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. Group, a lower alkoxy group or a sulfonic acid group, R ⁵ represents a hydrogen atom or a lower alkyl group, and X represents (M is as defined above, and 1 is 0 or 1.), Y is X, chlorine atom, fluorine atom, amino group, aromatic amine residue, aliphatic amine residue, hydroxyl Group and a hydroxy compound residue, m represents 1, 2 or 3, n represents 0 or 1, and a benzene ring, A, B and C may represent a naphthalene ring) The subject matter is a compound.

In the trisazo compound represented by the general formula [I] of the present invention, examples of the alkali metal represented by M include sodium and potassium.

The lower alkyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ and the lower alkoxy group include an alkyl group having 1 to 4 carbon atoms,
And an alkoxy group, particularly preferably a methyl group,
A methoxy group can be mentioned.

The aliphatic amine residue represented by Y is C _{1 to} C ₄
A monoalkylamino group, a C _{1 to} C ₄ dialkylamino group, a monoethanolamino group, a diethanolamino group,
-NHC ₂ H ₄ SO ₃ Na group, -NHCH ₂ COONa group, -NHC ₂ H ₄ SO ₂ C ₂ H ₄ Cl
Group, a cyanomethylamino group, a cyanoethylamino group, a morpholino group, a piperidino group, and the like. Examples of the aromatic amine residue include an anilino group, N-methylaniline, N
-Ethylaniline or an anilino group substituted with a chlorine atom, a nitro group, a carboxyl group, a sulfonic acid group, a lower alkyl group or a lower alkoxy group, and the like, and the hydroxy compound residue is a C ₁ -C ₄ alkoxy group. Alternatively, a phenyloxy group substituted with a chlorine atom, a nitro group, a carboxyl group, a sulfonic acid group, a lower alkyl group, a lower alkoxy group or the like can be used.

The trisazo compound represented by the general formula [I] shown above can be produced as follows. For example, the following general formulas [II], [III], and [IV] (Wherein R ¹ , R ² , R ³ , R ⁴ , m, and benzene rings A, B and C are the same as defined above), the compound is subjected to ordinary diazotization and coupling twice, and the following general formula [ V] It is a disazo body represented by.

On the other hand, the following general formulas [VI] and [VII] (In the formula, Z represents a chlorine atom or a fluorine atom, and n,
R ⁵ is as defined above. ) Is condensed in an aqueous medium to give a compound represented by the following general formula [VIII] (Wherein n, Z and R ⁵ are the same as defined above) are first prepared.

Then, by the following or method, the general formula (Wherein n, R ⁵ , X and Y are as defined above) are prepared.

In the general formula [I] shown above, Y is (Wherein 1 and M are as defined above): 1 mole ratio of the compound represented by the above general formula [VIII] The compound represented by 2 mol ratio is condensed in hot water at 80 ° to 90 ° C.

In the general formula [I] shown above, when Y represents a chlorine atom or a fluorine atom: 1 mole ratio of the compound represented by the general formula [VIII] And 1 mole ratio of the compound represented by are condensed in hot water at 30 to 40 ° C.

When Y represents an amine residue or a hydroxy compound residue in the general formula [I] shown above: 1 mole ratio of the compound represented by the above general formula [VIII] and Y'H
(Wherein Y'represents an amine residue or a hydroxy compound residue) with 1 mole ratio of the compound. Then 1 mol ratio of the compound represented by and condensation is performed in hot water at 80 to 90 ° C.

Then, the triazo compound of the above general formula [I] is prepared by coupling the compound of the above general formula [IX] with the disazo compound of the above [V] and the diazonium compound diazotized in a water-acetic acid medium. be able to.

The trisazo compound of the present invention thus produced can be used as a dye itself.

Fibers which can be dyed with the trisazo compound of the present invention include cellulosic fibers such as cotton, viscose rayon, kyupurammonium 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 trisazo compound of the present invention, dyes necessary for dyeing fibers other than cellulosics, for example, disperse dyes described in Color Index (Third Edition) are added to the dye bath at the same time. Can be dyed.

When the cellulosic fiber is dyed using the trisazo compound of the present invention, for example, the trisazo compound represented by the general formula [I] and the dye bath during dyeing are adjusted to pH 5 to 5
Buffers necessary to maintain 10 (for example, carbonic acid, phosphoric acid, acetic acid, citric acid, etc. and a sodium salt or potassium salt of these acids, singly or in a mixture, usually 0.5 to 5.0 g /
), And, if necessary, an electrolyte (usually 1 to 150 g / sodium chloride or sodium sulphate, etc.) is added to the dye bath, and the cellulose fibers are added to the dye bath at a temperature of 100 to 150 ° C. Good dyeing can be carried out by heating for 30 to 50 minutes.

Further, in order to dye a mixed-spun fabric, a mixed-woven knitted fabric, or the like produced by mixing other fibers such as polyester fibers with cellulosic fibers, the trisazo compound represented by the above general formula [I] of the present invention, By adding the disperse dye described in the Color Index to the dye 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 cellulosic fibers and other fibers from separate baths by combining the dyeing method with the trisazo compound of the present invention and the dyeing method for fibers other than cellulosic fibers It is also possible to adopt the law.

EXAMPLES Hereinafter, the method of the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.

Example 1 A monoazo compound formed by diazotizing and coupling 2-naphthylamine-3,6,8-trisulfonic acid (38.3 g) with 2-methoxy-5-methylaniline (13.7 g) by a conventional method was further added to 2-methoxy- The following formula was obtained by diazotization and coupling with 5-methylaniline (13.7 g) by a conventional method. A disazo compound represented by On the other hand, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid 3
After condensing 1.9 g and cyanuric chloride 18.5 g at 0 ° C or lower, 4-aminobenzenesulfonic acid 17.3 g is condensed at 20 ° C to obtain the following formula. First, the compound represented by
And 6 g of sodium hydroxide were added, and the mixture was stirred at 80 ° C. for 10 hours to replace chlorine atoms with nicotinic acid. A diazo solution obtained by diazotizing the above-mentioned disazo compound with a water-acetic acid system was added to the reaction solution, followed by coupling at 0 to 5 ° C., followed by salting out with potassium chloride to obtain the following structural formula (in the form of a free acid). 9) g of a trisazo compound having the following analytical value λmax by visible light absorption.

0.2 g of the trisazo compound represented by the above structural formula, 1 glauber's salt
_{6g, Na 2 HPO 4 · 12H} 2 O0.4g and KH ₂ PO as a buffering agent
₄ 0.1 g was added to 200 ml of water to adjust the pH to 7, and 10 g of unsilked cotton knitted fabric was added to the dyeing bath in 30 minutes.
The temperature was raised to 0 ° C., 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 greenish dark blue dyed product.
The dyeing degree 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.

Example 2 25.3 g of aniline-2,5-disulfonic acid was treated with 2-methoxy-
The monoazo compound formed by diazotizing and coupling with 5-methylaniline (13.7 g) by a conventional method was further diazotized and coupled with 2-methoxy-5-acetylaminoaniline (18.0 g) by a conventional method to give the following formula. A disazo compound represented by On the other hand, 2-amino-5-hydroxynaphthalene-7-sulfonic acid 23.9
g, and 18.5 g of cyanuric chloride were condensed at 0 ° C or lower, 36 g of nicotinic acid and 12 g of sodium hydroxide were further added, and the mixture was stirred at 80 ° C for 10 hours to replace chlorine atoms with nicotinic acid. First, a compound represented by the following formula was prepared, the above-mentioned disazo solution was added to the reaction solution, coupling was performed at 0 to 5 ° C at pH 7.5, and the reaction solution was spray-dried to obtain the following structural formula (free acid 88.3 g of the trisazo compound having the following analysis by visible light absorption.

0.2 g of the trisazo compound represented by the above structural formula, 1 glauber's salt
_{6g, Na 2 HPO 4 · 12H} 2 O0.5g and KH ₂ PO as a buffering agent
₄ Add 0.02 g of water to 200 ml of water and add 10 g of unsilked cotton knit to the dyebath.
The mixture was heated up to 30 minutes and dyed at the same temperature for 30 minutes, washed with water, soaped, washed with water and dried to obtain a dark blue dyeing product. The dyeing bath had a pH of 8 before and after dyeing. Was extremely thick, and the light fastness, chlorine fastness, and sweat-sunlight fastness were all good.

Example 3 0.2 g of the trisazo compound produced in Example 2 and the structural formula 0.2 g of the monoazo dye represented by the formula, 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 a buffer agent in water 200
50% polyester / cotton in the dye bath prepared in addition to ml:
50 g of 50 mixed-spun cloth was put thereinto, the temperature was raised to 130 ° C. over 30 minutes, and 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 dark blue dyeing having good color uniformity. The dyebath had a pH of 8 before and after dyeing.
Further, 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.

Examples 4 to 36 By the method similar to the method described in Example 1, the trisazo compound represented by the above general formula [I] and shown in Table 1 below (shown in the form of free acid) was produced. . The analytical values of the obtained compounds and the results of dyeing cotton cloth are shown in Table 1.

Claims (1)

[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 lower alkyl group, a lower alkoxy group or a sulfonic acid group, R ² and R ⁴ are hydrogen atoms,
Represents a lower alkyl group, a lower alkoxy group, an acetylamino group or a sulfonic acid group, R ³ represents a lower alkyl group,
Represents a lower alkoxy group or a sulfonic acid group, R ⁵ represents a hydrogen atom or a lower alkyl group, and X represents (M is as defined above, and 1 is 0 or 1.), Y is X, chlorine atom, fluorine atom, amino group, C ₁ -C ₄ monoalkylamino group, dialkylamino group, monoethanol amino group, diethanolamino group, -NHC ₂ H ₄ SO ₃ Na groups, -NHCH ₂ CO
ONa _{group, -NHC 2 H 4 SO 2 C} 2 H 4 Cl group, cyanomethyl group, cyanoethyl group, morpholino group,
Piperidino group, anilino group, N-methylanilino group, N
-Ethylanilino group or chlorine atom, nitro group, carboxyl group, sulfonic acid group, anilino group or hydroxyl group substituted by lower alkyl group or lower alkoxy group, C ₁ -C ₄ alkoxy group or chlorine atom, nitro group, carboxyl Represents a phenyloxy group substituted with a group, a sulfonic acid group, a lower alkyl group or a lower alkoxy group, m represents 1, 2 or 3, n represents 0 or 1, and benzene rings A, B and C represent Triazo compound represented by naphthalene ring).