JPH051827B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel trisazo compound. BACKGROUND ART In recent years, there has been an increasing demand for blended fabrics of cellulose fibers and other fibers, particularly blended fabrics with polyester fibers (hereinafter simply referred to as C/P fibers). Traditionally, when dyeing cellulose fibers, reactive dyes are 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.
The dyeing process is carried out at a pH of 10 or higher and a temperature of 100°C or lower.When dyeing polyester fibers, disperse dyes are used and dyeing is carried out at a temperature of about 130°C. When dyeing 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. However, in order to simplify the dyeing process, the above C/
If P fibers were to be dyed in the same process (one-bath method), two different dyes would be used in combination, a reactive dye and a disperse dye. When using disperse dyes, it is necessary to raise the pH to 10 or higher using an acid binder in order to fully dye the reactive dye on the cellulose fiber side, but the presence of an acid binder accelerates the decomposition of the disperse dye. The dyeing of the disperse dye to the polyester fiber is insufficient, and high temperature conditions (usually 130°C) are required to dye the disperse dye to the polyester fiber side, but under the high temperature mentioned above, There were problems such as accelerating the hydrolysis of reactive dyes and significantly inhibiting the dyeing of cellulose fibers. Problems to be Solved by the Invention The object of the present invention is to provide a trisazo compound that can dye cellulose fibers under the pH and dyeing conditions when dyeing polyester fibers with decomposed dyes. be. Means for Solving the Problems The present invention is based on the general formula [] (In the formula, M represents a hydrogen atom or an alkali metal, R ⁰ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a carboxyl group, and R ¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group,
represents a carboxyl 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, a carboxyl group, or a sulfonic acid group, R ³ represents a lower alkyl group or a lower alkoxy group, and X represents a chlorine atom or a fluorine atom. represents an atom, and Y is an aromatic amino residue (however,

(excluding formula), represents an aliphatic amino residue or an optionally etherified hydroxyl group, R ⁵ and R ⁶ represent a hydrogen atom, a methyl group, a methoxy group, or a sulfonic acid group, and n is 0 or 1, and the benzene ring B may represent a naphthalene ring). Trisazo compound represented by the general formula [] of the present invention (hereinafter simply referred to as trisazo compound)
In the above, examples of the alkali metal represented by M include lithium, sodium, potassium, etc., and the lower alkyl group and lower alkoxy group represented by R ⁰ , R ¹ , R ² , R ³ and R ⁴ have a carbon number of 1 to 4 alkyl groups and alkoxy groups,
Particularly preferred are methyl group and methoxy group. The aliphatic amino group represented by Y includes an amino group, a C ₁ to C ₄ monoalkylamino group, and a C ₁ to C 4 monoalkylamino group.
C ₄ dialkylamino group, monoethanolamino group, diethanolamino group, -NHC ₂ H ₄ SO ₃ Na
group, -NHCH ₂ COONa group, -NHC ₂ H ₄ SO ₂ C ₂ H ₄ C ₁
Aromatic amino groups include anilino group, N
-Methylaniline, N-ethylaniline, or 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, etc., and the optionally etherified hydroxyl group Ha-OH
group, _C1 - _C4 alkoxy group or chloro atom,
Examples include phenyloxy groups substituted with a nitro group, carboxyl group, sulfonic acid group, lower alkyl group, or lower alkoxy group. The trisazo compound represented by the general formula [] can be produced as follows. For example, the following general formulas [], [] and []

【formula】

【formula】

[Formula] (In the formula, R ⁰ , R ¹ , R ² , R ³ , R ⁴ , m and benzene ring B are the same as defined above.) The compound represented by formula〔〕 It is a disazo compound shown by On the other hand, the following formulas [], [] and []

【formula】

[Formula] Y-H [] (In the formula, n, (In the formula, n, X and Y are the same as defined above.) A compound represented by the following is produced. Next, the trisazo compound represented by the general formula [] is produced by coupling the compound represented by the general formula [] with a diazonium compound obtained by diazotizing the diazo compound of the above [] in a water-acetic acid medium. be able to. 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, cuprammonium rayon, and hemp. Furthermore, it can also be applied to dyeing nitrogen-containing fibers such as polyamide, wool, and silk. Furthermore, cellulose fibers in mixed fibers such as polyester, triacetate, polyacrylonitrile, polyamide, wool, silk, etc. containing cellulose fibers can of course be dyed well. In the fiber dyeing method using the trisazo compound of the present invention, dyes necessary for dyeing non-cellulose fibers, such as disperse dyes listed in the Color 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 trisazo compound of the present invention, for example, the trisazo compound represented by the above general formula [] and the buffer necessary to maintain the dye bath at pH 5 to 10 during dyeing are used. agent (for example, acids such as carbonic acid, phosphoric acid, acetic acid, citric acid, and sodium salts or potassium salts of these acids, usually about 0.5 to 5.0 g/mixture) and, if necessary, electrolyte (sodium chloride or sulfuric acid). A good dyeing process is achieved by preparing a dye bath containing sodium, etc. (usually about 1 to 150 g/approx.), adding cellulose fibers to this dye bath, and heating them at a temperature of 100 to 150 degrees Celsius for 30 to 50 minutes. It can be carried out. In addition, blended fabrics manufactured by adding other fibers such as polyester fibers to cellulose fibers,
In order to dye mixed woven and knitted fabrics, etc., a trisazo compound represented by the above general formula [] of the present invention and a disperse dye listed in the above Color Index are added to the dye bath to dye cellulose fibers. Polyester fibers can be dyed at the same time using a one-bath, one-step method. In addition, when dyeing blended fabrics, blended knitted fabrics, etc., as described above, the conventional one-bath two-step method of dyeing one fiber and then dyeing the other fiber in the same bath is used. May be applied, and furthermore,
It is also possible to adopt a two-bath method 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. . EXAMPLES Hereinafter, the method of the present invention will be specifically explained using examples, but the present invention is not limited to the following examples. Example 1 Production of a monoazo compound produced by trisazo formation and coupling: 17.3 g of 4-aminobenzenesulfonic acid was mixed with 17.3 g of 2-aminobenzenesulfonic acid to form a diazo compound in a conventional manner, and then 2-methoxy-5-methyl By diazotizing and coupling with 13.7g of aniline in a conventional manner, the following structural formula is obtained. A disazo compound represented by: on the other hand,
1-amino-8-hydroxynaphthalene-3,6
- After condensing 31.9 g of disulfonic acid and 13.5 g of cyanuric fluoride at below 0°C, 17.3 g of 2-aminobenzenesulfonic acid was condensed at 20°C to form the following structural formula: A diazo solution obtained by diazotizing the above disazo compound with water-acetic acid system is added to the reaction solution, and after coupling, salting out with potassium chloride produces a trisazo compound represented by the following structural formula. was manufactured. The maximum absorption wavelength λmax (water) of this compound was 582 nm. Staining method: 0.2 g of trisazo compound shown by the above structural formula in the form of free acid, 16 g of Glauber's salt, as a buffering agent.
Add 0.4 g of Na ₂ HPO ₄・12H ₂ O and 0.1 g of KH ₂ PO ₄ to water.
In addition to 200 ml, add 10 g of unmercered cotton knitted fabric to a dye bath adjusted to pH 7, raise the temperature to 120°C over 30 minutes, dye it at the same temperature for 60 minutes, wash with water, soap, wash with water, and dry. A dyed product was obtained. The degree of dyeing of this dye was very good, and the dyed product obtained was extremely rich and had good light fastness, especially good chlorine fastness and sweat and daylight fastness. Example 2 Production of trisazo compound: A monoazo compound produced by diazotizing and coupling 17.3 g of 2-aminobenzenesulfonic acid with 22.7 g of 1-naphthylamine-7-sulfonic acid in a conventional manner was further diazotized with 2-methoxy-5- By diazotizing and coupling with 18.0 g of acetylaminoaniline in a conventional manner, the following structural formula is obtained. A disazo compound represented by: On the other hand 2
The following structural formula is a condensate of 23.9 g of -amino-5-hydroxynaphthalene-7-sulfonic acid, 13.5 g of cyanuric fluoride, and 25.3 g of aniline-2,5-disulfonic acid. After producing a compound represented by the following and diazotizing and coupling this with the previously produced disazo compound, the reaction solution was spray-dried to produce a trisazo compound represented by the following structural formula. The λmax (water) of this compound was 569 nm. Dyeing method: 0.2 g of the trisazo compound shown by the above structural formula in free acid form, the following structural formula Polyester/cotton = 50: To a dye bath prepared by adding 0.2 g of the monoazo dye shown by, 12 g of Glauber's salt, and 0.4 g of sodium bicarbonate as a buffer to 200 ml of water, polyester/cotton = 50:
Add 10g of blended fabric of 50% and raise the temperature to 130℃ over 30 minutes. After dyeing at the same temperature for 60 minutes, wash with water, soap, wash with water, and dry to obtain a reddish dark blue dyed product with good color consistency. Ta. This dyeing bath has a PH level before and after dyeing.
It was 8. Furthermore, the dyeing property was very good, and the dyed product obtained was extremely rich, and the light fastness, chlorine fastness, and sweat fastness to daylight were all good. Example 3 According to the method described in Example 1, the following general formula A trisazo compound represented by the formula was prepared, and cotton cloth was dyed using the compound. The results are shown in Table 1.

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. General formula [] (In the formula, M represents a hydrogen atom or an alkali metal, R ⁰ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a carboxyl group, and R ¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group,
represents a carboxyl 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, a carboxyl group, or a sulfonic acid group, R ³ represents a lower alkyl group or a lower alkoxy group, and X represents a chlorine atom or a fluorine atom. represents an atom, and Y is an aromatic amino residue (however,
(excluding formula), represents an aliphatic amino acid group or an optionally etherified hydroxyl group, R ⁵ and R ⁶ represent a hydrogen atom, a methyl group, a methoxy group, or a sulfonic acid group, and n is 0 or 1, and benzene ring B may represent a naphthalene ring).