JPH0453907B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a novel disazo compound and a method for dyeing cellulose fibers using the same. The disazo compound of the present invention is characterized in that it dyes natural or regenerated cellulose fibers, particularly cotton or cotton-containing fibers, in a yellow color with excellent color fastness. ``Prior art'' Conventionally, naphthol dyes, threne dyes, sulfur dyes, reactive dyes, direct dyes, etc. have been provided as dyes for dyeing natural or regenerated cellulose fibers, but the degree of attainment of the required fastness and the dyeing are difficult. There are advantages and disadvantages regarding the difficulty of processing operations or process control, the processing load of dyeing wastewater, etc. In addition, when dyeing blended or interwoven fibers of cellulose fibers and other types of fibers, for example, synthetic fibers and cellulose blended fibers, especially polyester and cotton blended fibers (hereinafter abbreviated as T/C blend), polyester fibers can be dyed using disperse dyes. The dyeing process is generally carried out at high temperatures (120-130
°C) and requires an acidic bath, so a neutral bath is usually used.
This does not necessarily match the dyeing conditions for cellulose fibers, which are carried out at 90 to 100°C. Therefore, the dyeing process of T/C blends is often carried out by so-called two-bath dyeing or one-bath two-stage dyeing using direct dyes, reactive dyes, etc. in combination with disperse dyes, which improves dyeing process by saving energy and labor. From the viewpoint of improving efficiency, one-bath single-stage T/C mixed dyeing has become an issue. Conventional direct dyes also meet these challenges to some extent, but direct dyes generally have low fastness, especially washing fastness, sweat fastness to light fastness, and chlorine fastness, and their dyeing reproducibility is insufficient. There are often limits to the scope of application. For example, we developed a yellow direct dye that enables dyeing by a one-bath, one-step method of mixing T/C.
No. 74163 was provided, but it was found that these dyes had a rather low directivity to cellulose fibers and were highly dependent on the salt concentration added to the dye bath, so that the dyeing reproducibility was somewhat difficult. "Problems to be Solved by the Invention" It is desired to develop a direct dye with good dyeing reproducibility in dyeing a T/C mixture by a one-bath one-step method using a disperse dye and a direct dye in combination. "Means for Solving the Problems" The present inventors have completed the present invention as a result of their earnest efforts to solve the above-mentioned problems. That is, the present invention provides the formula (In formula (), R ₁ and R ₃ are each independently a hydrogen atom,
Methyl group, ethyl group, methoxy group, ethoxy group,
acetylamino group, benzoylamino group or ureido group, R ₂ and R ₄ each independently represent a hydrogen atom, methyl group, ethyl group, methoxy group or ethoxy group, X and Y each independently represent an alkyl group or hydroxyalkyl group Amino group substituted with (however, the total number of carbon atoms in the alkyl group and hydroxyalkyl group is 2 to
4), a cyclohexylamino group, a piperidino group, a morpholino group, a benylamino group, or an anilino group which may be substituted with a chlorine atom, a methyl group, a methoxy group, an acetylamino group, a sulfamoyl group, or a carbamoyl group, respectively. The present invention provides a disazo compound represented by the following formula (in which the carboxyl group is bonded to the benzene nucleus at the 2 or 3 position) and a method for dyeing cellulose fibers using the disazo compound. The disazo compound of formula () can be produced, for example, by the following method. First, as a free acid, the formula ()
Or produce an aminoazo compound represented by (). (In formulas () and (), R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as above.) The aminoazo compounds of formulas () and () usually contain 2-amino-4,8-naphthalenedisulfonic acid. and corresponding anilines or anilines of N-ω-methanesulfonic acid (e.g. aniline,
2-methylaniline, 3-methylaniline, 2-
Methoxyaniline, 3-methoxyaniline,
2-ethoxyaniline, 2,5-dimethylaniline, 2-methoxy-5-methylaniline, 2
-Ethoxy-5-methylaniline, 2,5-dimethoxyaniline, 2,5-diethoxyaniline, 3-acetylaminoaniline, 3-benzoylaminoaniline, 3-ureidoaniline, 2
-methoxy-5-acetylaminoaniline, etc. or their N-ω-methanesulfonic acid derivatives), or when N-ω-methanesulfonic acid derivatives are used as couplers, by hydrolysis after the coupling reaction. Manufactured. Next, cyanuric trihalides (e.g., cyanuric bromide, cyanuric fluoride, and preferably cyanuric chloride) are condensed (primary condensation) with the aminoazo compound of formula () or formula (), respectively represented by formula () or formula (). An azo compound is produced. [In the formulas () and (), R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as above, and Z represents halogen. ] Next, 2,5-diaminobenzoic acid and the formula () and /
Alternatively, azo compounds of formula () are condensed (secondary condensation) in any order. The resulting disazo compound and alkyl or alkanolamines (e.g. monoethanolamine,
N-methyl monoethanolamine, diethanolamine, mono- or dipropanolamine, etc.), cyclohexylamine, piperidine, morpholine,
benzylamine or optionally substituted anilines (e.g. aniline, p-carbamoylaniline, o-toluidine, m-toluidine, o-anisidine, p-sulfamoylaniline, 2,5-
Xylidine, 2,4,6-mesidine, p-cresidine, p-aminoacetanilide, m-aminoacetanilide, m-chloroaniline, 3,4-
dichloroaniline, etc.) to obtain a disazo compound of the general formula (). The condensation reaction with cyanuric trihalide can be carried out in a conventional manner, but preferred reaction conditions are as follows. The primary condensation is carried out at a temperature of 0 to 25°C and a pH of 3 to 7, preferably 5 to 15°C and a pH of 4 to 6.5, and the secondary condensation is carried out at a temperature of 30 to 6.5.
70℃, PH3~8, preferably temperature 40~60℃, PH4~
In 7, the tertiary condensation is carried out at a temperature of 70-105°C and a pH of 3-9, preferably a temperature of 80-100°C and a pH of 5-8, respectively. The disazo compound of formula () is isolated by a conventional method after the tertiary condensation is completed. That is, the reaction solution may be evaporated and concentrated, or salted out, overseparated, and dried by a conventional method. The novel disazo compound of the present invention dyes cellulose fibers to a yellow hue under the dyeing conditions used in dyeing methods known per se, or in dyeing polyester fibers with disperse dyes, such as high-temperature dyeing methods and carrier dyeing methods. can do. The compounds of the present invention can be used alone or in combination with other types of dyes such as disperse dyes, basic dyes, acid dyes, etc.
What should be noted is that it has good high-temperature acidic suitability, so T/C blends can be dyed in one step in one bath using a disperse dye for polyester without any problems in terms of dyeing operations, fastness of dyed products, etc. The disazo compound of the present invention exhibits high directivity to cellulose fibers, has good solubility of the dye, and has low salt concentration dependence, resulting in good dyeing reproducibility. The resulting dyed product has excellent fastness properties, particularly sweat fastness to light, chlorine fastness, and wet fastness. Furthermore, when a disperse dye and the diazo compound of the present invention are used together for dyeing by a T/C mixed one-bath one-step method, the same excellent dyeing reproducibility and fastness can be obtained. "Example" The present invention will be explained in more detail by means of an example.
In the examples, carboxyl groups and sulfonic acid groups are expressed in free form. Example 1 46.4 parts of an aminoazo compound obtained by coupling diazotized 2-amino-4,8-naphthalenedisulfonic acid to 3-acetylaminoaniline under weak acidity was dissolved in 500 parts of water. After adding 18.5 parts of cyanuric chloride to this solution at 5-10℃, the pH was adjusted to 5-6 by adding sodium carbonate.
The reaction was carried out (primary condensation). After the reaction was completed, 7.6 parts of 2,5-diaminobenzoic acid dissolved in 100 parts of water was added to the reaction solution, and the mixture was gradually heated to 50 to 60°C for reaction (secondary condensation).
During the reaction, the pH was adjusted to 6 by adding sodium carbonate.
It was maintained at ~7. After the reaction was completed, 15 parts of diethanolamine was added and the mixture was heated to 90-95°C to react (tertiary condensation). During the reaction, the pH was maintained at 7-8 by adding sodium carbonate. 20% (by weight) of the reaction solution after completion of the reaction
of sodium chloride was added, and the precipitated crystals were separated. 67.7 parts of the following compound was obtained. This compound dissolves well in water giving a yellow solution,
Its maximum absorption wavelength (λmax) was 402 nm (in water, the same applies hereinafter). This compound showed high substantivity on cotton and gave yellow dyeings. After this product is treated with the polyamine fixing agent described below, the fastness is 5th grade light resistance, 4th grade washing resistance, 4th grade sweat resistance, and 4th grade light resistance.
The chlorine content was extremely good, being grade 4. Examples 2 to 7 The compounds shown in the table below were produced according to Example 1, but in place of 15 parts of diethanolamine during the tertiary condensation reaction, 9 parts of monoethanolamine, 10 parts of N-methylmonoethanolamine, 10 parts monopropanolamine, 15 parts cyclohexylamine, 15 parts aniline or 12 parts morpholine were used. λmax of the generated compound and its aqueous solution
are shown in the table below.

【table】

[Table] Each cotton was dyed to a uniform yellow color and the color fastness was good. Example 8 Aminoazo compound obtained by coupling diazotized 2-amino-4,8-naphthalenedisulfonic acid to 3-methylaniline under weak acidity
42.1 parts were dissolved in 500 parts of water. 18.5 to this solution
After adding part of cyanuric chloride at 5 to 10°C, the pH was maintained at 5 to 6 by adding sodium carbonate to react (primary condensation). After the reaction was completed, a solution of 7.6 parts of 2,5-diaminobenzoic acid dissolved in 100 parts of water was added to the reaction solution, and the mixture was gradually heated to 50-60°C.
(secondary condensation). During the reaction, pH is adjusted by adding sodium carbonate.
It was kept at 6-7. After the reaction is complete, add 12 parts of morpholine to the mixture.
The mixture was heated to 90-95°C to cause a reaction (tertiary condensation). During the reaction, the pH is adjusted to 7~ by adding sodium carbonate.
It was held at 8. After the reaction was completed, 20% sodium chloride was added to the reaction solution, and the precipitated crystals were separated. 62.0 parts of the following compound was obtained. This compound dissolved well in water and gave a yellow solution with a maximum absorption wavelength (λmax) of 400 nm. Examples 9 to 15 Compounds represented by the following formulas were produced according to Example 8, but in place of 12 parts of morpholine during the tertiary condensation, 15
1 part of benzylamine, 15 parts of N-methylaniline, 15 parts of o-toluidine, 12 parts of piperidine, 25 parts of p-sulfamoylaniline, 16 parts of p-anisidine, and 18 parts of p-carbamoylaniline were used. . The produced compounds and their aqueous solution λmax are shown in the table below.

[Table] These compounds dyed cotton yellow and the fastness of the dyed product was excellent. Example 16 A compound was produced according to Example 8, but during the tertiary condensation reaction, 5 parts of morpholine was added instead of 12 parts of morpholine, and the mixture was heated to 85-90°C to react. During the reaction, the pH is adjusted to 7~ by adding sodium carbonate.
It was held at 8. After the reaction was completed, 8 parts of aniline was added and heated to 90-95°C to react. During the reaction, the pH was maintained at 5-6 by adding sodium carbonate. After the reaction was completed, 20% sodium chloride was added to the reaction solution, and the precipitated crystals were separated. 62.3 parts of the following compound was obtained. This compound dissolves well in water giving a yellow solution,
Its λmax was 400nm. This compound showed high substantivity on cotton and gave yellow dyeings. After treatment with a polyamine fixing agent, the fastness is 5th grade light resistance, 4th grade washing,
It had extremely good sweat resistance of 4th grade and chlorine resistance of 4th grade. Example 17 21.1 parts of the aminoazo compound described in Example 8
Dissolved in 250 parts of water. After adding 9.3 parts of cyanuric chloride to this solution at 5 to 10°C, the pH was maintained at 5 to 6 by adding sodium carbonate to cause a reaction (primary condensation). After the reaction was completed, a solution of 7.6 parts of 2,5-diaminobenzoic acid dissolved in 100 parts of water was added to the reaction solution, and the mixture was slowly heated to react at 30 to 440°C (secondary condensation). During the reaction, the pH was maintained at 4 to 5 by adding sodium carbonate. After the reaction was completed, a reaction solution of the product obtained by reacting 23.2 parts of the aminoazo compound described in Example 1 and 9.3 parts of cyanuric chloride in the same manner as in Example 1 was added, and the resulting mixture was gradually heated to 50 Reacted at ~60°C (secondary condensation). During the reaction, the pH was maintained at 6-7 by adding sodium carbonate. After the reaction was completed, 12 parts of morpholine was added and heated to 90 to 95°C to cause a reaction (tertiary condensation). During the reaction, pH is adjusted by adding sodium carbonate.
It was kept at 7-8. After the reaction was completed, 20% sodium chloride was added to the reaction solution, and the precipitated crystals were separated. 64.0 parts of the following compound was obtained. This compound dissolved well in water and gave a yellow solution with a λmax of 401 nm. It showed high directivity on cotton and gave a yellow dyed product. After treatment with a polyamine fixing agent, the fastness is 5th grade lightfastness, 4th grade washing, and 4th grade sweat and light fastness.
It was very good with grade 4 and grade 4 chlorine. Examples 18 to 29 Below, compounds obtained using the above formula () obtained using 2-amino-4,8-naphthalenedisulfonic acid and the corresponding anilines and/or aminoazo compounds and amines of the above formula () The compounds and their λmax in aqueous solution are shown in the table below.

【table】

【table】

[Table] Example 30 Atmospheric pressure dyeing of cotton 1 part of the disazo compound of Example 8 was dissolved in 4000 parts of water, and then 60 parts of anhydrous sodium sulfate was added and dissolved to prepare a dye bath at about 30°C. 200 parts of a jersey knitted fabric made of cotton was placed in a dye bath, heated to 90°C over about 40 minutes, and held at the same temperature for 30 minutes. The dyed cotton jersey knitted fabric is coated with a polyamine-based fixing agent (Sanyo Kasei, San Fixtures 555).
After treatment, it was washed with hot water, water, and dried. A cotton jersey knitted fabric was obtained which was uniformly dyed yellow, and its fastness was extremely good, being 5th grade light resistance, 4th grade washing resistance, 4th grade sweat resistance, and 4th grade chlorine resistance. In addition, each fastness test was based on the following standards. Light fastness: JISL0842 (1971) Washing: JISL0844 (1973) A-2 Sweat light fastness: JISL0888 (1977) Alkaline Chlorine: ISO105-E03-1978 20ppm available chlorine Example 31 High temperature acid bath dyeing of cotton Example 8 Disazo A dye bath was prepared in the same manner as in Example 30 using the compound, and glacial acetic acid was added to adjust the pH to 4.5.
A dye bath was prepared. Add 200 pieces of cotton jersey knitted fabric to the dye bath for approximately 50 minutes.
The temperature was raised to 130°C over several minutes and held at the same temperature for 30 minutes. (Using a closed pressure dyeing machine) A cotton jersey knitted fabric uniformly dyed yellow was obtained. A dyeing result equivalent to that of Example 30 was obtained without problems such as poor dyeing or decomposition under conditions of a high-temperature acid bath, which was assumed to be dyeing conditions for polyester fibers. Example 32 High-temperature bath dyeing of polyester/cotton blends 0.5 part of the disazo compound of Example 8, 100 parts of anhydrous sodium sulfate, Kayalon Polyester Light Yellow 5G
-S (Nippon Kayaku, disperse dye) 1.0 part, Kayalon
A dye bath with a pH of 4.5 was prepared using 0.3 parts of Polyester Yellow BRL-S (manufactured by Nippon Kayaku, disperse dye), 6.4 parts of sodium acetate trihydrate, 4.2 parts of acetic acid, and 4000 parts of water. The dye bath was heated to 50℃, 200 parts of a polyester/cotton (50/50) blend was added, and the process was carried out for about 40 minutes.
After raising the temperature to 130℃ and staining at the same temperature for 45 minutes,
The temperature was lowered to 90°C in 15 minutes and maintained for an additional 15 minutes. The dyed product was washed with water and treated with the above-mentioned polyamine fixing agent, followed by soaping, hot water washing, water washing and drying. A polyester/cotton blend dyed in a uniform yellow color was obtained, and its fastness was extremely good. "Effects of the Invention" A disazo compound with good dyeing reproducibility was obtained because the compound is highly direct and has low salt concentration dependence, and is suitable for dyeing by a one-bath one-step method of T/C mixture.

Claims (1)

[Claims] 1. As a free acid, the formula (In formula (), R ₁ and R ₃ are each independently a hydrogen atom,
Methyl group, ethyl group, methoxy group, ethoxy group,
acetylamino group, benzoylamino group or ureido group, R ₂ and R ₄ each independently represent a hydrogen atom, methyl group, ethyl group, methoxy group or ethoxy group, X and Y each independently represent an alkyl group or hydroxyalkyl group Amino group substituted with (however, the total number of carbon atoms in the alkyl group and hydroxyalkyl group is 2 to
4), a cyclohexylamino group, a piperidino group, a morpholino group, a benzylamino group, or an anilino group optionally substituted with a chlorine atom, a methyl group, a methoxy group, an acetylamino group, a sulfamoyl group, or a carbamoyl group, respectively. . However, in formula (), the carboxyl group is bonded to the benzene nucleus at the 2 or 3 position) Disazo compound 2 represented by the formula (as a free acid) (In formula (), R ₁ and R ₃ are each independently a hydrogen atom,
Methyl group, ethyl group, methoxy group, ethoxy group,
acetylamino group, benzoylamino group or ureido group, R ₂ and R ₄ each independently represent a hydrogen atom, methyl group, ethyl group, methoxy group or ethoxy group, X and Y each independently represent an alkyl group or hydroxyalkyl group Amino group substituted with (however, the total number of carbon atoms in the alkyl group and hydroxyalkyl group is 2 to
4), a cyclohexylamino group, a piperidino group, a morpholino group, a benzylamino group, or an anilino group optionally substituted with a chlorine atom, a methyl group, a methoxy group, an acetylamino group, a sulfamoyl group, or a carbamoyl group, respectively. . However, in formula (), the carboxyl group is bonded to the benzene nucleus at the 2 or 3 position.