JPS6230157A - Disazo compound and dyeing method using said compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I[R1 and R3 are H, methyl, ethyl, methoxy, ethoxy, acetylamino, benzoylamino or ureido; R2 and R4 are H, methyl, ethyl, methoxy or ethoxy; X and Y are 2-4C alkyl, etc.-substituted amino, cyclohexylamino, piperidino, morpholino, benzylamino or (substituted) anilino, provided that the carboxyl group is linked to the benzene nucleus at the 2- or 3-position] as a free acid. EXAMPLE:A compound expressed by formula II. USE:A dye for dyeing cellulosic fibers to yellow color. PREPARATION:For example, an aminoazo compound expressed by formula III or IV is first prepared as a free acid, and firstly condensed with a cyanuric trihalide to produce an azo compound expressed by formula V or VI (Z is halogen), which is then secondly condensed with 2,5-diaminobenzoic acid. The resultant product is then thirdly condensed with an alkyl- or alkanolamine, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" 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, thren dyes, sulfur dyes, 1-reactive dyes, direct dyes, etc. have been provided as dyes for dyeing natural or regenerated cellulose fibers, but the degree to which they achieve the required fastness and the dyeing There are advantages and disadvantages regarding the difficulty of processing operations or process control, the processing load of dyeing wastewater, etc.

Also, blended or knitted fibers of cellulose fibers and other types of fibers 1
For example, when dyeing synthetic fibers and cellulose blended fibers, especially polyester and cotton blended fibers (hereinafter referred to as T/C blend), the dyeing process of polyester fibers using disperse dyes is generally carried out at high temperatures (120-130°C) and in an acidic bath. These conditions do not necessarily match the above-mentioned dyeing conditions for cellulose fibers, which are usually carried out in a neutral bath at 90 to 100°C. Therefore, dyeing of T/C blends is often done in combination with disperse dyes.'
So-called two-bath dyeing or two-bath two-stage dyeing using direct dyes, one-reactive dyes, etc. is being carried out, and from the perspective of improving the efficiency of the dyeing process, such as saving energy and labor, one-bath one-stage dyeing in T/C mixed dyeing is an issue. It has become. Conventional direct dyes also meet these challenges to some extent, but direct dyes generally have poor fastness, especially washing fastness.

Due to low sweat fastness to light fastness, low chlorine fastness, and insufficient dyeing reproducibility, there are often limits to the range of its applicability.

For example, we developed JP-A-59-74463 as a yellow direct dye that enables dyeing by a one-bath one-step method of T/C mixture.
However, 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 combination of a disperse dye and a direct dye.

"Means for Solving the Problems" The present inventors have solved the above-mentioned problems, that is, the present invention is a free acid of the formula (formula (D), in which R1 and R5 are each independently a hydrogen atom.

Methyl group, ethyl group, ethquin group, ethoxy group.

an acetylamino group, a benzoylamino group or a ureido group, and R2 and R4 are each independently a hydrogen atom.

A methyl group, ethyl group, methoxy group or ethoxy group,
and Y are each independently an amino group substituted with an alkyl group or a hydroquine alkyl group (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 benzyl Amino group or chlorine atom, methyl group, methoxy group.

Each represents an acetylamino group, a sulfamoyl group, or a group. However, in formula (1), the carboxyl group is 2
or bonded to the benzene nucleus at position 5) 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 (n) or (lI[)
An aminoazo compound represented by is produced.

(In formulas (II) and (11), R,, R2, R3 and R4 have the same meanings as above) Aminoazo compounds of formulas (n) and (III) are usually 2-
Amino-4,8-naphthalenedisulfonic acid is diazotized to form the corresponding aniline or aniline-N-methanesulfonic acid (e.g. aniline, 2-methylaniline, 3-methanesulfonic acid).
-Methylaniline, 2-methoxyaniline, 3-methoxyaniline, 2-ethoxyaniline, 2,5-dimethylaniline, 2-methoxydi-5-methylaniline, 2-ethoxyaniline, 2,5 -dimethoxyaniline, 2,5-diethoquinanilino, 5
-acetylaminoaniline, 5-benzoylaminoaniline, 3-ureidoaniline, 2-methoxy-5-acetylaminoaniline, etc. or their N-methanesulfonic acid derivatives) or N-methanesulfonic acid. When a derivative is used as a coupler, it is produced by hydrolysis after a campling reaction.

Next, a cyanuric trihalide (e.g., cyanuric bromide, cyanuric fluoride, and preferably cyanuric chloride) and an aminoazo compound of formula (It) or formula (lit) are condensed (-condensation), and each of the four formulas (IV) or An azo compound represented by formula (V) is produced.

[In the formulas (■) and (V), R1, R2, R3 and R4 have the same meanings as above, or 2 represents halogen. ] Next 2,5
- Diaminobenzoic acid and the azo compound of formula (■) and/or formula (/V) are condensed (secondary condensation) in any order.

The obtained disazo compound and alkyl or alkanolamines (e.g. monoethanolamine, N-methyl hepisoethanolamine jetanolamine, mono- or dibrobanolamine, etc.), cyclohexylamine, piperidine, morpholine, benzylamine or substituted Examples of aniline MC that may be used include aniline, p-carbamoylaniline.

0-toluidine, m-)luidine, O-anisidine, p
-sulfamoylaniline, 2,5-xylidine, 2,
4.6-mesidine, p-clecdine, p-aminoacetanilide, m-aminoacetanilide, m-chloroaniline, 5.4-dichloroaniline, etc.) (tertiary condensation) to obtain a disazo compound of the general formula CD.

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, the temperature is 5 to 15°C, the pH is 4 to 6.5, and the secondary condensation is carried out at a temperature of 30 to 7.
0°C, pH 3-8, preferably temperature 40-60°C, pH 4
~7, and the tertiary condensation is carried out at a temperature of 70-105°C and a pH of ~9.
It is preferably carried out at a temperature of 80 to 100°C and a pH of 5 to B, respectively. The disazo compound of formula (1) is isolated by a conventional method after the tertiary condensation is completed.

That is, the reaction solution may be concentrated by evaporation or salted out by a conventional method, separated by filtration, and dried.

The novel disazo compound of the present invention can be used for dyeing cellulose fibers using a known dyeing method, or for example, using a high-temperature dyeing method for dyeing polyester fibers with disperse dyes.

It can be dyed to a yellow hue under the dyeing conditions used in carrier dyeing methods.

The compounds of the present invention can be used alone or in combination with other types of dyes such as disperse dyes, basic dyes, and finish dyes. Because of its acidic suitability, T/C blends can be dyed in a single bath using a disperse dye for polyester without any problem 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 dependence on salt concentration, 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 way of examples.

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 SaO part of water. . After adding 18.5 parts of cyanuric chloride to this solution at 5 to 10°C, the pH was adjusted to 5 to 6 by adding IJ carbonate, and the reaction was carried out (secondary condensation). After the reaction is complete, add 7.6 parts of 2 to this reaction solution.
, 5-diaminobenzoic acid dissolved in 100 parts of water was added, and the mixture was gradually heated to 50-60°C to react (secondary condensation). During the reaction, the pH was maintained at 6-7 by adding sodium carbonate.

After the reaction was completed, 15 parts of jetanolamine were added and the mixture was heated to 90-95°C to react (tertiary condensation).

During the reaction, the pH was adjusted to 7 by adding IJium (carbonate).
It was maintained at ~8.

After the reaction was completed, 20% (by weight) of sodium chloride was added to the reaction solution, and the precipitated crystals were separated.

67.7 parts of the following compound was obtained.

This compound dissolves well in water to give a yellow solution, and its maximum absorption wavelength (λnax) is 402 nm (in water).

The same applies hereafter). This compound showed high substantivity on cotton and gave yellow dyeings. After this product is treated with a polyamine fixing agent to be described later, its fastness is 5th grade light resistance, 4th grade washing resistance, and 4th grade sweat resistance.

The chlorine level was 4th grade, which was extremely good.

Examples 2 to 7 The compounds shown in the table below were produced according to Example 1, but 9 parts of monoethanolamine was used instead of 15 parts of jetanolamine during the tertiary condensation reaction.

10 parts of N-methylmonoethanolamine, 1 part of motuprobanolamine, 15 parts of cyclohexylamine, 15 parts of aniline or 12 parts of morpholine were used. The produced compounds and their aqueous solution λmaX are shown in the table below.

Each cotton was dyed to a uniform yellow color and the color fastness was good.

Example 8 42.1 parts of an aminoazo compound obtained by cambling diazotized 2-amino-4,8-naphthalenedisulfonic acid with 3-methylaniline under weak acidity was dissolved in 500 parts of water. After adding 18.5 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 react (-order condensation).
After completion of the reaction, 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 react at 50 to 60°C (secondary condensation).

During the reaction, the pH is adjusted to 6-7 by adding sodium carbonate.
was held at

After the reaction is complete, add 12 parts of morpholine and bring the mixture to 90-90%
The mixture was heated to 95°C to cause a reaction (tertiary condensation).

During the reaction, the pH is adjusted to 7-8 by adding sodium carbonate.
was held at

After the reaction was completed, 20% sodium chloride was added to the reaction solution, and the precipitated crystals were collected from house to house.

The following compound 62. o parts were obtained.

This compound dissolved well in water to give a yellow solution, and its maximum absorption wavelength (λmax) was 400 nm.

Examples 9 to 15 Compounds represented by the following formulas were produced according to the example day, but when using a tertiary mesh, instead of 12 parts morpholine, 15 parts benzylamine, 15 parts N-methylaniline, and 15 parts o- Toluidine 12 parts piperidine 125 parts p-sulfamoylaniline, 16 parts p-anidine, 18 parts p-
Carbamoylaniline was used.

The produced compounds and their aqueous solution λmaX are shown in the table below.

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 to 90°C to react. During the reaction, the pH was maintained at 7-8 by adding sodium carbonate. 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 to 6 by adding IJ (carbonate).

After the reaction was completed, 20% sodium chloride was added to the reaction solution, and the precipitated crystals were collected from house to house.

62.3 parts of the following compound was obtained.

This compound dissolves well in water, giving a yellow solution, and its content
ax was 400 nm.

This compound showed high substantivity on cotton and gave yellow dyeings. After treatment with a polyamine fixing agent, the fastness was extremely good: 5th grade in light, 14th grade in washing, 4th grade in perspiration, and 4th grade in chlorine.

Example 17 21.1 parts of the aminoazo compound described in Example 8 was added to 250
of water. After adding 9.3 parts of ammonium chloride to this solution at 5 to 10°C, the pH was maintained at 5 to 6 by adding sodium carbonate and the reaction was carried out (-order 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 slowly heated to react at 50 to 40°C (during the secondary condensation reaction). The pH was maintained at 4-5 by adding sodium carbonate.

The resulting mixture was gradually heated to react at 50 to 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, the pH was adjusted to 7-8 by adding sodium carbonate.
was held at

After the reaction was completed, 20% sodium chloride was added to the reaction solution, and the precipitated crystals were collected from house to house. The following compound 64.
I got 0 copies.

This compound dissolves well in water and gives a yellow solution.
λmaX was 401 nm.

It showed high directivity on cotton and gave a yellow dyed product.

After treatment with a polyamine fixing agent, the fastness was extremely good, being 5th grade to light, 4th grade to washing, 4th grade to sweat and light resistance, and 4th grade to chlorine.

Examples 18 to 29 Hereinafter, aminoazo compounds and amines of the above formula (II) and/or the above formula ([[l) obtained from 2-amino-4,8-naphthalenedisulfonic acid and the corresponding anilines are used. and λma in the aqueous solution of the compound obtained by
X is shown in the table below.

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 give about 5.
A dyebath at 0°C was prepared.

200 parts of a jersey knitted fabric made of cotton was placed in a dye bath, the temperature was raised to 90°C over about 40 minutes, and the temperature was maintained at the same temperature for 30 minutes.

The dyed cotton jersey knit fabric was treated with a polyamine fixing agent (Sanyo Kasei, Sunfix 555), then washed with hot water, water, and dried.

A knitted cotton jersey fabric is obtained that is uniformly dyed yellow, and its fastness is 5th grade for sunlight, 4th grade for washing, 4th grade for sweat light resistance, and 4th grade for chlorine fastness.
It was in extremely good condition.

In addition, each fastness test was based on the following standards.

Light resistance: J, Engineering, E1. L0842 (1971) Laundry: J, Engineering, 已 L0844 (1973) A-2
Sweat light resistance: : J, X, B, L0888 (1977) Alkaline chlorine: Eng, S, 0. 105-EO3-19
7820 pIIn Available Chlorine Example 31 High-temperature acidic bath dyeing of cotton A dye bath was prepared in the same manner as in Example 30 using the disazo compound of Example 8, and glacial acetic acid was further added to prepare a dye bath with a pH of 4.5.

200 parts of a cotton jersey knitted fabric was put into a dye bath, and the temperature was raised to 130°C over about 50 minutes and maintained at the same temperature for 30 minutes. (
A knitted cotton jersey fabric was obtained which was uniformly dyed yellow (using a closed pressure dyeing machine).

There were no problems such as poor dyeing or decomposition under the conditions of a high-temperature acid bath, which simulates the dyeing conditions of polyester fibers (Example 30)
The same staining results were obtained.

Example 32 High-temperature one-bath dyeing of a polyester/cotton blend 0.5 parts of the disazo compound of Example 8, 1 part of anhydrous sodium sulfate
00 part, Kayalon Po1yeeter
Light, t; Yellowr 5G-8 (Nippon Kayaku 1 disperse dye) 1.0 part.

Kayalon Polyester Yellow
BRL-8 (manufactured by Nippon Kayaku.

Disperse dye) 0. ! 1 part, acetic acid) IJium trihydrate 6
・A dye bath with a pH of 4.5 was prepared using 4 parts of acetic acid, 4.2 parts of acetic acid, and 4000 parts of water.

This dye bath was heated to 50°C, and polyester/cotton (5015
0) Add 200 parts of the blended product and heat to 150℃ for about 40 minutes.
After dyeing at the same temperature for 45 minutes, 9
The temperature was lowered to 0°C and held for an additional 15 minutes.

After washing the dyed product with water, it was treated with the above-mentioned polyamine fixing agent, followed by nubbing, washing with hot water, washing with water, 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 was obtained which is suitable for dyeing by a one-bath one-step method of T/C mixture and has good dyeing reproducibility because the compound is highly direct and has little dependence on salt concentration.

Claims (1)

[Claims] 1. As a free acid, there are formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In formula (I), R_1 and R_3 each independently represent a hydrogen atom, a methyl group, an ethyl group, a 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, and X and Y each independently represent an amino group substituted with an alkyl group or hydroxyalkyl group (however, (total number of carbon atoms is 2 to 4), cyclohexylamino group, piperidino group, morpholino group, benzylamino group or chlorine atom, methyl group, methoxy group, acetylamino group,
Each represents an anilino group which may be substituted with a sulfamoyl group or a carbamoyl group. However, the formula ( I
), the carboxyl group is bonded to the benzene nucleus at the 2 or 3 position) Disazo compound 2 represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. are available as the free acid ▼ ( I ) (Formula ( I ), R_1 and R_3 each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, an acetylamino group, a benzoylamino group or a ureido group,
R_2 and R_4 each independently represent a hydrogen atom, methyl group, ethyl group, methoxy group, or ethoxy group, and X and Y each independently represent an amino group substituted with an alkyl group or hydroxyalkyl group (however, (total number of carbon atoms is 2 to 4), cyclohexylamino group, piperidino group, morpholino group, benzylamino group or chlorine atom, methyl group, methoxy group, acetylamino group,
Each represents an anilino group which may be substituted with a sulfamoyl group or a carbamoyl group. However, in formula (1), the carboxyl group is bonded to the benzene nucleus at the 2 or 3 position.