JPS63130670A - Monoazobenzothiazole compound and method of dyeing or printing hydrophobic fibrous material therewith - Google Patents

Abstract

PURPOSE:To obtain the title compound which can dye hydrophobic fibers red to give a dyed product with excellent color fastness to washing, by coupling a diazotized 2-amino-4,6-dibromobenzothiazole. CONSTITUTION:An N,N-di(hydroxyethyl)aniline derivative of formula I (wherein X is H, Cl or methyl) is reacted with a compound of formula II (wherein R is 1-4C alkyl) in an organic solvent in the presence of a deoxidizer, thereby giving an aniline derivative of formula III. 2-Amino-4,6-dibromobenzothiazole of formula IV is dispersed in a mineral acid and/or an organic acid. This dispersion is heated to 70-100 deg.C and then cooled to 5 deg.C or lower, to which NaNO2 or nitrosylsulfuric acid is added for diazotization. The diazotized compound is then added to a solution of the aniline derivative in a mineral acid and/or an organic acid at 10 deg.C or lower to be coupled at pH 1-5, thus giving a monoazobenzothiazole compound of formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a monoazobenzothiazole compound and a method for dyeing or printing hydrophobic fiber materials using the same.

(Prior art) In recent years, in line with the trend of people increasing their sense of leisure and becoming more sophisticated, the demand for textile products such as sportswear in deep and vivid colors has been increasing. In particular, there is a strong desire to develop disperse dyes that can dye or print polyester fibers in deep, vivid colors with good fastness.

Since sportswear and the like are frequently washed at home, there is a high demand for wet fastness, and in particular there is a strong demand for dyes that are less likely to fade during home washing and less likely to contaminate other fibers.

However, conventional dyes have not always been completely satisfactory as described below. In other words, in order to add high value as a recent trend, a number of post-processing processes such as softening, anti-static, and improving texture have been carried out.As these post-processing processes are carried out at high temperatures, the dye bleeds. Washing fastness decreases. In addition, in recent years, synthetic detergents containing sodium alkylbenzene sulfonate as the main ingredient have been mainly used in home laundry, but the effect of synthetic detergents on dyed fabrics is different from that of traditional soaps, and they are generally used on other fibers, especially polyamides. More contamination on acetate fibers. Therefore, when polyamide fibers are used for patterning, it becomes a serious problem. Furthermore, in the JIS-LO844A-4 method, which was Japan's representative test method standard, Marcel soap was used as a detergent, so the test results no longer match the actual usage by consumers. For this reason, in 1932, JIS revised to add JIS-Kg, 371 as a test method for home laundry.
Similarly, in the United States, the AATCC
In Europe, 150 amendments were issued or enacted in 1980 and 1982, respectively.

Dyed products that were evaluated as having good fastness according to the conventional JISA-4 method do not necessarily give good results under test conditions suitable for home washrooms, such as these.

Discoloration and contamination of other fibers during home washing as mentioned above,
KJ4 has become a serious problem with red dyes.

This is because red dyes are often used for deep color dyeing, which not only tends to cause discoloration and contamination of other fibers due to the dye bleed mentioned above, but also makes hot water contamination more noticeable than with other colors. This is because it is easy.

Examples of monoazobenzothiazole disperse dyes capable of dyeing hydrophobic fibers, especially polyester fibers red, include, for example, Japanese Patent Publication No. 45-7712 and Japanese Patent Publication No. 60-29784.
The compounds disclosed in these publications are desired to solve the above-mentioned open circuit problem.

(Problems to be Solved by the Invention) The present inventors have dyed or printed hydrophobic fibers, particularly polyester fibers, in red with excellent dyeability, and dyed or printed them with sunlight, sublimation,
As a result of extensive research in order to find a compound that can provide dyed products with excellent fastness to water, etc., and especially excellent fastness to washing,
The present invention has now been completed.

(Means for Solving the Problems) The present invention is based on the following general formula: The present invention provides a monoazobenzothiazole compound represented by the following formula and a method for dyeing or printing a hydrophobic SaW material using the monoazobenzothiazole compound.

In the above general formula, X is a hydrogen atom, a chlorine atom or a methyl group, preferably a hydrogen atom or a methyl group, particularly preferably a methyl group. Alkyl groups include methyl, ethyl, n-propyl, 1so-propyl, n-butyl,
is.

Examples thereof include -butyl, but methyl and ethyl groups are preferred, with methyl Kaoru being particularly preferred.

The compound represented by the general formula (1) can be produced, for example, by the following method. 2- shown below
Amino-4,6-dibromobenzothiazole- is dissolved or dispersed in a mineral acid such as hydrochloric acid, sulfuric acid, or phosphoric acid, or an organic acid such as acetic acid or propionic acid, or a mixed solvent thereof.

Diazotization is carried out using sodium nitrite or nitrosyl sulfuric acid when cold, preferably below 5°C. At that time, depending on the case, the benzothiazole represented by the above formula (II) is dispersed in the above-mentioned mineral acid, organic acid, or a mixed solvent thereof, heated to preferably 70 to 100°C, and then heated to the above-mentioned temperature. If diazotization is performed by cooling, it is expected that the reaction will proceed smoothly. On the other hand, the aniline derivative represented by the following general formula (in the formula, X and R represent the above-mentioned taste) is mixed with a mineral acid such as hydrochloric acid or sulfuric acid, an organic acid such as acetic acid or propionic acid, or methanol. , dissolved in an organic solvent such as ethanol, dimethylformamide, tetrahydrofuran, or a mixed solvent thereof, and adding the diazonium compound thereto in the cold, preferably at 10° C. or below,
Coupling. At that time, depending on the case, sp
It is preferable to adjust H to 1 to 5 because coupling occurs quickly. After the reaction is completed, the precipitated crystals are separated and
A monoazobenzothiazole compound represented by the general formula (1) is obtained.

The coupling component represented by the above general formula (@) is represented by the following general formula (IV) (wherein, X has the above-mentioned meaning).
-Di(hydroxyethyl)aniline donor is dissolved in an organic solvent such as toluene, pyridine, dimethylformamide, tetrahydrofuran, etc., and in the presence of a deoxidizing agent such as pyridine or triethylamine, the following general formula (V) Ct CO2R (v) (In the formula, R has the above-mentioned meaning.) It can be produced by reacting with a chlorocarbonic acid ester represented by the following formula. In this case, it is particularly preferable to use pyridine as a solvent since it also acts as a deoxidizing agent.

As the aniline derivative represented by the general formula (Ill).

Specifically, the following are exemplified.

N,N-di(methoxycarbonyloxyethyl)anilineN,N-di(methoxycarbonyloxyethyl)-m-
Toluidine N,N-di(methoxycarbonyloxyethyl)-m-
Chloroaniline N,N-di(ethoxycarbonyloxyethyl)aniline N,N-di(ethoxycarbonyloxyethyl)-m-
Toluidine N,N-di(ethoxycarbonyloxyethyl)-m-
Chloroaniline N,N-di(n-propoxycarbonyloxyethyl)
Aniline N,N-di(n-propoxycarbonyloxyethyl)
-m-)Luidine N,N-di(iso-propoxycarbonyloxyethyl)aniline N,N-di(n-butoxycarbonyloxyethyl)aniline N・N-di(1so-butoxycarbonyloxyethyl)aniline N・N -di(5ec-butoxycarbonyloxyethyl)aniline The compound represented by the general formula (υ) is a 2-aminobenzothiazole compound represented by the formula (II), which is a compound represented by the general formula (υ).
It can also be produced by coupling with the N,N-di(hydroxyethyl)aniline derivative represented by IV) and then reacting with a chlorocarbonate represented by general formula (V).

The monoazobenzothiazole compound of the present invention represented by the general formula (R) is useful as a disperse dye for hydrophobic fiber materials, especially polyester fiber materials.For example, the compound of the present invention is mixed with a suitable dispersant, e.g. A dye dispersion can be obtained by grinding into fine particles in an aqueous medium together with a condensate of naphthalene sulfonic acid and formaldehyde or gnonin sulfonic acid.The dye dispersion can be used as it is in liquid form or in powder form by spray drying etc. Dyeing can be carried out by immersing the hydrophobic fiber material in an aqueous dyebath at 105°C or higher under pressure, preferably at 110°C.
It can be carried out at 140°C. Alternatively, dyeing can be carried out in the presence of a carrier such as 0-phenylphenol or trichlorobenzene at a relatively cool temperature, for example in the sN state of water, or by padding the fabric with a dye dispersion and dyeing at a temperature of 150 to 280°C.
It is also possible to dye using so-called thermosol dyeing, which involves dry heat treatment for 80 to 60 seconds.

On the other hand, in the case of textile printing, dyeing can be carried out by kneading the dye dispersion with a suitable sizing agent, padding the cloth with this, and subjecting it to steaming or thermosol treatment. A solvent dyeing method using an organic solvent such as trichlorethylene or perchlorethylene as a dyeing medium is also possible.

The resulting dyed material is softened if necessary.

It can be subjected to various post-processing such as water-repellent processing, texture improvement processing, anti-static processing, sanitary processing, etc., and has the characteristic that various fastness properties, especially washing fastness, do not deteriorate even after post-processing. .

Using the compound of the present invention represented by general formula (1), hydrophobic t! The dyed products obtained by dyeing or printing q4 fiber materials, especially polyester fiber materials, have excellent color fastness such as light fastness, sublimation fastness, and wet fastness, and are especially good in washing fastness even after heat setting or post-processing. It has the characteristic that the degree does not decrease. For example, when polyester fiber material is dyed in a deep color (JIS 2 part 1 density) and then heat set, the washing fastness is significantly superior to that of existing red dyes even under the above-mentioned test conditions suitable for home washing. ing.

In addition, the compound of the present invention can be used to easily obtain dyed products of deep color from the dyestuff, which has excellent dyeability, especially dyeing power and build-up property. The compounds of the present invention offer particularly excellent performance in the dyeing of such clothing. It may be used in combination with other dyes, and good results such as improved dyeing properties and changes in color tone can be expected.

EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited by these Examples. In the examples, parts are parts by weight.

Example 1 81 parts of 2-amino-4,6-dibromobenzothiazole was fractionated into 450 parts of 85% phosphoric acid, heated to 90°C,
After being kept at the same temperature for 2 hours, it was cooled, and 7 parts of sodium nitrite was gradually added while keeping the temperature below 0°C to diazotize it. on the other hand,
N,N-di(methoxycarbonyloxyethyl)-m-
) 84 parts of a pyridine solution containing 9281 parts of ruby was mixed with 860 parts of methanol, and the diazonium compound was added thereto while cooling to below 5°C. After this, water 1
200 parts were added, and the precipitated crystals were separated from P and dried to obtain 54 parts of a monoazobenzothiazole compound represented by the following formula (1).

The maximum absorption wavelength λ of the obtained compound was 530 nm, and the melting point was 174.5 to 176.0°C.

1.0 part of the compound represented by formula (1) above was atomized and dispersed in an aqueous medium together with 8.0 parts of a condensate of naphthalene sulfonic acid and formaldehyde.

10 parts of Tetron jersey (polyester cloth, Teijin ■ product) was immersed in a dye bath containing 0.6 parts of powder obtained by drying this dye dispersion, and dyed for 60 minutes at 180 to 185°C under pressure. . The dyed material was then mixed with 8 parts of caustic soda, 8 parts of hydrosulfide, and 8 parts of betaine type amphoteric surfactant.
After photo-cleaning for 10 minutes at 85°C with a treatment solution consisting of 500 parts and 8000 parts of water, washing with water and drying, a vivid bluish-red dyed product was obtained, with excellent light fastness, sublimation and wet fastness. It was something like that.

The obtained dyed product was subjected to a softening and antistatic treatment according to the following method.

In the pad tank, add Sumitex Softener LK-1 (softening agent made by Sumitomo Chemical Co., Ltd. > 10971) and Smithat F-1 (made by Sumitomo Chemical Co., Ltd., an inhibitor') 5
A pad having a composition of f/l was used and the dyed material was immersed in the pad, and then squeezed uniformly to a richness increase rate of 80%. The dyed material was soaked again, wrung out in the same manner, and subjected to intermediate drying at 80° C. for 2 minutes, followed by heat setting at 170° C. for 1 minute.

``When the washing fastness of the dyed product thus obtained after post-processing was measured, excellent results were obtained.

Example 2 A compound represented by the following formula (2) was synthesized according to the method described in Example 1. The maximum absorption wavelength λDMF of this compound is 5' l l
nm, and the melting point was 177.1-180.8 ax °C.

8.7 parts of lignin sulfonic acid was added to 1.8 parts of the compound represented by the formula (2) and dispersed into fine particles.
A printing paste was prepared by mixing 60 parts of half emulsion paste with the following composition.

0/W emulsion 800 parts Maypro Gum NP 12% paste 694 parts Sodium chlorate 4 parts Total 1000 parts This printing paste was used to print on Tetron Tropical (polyester cloth, manufactured by Teijin ■), and after drying, it was placed in a high temperature steamer at normal pressure.
The film was steamed at 170° C. for 7 minutes to fix it, and then subjected to reduction cleaning treatment, washing with water, drying, and softening/antistatic treatment according to the method described in Example 1. The vivid yellowish-red dyeing thus obtained can be produced by radiation, sublimation and wet 71Si!
It has excellent fastness, especially washing fastness.

Example 8 A compound represented by the following formula (8) was synthesized according to the method described in Example 1. The maximum absorption wavelength λDMF of this compound was 521 parts m.

When a polyester cloth was dyed using the ax keratin compound according to the method described in Example 1, a bright yellowish-red dyed product with excellent washing fastness was obtained.

Example 4 An f arsenic compound represented by the following formula (4) was synthesized according to the method described in Example 1. The maximum absorption wavelength λDM' of this compound (!528
nm Tea Tsuta.

ax When a polyester cloth was printed using this compound according to the method described in Example 2, a bright yellowish-red dyed product with excellent washing fastness was obtained.

Example 5 According to the method described in Example 1, the compounds shown in Table 2 below were synthesized, and a polyester cloth was dyed using this,
A dyed product having the color tone shown in the same table was obtained.

The fastness to wash 11i of these dyed products was excellent.

Table 2 (Continuation h of Table 2)

Claims (2)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents a hydrogen atom, a chlorine atom, or a methyl group, and R represents an alkyl group having 1 to 4 carbon atoms. A monoazobenzothiazole compound represented by (2) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents a hydrogen atom, a chlorine atom, or a methyl group, and R represents an alkyl group having 1 to 4 carbon atoms. A method for dyeing or printing a hydrophobic fiber material, characterized by using a monoazobenzothiazole compound represented by: