JPH0745631B2 - Benzothiazole monoazo dye - Google Patents

Description

TECHNICAL FIELD The present invention relates to a benzothiazole-based monoazo dye, and more particularly, to a monoazo dye excellent in wet fastness after post-processing.

2. Description of the Related Art Recently, various post-treatments such as water-repellent treatment, texture improving treatment, antistatic treatment and sanitary treatment have been performed on polyester cloth.

Since the post-processing as described above is generally performed at a high temperature, the dye bleeds from the already dyed fiber and the like, which causes a problem that various fastnesses of the fiber and the like, particularly wet fastness, are deteriorated.

For example, benzothiazole-based monoazo dyes represented by the following structural formulas are known (see JP-A-60-108469), but these dyes also show a certain level of goodness when not subjected to post-processing. Although it has a wet fastness, for example, the wet fastness when subjected to polyurethane processing or silicon processing is significantly deteriorated. This tendency is particularly remarkable when silicon processing is applied.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention is a monoazo dye capable of dyeing synthetic fibers, particularly polyester fibers, or cloth produced therefrom, in red or blue, It is an object of the present invention to provide a benzothiazole-based monoazo dye excellent in wet fastness such as fastness to washing, fastness to alkali sweat, fastness to water and the like without causing bleeding even after post-processing.

Means for Solving the Problems The present invention has the general formula [I] (In the formula, X and Y each represent a hydrogen atom, a chlorine atom, a bromine atom or a nitro group, Z represents a hydrogen atom, a methyl group or an acylamino group, R ¹ represents an alkyl group, and R ₂ represents a phenyl group. , A cyclohexyl group, a C ₄ -C ₈ alkyl group, a thiophenyl group or an aralkyl group).

In the general formula [I], the alkyl group represented by R ¹ is
Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, and a pentyl group. Examples of the aralkyl group represented by R ² include a benzyl group and a phenethyl group.

Among the benzothiazole type monoazo dyes of the present invention represented by the general formula [I] shown above, particularly preferable dyes are X.
Is a chlorine atom or a nitro group, Y is a chlorine atom or a hydrogen atom, R ₁ is a C ₁ -C ₄ alkyl group, R ² is a phenyl group or a cyclohexyl group. ,
The thing in which Z represents a hydrogen atom is mentioned.

The benzothiazole-based monoazo dye of the present invention is a novel point in that R ² is structurally particularly specified with respect to a known dye,
Due to the specification of this structure, among the post-working fastness resistances that have been recently demanded, it has extremely excellent wet fastness resistance after post-processing even for some severe processings such as silicon working resistance.

The benzothiazole-based monoazo dye represented by the general formula [I] shown above is, for example, a compound represented by the general formula [II] (Wherein, X and Y are the same as defined above), the amines represented by the following general formula [III] (In the formula, Z, R ¹ and R ² are the same as defined above), and thus can be easily produced.

Fibers that can be dyed with the benzothiazole-based azo dye of the present invention include polyethylene terephthalate, polyester fibers composed of a polycondensate of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, or cotton, silk or wool. Blended products and blended products of the above-mentioned polyester fibers with natural fibers such as

In order to dye polyester fibers with the dye of the present invention, the dye represented by the general formula [I] shown above is insoluble or sparingly soluble in water. Therefore, naphthalene sulfonic acid and formaldehyde are used as dispersants by a conventional method. The condensate, higher alcohol sulfate ester, higher alkylbenzene sulfonate, etc. may be used to prepare a dyeing bath or printing paste dispersed in an aqueous medium, and the dyeing or printing may be carried out. For example, in the case of dip dyeing, a polyester fiber or a blended product thereof can be dyed with excellent fastness by applying an ordinary dyeing treatment method such as a high temperature dyeing method, a carrier dyeing method and a thermosol dyeing method. At that time, if the acidic substance such as formic acid, acetic acid, phosphoric acid, ammonium sulfate or the like is added to the dyeing bath, a better result can be obtained.

Further, the benzothiazole type monoazo dyes of the present invention represented by the general formula [I] shown above may be used as a mixture of two or more kinds, or may be used in combination with the dyes of other types. this house,
When two or more benzothiazole-based monoazo dyes of the present invention represented by the general formula [I] shown above are used in combination, favorable effects such as improvement in dyeability may be obtained due to the interaction of the dyes.

EXAMPLES Next, 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 The following structural formula 0.5 g of the azo dye represented by (50:50 mixture) was dispersed in 3 liters of water containing 1 g of a naphthalene sulfonic acid-formaldehyde condensate and 2 g of a higher alcohol sulfate ester to prepare a dyeing bath. After immersing 100 g of polyester fiber in this dyeing bath and dyeing at 130 ° C. for 60 minutes, soaping, washing with water and drying were carried out, and a clear bluish red dyed fabric was obtained. The obtained dyed cloth had good fastness to light, fastness to sublimation and fastness to water, and also had good temperature stability and pH stability during dyeing of the above dye.

Further, the wet fastness (wash fastness, alkali sweat fastness and water fastness) after the obtained dyed cloth was further silicon-processed (handling-improving process) was judged according to the following method, and the results are shown in Table 1. It was shown to. In addition, we measure the alkali sweat fastness when we give polyurethane processing instead of silicon processing,
It is also shown in Table 1.

(1) Silicon processing method After immersing in a 1% solution of PORON M-R (manufactured by Shin-Etsu Silicon Co., Ltd.), it was cured at 160 ° C for 2 minutes.

(2) Washing fastness A multi-fiber was attached to a dyed cloth treated with silicone, and a washing test was performed according to AATCC Washing No. IIA to determine the contamination of the nylon fiber of the multi-fiber on a gray scale.

(3) Alkaline sweat fastness Silicone dyed cloth is tested according to JIS L-0848A method, but the attached cloth is tested using nylon cloth and silk cloth. It was judged by.

(4) Water fastness A dyed cloth treated with silicon is tested according to JIS L-0846A method, except that the attached cloth is silk cloth instead of nylon cloth. It was judged on a scale.

The dye used in this example was made as follows.

2-amino-5,6-dichlorobenzothiazole 2.2 g, 2
A diazo solution was prepared by diazotizing a mixture of 2.2 g of -amino-6,7-dichlorobenzothiazole with 65% sulfuric acid in nitrosyl sulfuric acid at 0 ° C for 2 hours.

Also, N-ethyl-N-2- (o-phenylphenoxy)
6.3 g of ethylaniline was dissolved in methanol to prepare a coupling solution.

The above diazo solution was added dropwise to this coupling solution at 0 to 2 ° C. to carry out a coupling reaction, and after reacting at 0 ° C. for 3 hours, precipitated crystals were separated by filtration, washed with water and dried to give red crystals.
I got 8.0g. The λmax (acetone) of this product was 528 nm.

Example 2 The following structural formula 0.5 g of the dye (50:50 mixture) shown in 1) was mixed with 0.5 g of a naphthalenesulfonic acid-formaldehyde condensate and finely pulverized with a paint shaker to obtain a finely divided dye. Thoroughly mix this with the base paste of the following composition to obtain 100 g of color paste.
Got

Stock paste composition carboxymethylcellulose-based sizing agent 30.0g tartrate 0.2g aromatic carriers 0.3 g (Sanfu Lauren SN, Nicca Chemical Industry Co., Ltd., Product name Water 68.5g Total 99.0g resulting color paste to the polyester fibers The product was imprinted on the product, intermediately dried at 100 ° C, then kept in steam heated at 170 ° C for 7 minutes to develop color, and then soaped, washed with water and dried to obtain light fastness, sublimation fastness and wetness. A red printed polyester fabric having good fastness was obtained.

In addition, Table 1 shows the wet fastness of the obtained dyed cloth after silicon processing.

The dye used in this example was prepared according to the method described in Example 1. Λmax (acetone) of this dye is 530nm
Met.

Comparative Examples 1 to 3 Polyester cloths were dyed with the dyes shown in Table 1 below. Table 1 shows the wet fastness of the obtained dyed cloth after the silicon processing.

As shown in Table 1, the monoazo dyes of Comparative Examples 1 and 2 are not significantly different from the benzothiazole-based monoazo dye of the present invention in wet fastness after polyurethane processing, but they are siliconized. In that case, the difference widens,
Although the monoazo dyes of Comparative Examples 1 and 2 have a large decrease in fastness, in the case of the benzothiazole monoazo dye of the present invention, a practically good level can be maintained.

Example 3 According to the method of Example 1, a polyester cloth was dyed with the dyes shown in Table 2 to obtain a dyed cloth having a color tone shown in Table 2.

The wet fastness (fastness to alkaline sweat) after siliconizing the obtained dyed cloth was measured, and the results shown in Table 2 were obtained.

The benzothiazole-based monoazo dye of the present invention is suitable for dyeing synthetic fibers, particularly polyester fibers in red to blue, and when the obtained dyed fabric is post-processed,
Bleeding does not occur, and the wet fastness of the dyed product after post-processing can be kept high even when silicon processing, which is said to cause particularly large damage in post-processing, is applied.

Claims (1)

[Claims] 1. A general formula [I] (In the formula, X and Y each represent a hydrogen atom, a chlorine atom, a bromine atom or a nitro group, Z represents a hydrogen atom, a methyl group or an acylamino group, R ¹ represents an alkyl group, and R ² represents a phenyl group. , A cyclohexyl group, a C ₄ -C ₈ alkyl group, a thiophenyl group or an aralkyl group).