JPH0665789B2 - Dyeing method of polyester / cellulose composite fiber - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for dyeing composite fibers composed of polyester fibers and cellulose fibers (hereinafter referred to as “polyester / cellulose composite fibers”). / Without contaminating the cellulose composite fiber
The present invention relates to a method of dyeing only polyester fibers in a reddish color tone with high wet fastness.

2. Description of the Related Art Recently, various types of composite fibers have been widely used in order to increase the added value of fibers. Polyester / cellulose composite fibers have also formed a large market by taking advantage of both of them, and as a dyeing method for this composite fiber, polyester fiber is previously used at a high temperature of about 120 to 140 ° C using a disperse dye. A method of dyeing, and then dyeing the cellulose fiber at a low temperature of about 60 to 70 ° C. using a reactive dye is often employed.

Problems to be Solved by the Invention In the above method, when dyeing the polyester fiber,
It is desirable not to contaminate the cellulose fibers. Disperse dyes used for dyeing polyester fibers are basically incapable of dyeing cellulose fibers, but conventionally, disperse dyes that have increased affinity to polyester fibers to improve dyeability are generally used. And it also has an increased affinity for cellulosic fibers, which results in significant contamination of the cellulosic fibers. As a result, when the cellulose fibers are dyed later with a reactive dye, there is a drawback that the sharpness of the cellulose fibers is lowered, and further, the rubbing fastness of the dyed cloth is lowered.

In order to prevent the defects after this, the disperse dyes that contaminate the cellulose fibers are conventionally removed by repeating the soaping, reduction, and washing steps after dyeing the polyester fibers, but the washing operation is troublesome. Moreover, the cleaning effect reached the limit to some extent.

On the other hand, when a disperse dye having a reduced affinity for polyester fiber is used, the staining property of the polyester fiber itself is lowered, although the staining property of the cellulose fiber is lowered, and There is a drawback that the wet fastness (particularly after post-processing) of the dyed fabric of the cellulose conjugate fiber is significantly lowered.

Therefore, there has been a demand for a dyeing method capable of dyeing only polyester fibers with high wet fastness without contaminating cellulose fibers.

Means and Actions for Solving Problems In view of the above circumstances, the present inventors have found that when dyeing a polyester / cellulose composite fiber with a disperse dye, there is no contamination on the cellulose fiber and the polyester fiber is high. As a result of extensive studies on a dyeing method capable of dyeing well with wet fastness, as a disperse dye, by using a monoazo dye having a substituted benzothiazole as a diazo component and a specific aniline as a coupling component, The present invention has been completed by finding out that the above-mentioned problems in the above technology are solved.

That is, the gist of the first invention of the present invention is to use a benzothiazole-based monoazo dye represented by the following general formula [I] and / or [II] as a dye in a method for dyeing a polyester / cellulose composite fiber. Then, there is a method for dyeing a polyester / cellulose composite fiber, which comprises dyeing only the polyester fiber without contaminating the cellulose fiber.

(In the formula, X represents a chlorine atom or a bromine atom, Y represents a chlorine atom, a bromine atom or a hydrogen atom, Z ¹ represents a hydrogen atom,
Represents a chlorine atom, a methyl group or an acetylamino group, R ¹
And R ² each represent a lower alkyl group, a lower acyloxyalkyl group, a lower alkoxycarbonyloxyalkyl group, a lower alkoxycarbonylalkyl group or a lower alkoxyalkoxycarbonylalkyl group, provided that Z ¹ represents a group other than an acetylamino group. When R ¹
Neither R ² nor R ² represents a lower alkyl group.) (In the formula, Z ² means the same definition as the above Z ^1, and R ³ and R ⁴ are
Lower alkyl group, benzoyloxyethyl group,
Lower alkyloxycarbonyloxyalkyl group, C ₄ ~
C ₆ alkylcarbonyloxy _{group, -C 2 H 4 OCOC 3 H} 6 Cl, representing the lower alkyloxycarbonyl group or phenoxycarbonyl ethoxycarbonyl group) Further, the second invention, for dyeing polyester / cellulose composite fibers In the method, a benzothiazole monoazo dye represented by the above general formula [I] and / or [II] is used as a dye to dye only a polyester fiber without contaminating the cellulose fiber, and then a cellulose fiber A method for dyeing polyester / cellulosic composite fibers, which comprises dyeing a cellulose fiber with a dye for use.

Hereinafter, the present invention will be described in detail.

In the benzothiazole-based monoazo dyes represented by the above general formulas [I] and [II], the lower alkyl group represented by R ^{1 to} R ⁴ is usually a linear or branched C _{1 to} C ₆ chain. And an alkyl group of C _{1 to} C ₄ is preferable. Examples of the lower acyloxyalkyl group represented by R ^{1 to} R ² include, for example, acetyloxyethyl group, propionyloxyethyl group, chlorobutyryloxyethyl group and the like, and examples of the lower alkoxycarbonyloxyalkyl group include , A methoxycarbonyloxyethyl group, an ethoxycarbonyloxyethyl group, a butoxycarbonyloxyethyl group and the like, and the lower alkoxycarbonylalkyl group includes
Examples thereof include a methoxycarbonylethyl group, an ethoxycarbonylethyl group, a butoxycarbonylethyl group, and the like. Examples of the lower alkoxyalkoxycarbonylalkyl group include a methoxyethoxycarbonylethyl group, an ethoxyethoxycarbonylethyl group, a butoxyethoxycarbonylethyl group, and the like. Is mentioned.

Among the monoazo dyes represented by the general formula [I] shown above, particularly preferable are, for example, X and Y are chlorine atoms, Z ¹ is a hydrogen atom, R ¹ is a lower alkyl group or a lower acyloxyalkyl group, Examples thereof include compounds in which R ² represents a lower acyloxyalkyl group. In addition, the general formula shown above [II]
Among the monoazo dyes represented by, Z ² is a hydrogen atom, R ³ is a lower alkyl group, R ⁴ is a benzoyloxyethyl group, —C ₂ H ₄ OCOC ₃ H ₆ Cl or phenoxyethoxycarbonyl. Examples thereof include compounds represented by alkyl groups.

The benzothiazole-based monoazo dyes represented by the general formulas [I] and [II] shown above are respectively represented by the following general formula [III] or [IV] (In the formula, X and Y are the same as defined above) The amines represented by the formula (9) are diazotized by a conventional method, and the following general formulas [V] or [VI] (In the formula, Z ¹ , R ¹ and R ² are respectively the same as defined above) (In the formula, Z ² , R ³ and R ⁴ are the same as defined above) and can be produced by coupling with an aniline.

The polyester / cellulose composite fibers used in the present invention include, for example, polyethylene terephthalate, polyester fibers composed of a polycondensation product of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, and the like, for example, cotton, bis Examples of the composite fiber include cellulosic fibers such as cosmic rayon, cupra ammonium rayon, and hemp. Among these, in particular, as the conjugate fiber that can obtain a remarkable effect when the dyeing method of the present invention is applied, a mixed fiber of polyethylene terephthalate fiber and cotton,
Mixed woven products can be mentioned. The composite ratio of these fibers is usually 95: 5 to 5:95 (weight ratio), preferably 80:20 to 20:
80 (weight ratio).

When dyeing the composite fibers as described above, usually, first, the polyester fiber is dyed, then, the cellulose fiber is dyed, a so-called two-stage dyeing method is adopted,
In the first invention, the first step of dyeing the polyester fiber is targeted.

The dyeing conditions in the dyeing step of the polyester fiber are the same as the dyeing conditions of the normal polyester fiber, and the benzothiazole monoazo dyes represented by the general formulas [I] and [II] shown above are used, for example, as naphthalenesulfonic acid as a dispersant. And a formaldehyde condensate, higher alcohol sulfate, higher alkylbenzene sulfonate, etc. were used to prepare a dyeing bath dispersed in an aqueous medium according to a conventional method, and the composite fiber was prepared at a temperature of 110 to 140 ° C. Dyes can be dyed.

The composite fiber after the dyeing of the polyester fiber is subjected to soaping and cleaning treatment by a conventional method, but in the case of the present invention, since the cellulose fiber is extremely less contaminated, the cleaning operation is simplified and the contamination It is possible to obtain a good dyed product.

Further, in the second invention, the dyeing of the cellulose fiber, which is performed subsequent to the dyeing of the polyester fiber, is not particularly limited, and the dyeing for cellulose such as a direct dye or a reactive dye is carried out by an ordinary method. can do.

In the present invention, in addition to the dip dyeing method, a known dyeing method such as a carrier dyeing method or a padding dyeing method can be similarly applied.

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 monoazo dye (50:50 mixture) represented by 1 was dispersed in water 3 containing 1 g of a naphthalenesulfonic acid formaldehyde condensate and 2 g of a higher alcohol sulfate ester to prepare a dyeing bath. 50 g of polyester cloth and 50 g of cotton cloth are put into this dyeing bath at the same time, and after dyeing at 130 ° C. for 30 minutes, soaping, washing with water and drying are performed, the polyester cloth is dyed in a bright red color, and the light fastness of the dyed cloth is The fastness to sublimation and the fastness to water were good. Further, the cotton cloth was scarcely contaminated, and the cotton contamination was good at 4 to 5 grade as judged by gray scale.

The dye used in this example was manufactured as follows.

4.4 g of 5,6- and 6,7-dichlorobenzothiazole (50:50 mixture) at 0 ° C. with nitrosyl sulfuric acid in 65% sulfuric acid.
Was diazotized for 2 hours to prepare a diazo solution.

Further, 4.1 g of N-ethyl-N-acetoxyethylaniline was dissolved in 200 ml of methanol to prepare a coupling solution.

Add 0 to 2 of the above diazo solution to the obtained coupling solution.
After adding dropwise at 0 ° C. to carry out a coupling reaction and reacting at 0 ° C. for 3 hours, precipitated crystals were separated by filtration, washed with water and dried to obtain 8.0 g of red crystals. Λ max (acetone) of this product is 52
It was 2 nm.

Example 2 The following structural formula 0.5 g of the dye (mixture of isomers) shown in (3) 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

The obtained color paste was printed on polyester-cotton blended fiber (50:50), intermediately dried at 100 ° C, and then held in superheated steam at 170 ° C for 7 minutes to develop color, and then soaping,
After washing with water and drying, a dyed cloth with little cotton stain was obtained. The dyed cloth had good wet fastness, light fastness and sublimation fastness.

The dye used in this example was produced according to Example 1. The λ max (acetone) of this dye was 524 nm.

Then, in order to check the stain resistance of the cotton part, only the cotton cloth was dyed under the same conditions and judged in the same manner as in Example 1. The results are shown in Table 1.

Example 3 The following structural formula Dyeing was performed in the same manner as in Example 1 using the monoazo dye (mixture of isomers) shown in (3) to obtain a dyed cloth dyed in a bright bluish red color with less contamination of the cotton part. 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. The dye used in this example was produced according to Example 1. The λ max (acetone) of this dye was 546 nm.

Then, the stain resistance of the cotton part was determined in the same manner as in Example 1. The results are shown in Table 1.

Example 4 The following structural formula The monoazo dye (mixture of isomers) shown in 1 was used for dyeing in the same manner as in Example 1 to obtain a dyed cloth dyed in bright red with almost no contamination of the cotton part. 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. The dye used in this example was produced according to Example 1. The λ max (acetone) of this dye was 521 nm.

Then, the stain resistance of the cotton part was determined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 1 and 2 In Example 1, monoazo dyes other than those represented by the general formulas [I] and [II] shown above were used as dyes, and dyeing was performed in the same manner, and the stain resistance of the cotton cloth was evaluated. The results are also shown in Table 1.

<Evaluation method of wet fastness after polyurethane processing> (1) Polyurethane processing method After immersing in a 1% solution of Hydran F-24K, it was cured at 160 ° C for 2 minutes.

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

(3) Alkaline sweat fastness Dyeing cloth treated with polyurethane is tested according to JIS L-0848A method, but the attached cloth is tested using nylon cloth and silk cloth, and the stain degree of silk cloth is gray scale. It was judged.

4) Water fastness Dyeing cloth treated with polyurethane is tested according to JIS L-0846A method, except that the attached cloth is silk cloth instead of nylon cloth. It was judged.

From the results shown in Table 1, in the case of the examples of the present invention, the dye stainability is excellent, and the wet fastness after polyurethane processing is also excellent, and it is a very valuable dye in the field of polyester / cotton blend spinning. I understand. As a result, when the dyed fabric obtained is subsequently dyed with a dye for cellulose fiber, or when dyeing is simultaneously performed with a dye for cellulose fiber at the same time, dullness of the cotton part is observed. In particular, a polyester / cotton blended fabric having excellent wet fastness is obtained.

On the other hand, in the case of the comparative example, although the dye structurally similar to that of the example is used, for example, when a dye having a good cotton staining property as in the comparative example 1 is selected, the wet fastness is lowered. On the contrary, when the one having the increased affinity and the improved wet fastness is selected for Comparative Example 2, the cotton stain resistance is significantly reduced, and the practical value is low.

Example 5 A polyester / cotton blended fabric was dyed using the monoazo dyes shown in Tables 2 and 3 below in the same manner as in Example 1, and dyeing having the color tone shown in Tables 2 and 3 below. A cloth was obtained. The alkaline sweat fastness and the stain resistance of cotton of the dyed cloth after the polyurethane processing were checked in the same manner as in Example 1. The results are shown in Tables 2 and 3.

EFFECTS OF THE INVENTION According to the present invention, a polyester / cellulose composite fiber is dyed using the benzothiazole monoazo dye represented by the above general formula [I] and / or [II], so that the cellulose fiber is hardly contaminated. In addition, only polyester fibers can be dyed in a red color tone having high fastness, particularly high wet fastness. Therefore, according to the present invention, the washing operation of the dyed dyed cloth is simplified, and in the subsequent dyeing of the cellulose fiber, the sharpness is not lowered and other adverse effects are not caused.

Claims (2)

[Claims] 1. A method for dyeing a composite fiber comprising polyester fiber and cellulose fiber, wherein a benzothiazole monoazo dye represented by the following general formula [I] and / or [II] is used as a dye, and cellulose is used. A method for dyeing composite fibers composed of polyester fibers and cellulose fibers, which comprises dyeing only polyester fibers without contaminating the fibers. (In the formula, X represents a chlorine atom or a bromine atom, Y represents a chlorine atom, a bromine atom or a hydrogen atom, Z ¹ represents a hydrogen atom,
Represents a chlorine atom, a methyl group or an acetylamino group, R ¹
And R ² each represent a lower alkyl group, a lower acyloxyalkyl group, a lower alkoxycarbonyloxyalkyl group, a lower alkoxycarbonylalkyl group or a lower alkoxyalkoxycarbonylalkyl group, provided that Z ¹ represents a group other than an acetylamino group. When R ¹
Neither R ² nor R ² represents a lower alkyl group.) (In the formula, Z ² means the same definition as the above Z ^1, and R ³ and R ⁴ are
Lower alkyl group, benzoyloxyethyl group,
Lower alkyloxycarbonyloxyalkyl group, C ₄ ~
It represents a C ₆ alkylcarbonyloxy _{group, -C 2 H 4 OCOC 3 H} 6 Cl, lower alkyloxycarbonyl group, or phenoxycarbonyl ethoxycarbonyl group) 2. A method for dyeing a composite fiber comprising polyester fiber and cellulose fiber, wherein a benzothiazole monoazo dye represented by the following general formula [I] and / or [II] is used as a dye, and cellulose is used. A method for dyeing composite fibers composed of polyester fibers and cellulose fibers, which comprises dyeing only polyester fibers without staining the fibers and then dyeing the cellulose fibers using a dye for cellulose fibers. (In the formula, X represents a chlorine atom or a bromine atom, Y represents a chlorine atom, a bromine atom or a hydrogen atom, Z ¹ represents a hydrogen atom,
Represents a chlorine atom, a methyl group or an acetylamino group, R ¹
And R ² each represent a lower alkyl group, a lower acyloxyalkyl group, a lower alkoxycarbonyloxyalkyl group, a lower alkoxycarbonylalkyl group or a lower alkoxyalkoxycarbonylalkyl group, provided that Z ¹ represents a group other than an acetylamino group. When R ¹
Neither R ² nor R ² represents a lower alkyl group.) (In the formula, Z ² means the same definition as the above Z ^1, and R ³ and R ⁴ are
Lower alkyl group, benzoyloxyethyl group,
Lower alkyloxycarbonyloxyalkyl group, C ₄ ~
It represents a C ₆ alkylcarbonyloxy _{group, -C 2 H 4 OCOC 3 H} 6 Cl, lower alkyloxycarbonyl group or phenoxyethanol ethoxycarbonyl group)