JPS63135578A - Dyeing of polyester/cellulose composite fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for dyeing composite fibers consisting of polyester fibers and cellulose fibers (hereinafter referred to as "polyester/cellulose composite fibers"). / Without contaminating cellulose composite fibers,
The present invention relates to a method for dyeing only polyester fibers in red tones with particularly high wet fastness.

BACKGROUND OF THE INVENTION Recently, various composite fibers have been used in large numbers with the aim of increasing the added value of fibers.

Polyester/cellulose composite fibers have also formed a large market by taking advantage of the advantages of both, but the method for dyeing these composite fibers is to dye them in advance using disperse dyes.
Polyester fibers are dyed at high temperatures of the order of ~140'C and then dyed at 60-70'C using reactive dyes, for example.
Many methods are used to dye cellulose fibers at low temperatures.

Problems to be Solved by the Invention In the above method, when dyeing polyester fibers,
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 with increased affinity for polyester fibers and improved dyeability were generally used. and it also has an increased affinity for cellulose fibers, resulting in significant contamination of the cellulose fibers. As a result, when the cellulose fibers are later dyed with reactive dyes, the sharpness of the cellulose fibers decreases, and furthermore,
It has the disadvantage that it has an adverse effect such as a decrease in the color fastness of the dyed fabric to rubbing.

In order to prevent these drawbacks, conventionally, after dyeing polyester fibers, the disperse dyes that contaminate cellulose fibers are removed by repeatedly performing saw pink, reduction, and washing processes, but the washing operations are cumbersome. Moreover, the cleaning effect reaches its limit after a certain point.

Conversely, when a disperse dye with reduced affinity for polyester fibers is used, although the staining property of cellulose fibers is reduced, the dyeing rate on the polyester fiber itself is reduced, and There is a drawback that the wet fastness (especially after post-processing) of dyed fabrics made of cellulose composite fibers is significantly reduced.

Therefore, there has been a need for a dyeing method that can dye only polyester fibers with high wet fastness without contaminating cellulose fibers.

Means and Effect for Solving the Problems In view of the above-mentioned circumstances, the present inventors have determined that when dyeing polyester/cellulose composite fibers using disperse dyes, there will be no contamination of the cellulose fibers, and the polyester fibers will be dyed at a high temperature. As a result of intensive research into a dyeing method that can dye with good wet fastness, we found that by using a monoazo dye containing substituted benzothiazoles as a diazo component and a specific aniline as a coupling component as a disperse dye, we succeeded in improving the conventional dyeing method. The inventors have discovered that the above-mentioned problems in the technology can be solved, and have completed the present invention.

That is, the first gist of the present invention is a method for dyeing polyester/cellulose composite fibers, which uses a benzothiazole monoazo dye represented by the following general formula [I] and/or [II] as the dye. The present invention provides a method for dyeing polyester/cellulose composite fibers, which is characterized by dyeing only polyester fibers without contaminating 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, and Zl represents a hydrogen atom, a chlorine atom, a methyl group or an acetylamino group,
R1 and R2 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 Zl represents a group other than an acetylamino group. (In the formula, Z means the same definition as Z1 above, and R3
and R4 each represent a lower alkyl group, benzoyloxyethyl group, lower alkyloxycarbonyloxyalkyl group, C4-C6 alkylcarbonyloxyalkyl group, C2H40COC3H6Cl, lower alkyloxycarbonylalkyl group or phenoxyethoxycarbonylalkyl group) A second invention provides a method for dyeing polyester/cellulose composite fibers, in which the dye is of the general formula [I
] and/or [II] without contaminating the cellulose fibers using the benzothiazole monoazo dye shown in
The present invention relates to a method for dyeing polyester/cellulose composite fibers, which comprises dyeing only polyester fibers and then dyeing cellulose fibers using a dye for cellulose fibers.

The present invention will be explained in detail below.

In the benzothiazole monoazo dyes represented by the general formulas [I] and [II], the lower alkyl group represented by R1-R4 is usually a linear or branched alkyl group of 01 to C6. Examples of lower acyloxyalkyl groups include acetyloxyethyl group, propionyloxyethyl group, chlorobutyryloxyethyl group, etc., and examples of lower alkoxycarbonyloxyalkyl groups include methoxycarbonyloxyethyl group, ethoxycarbonyl group, etc. Examples of lower alkoxycarbonyl alkyl groups include methoxycarbonylethyl group, ethoxycarbonylethyl group, butoxycarbonylethyl group, and lower alkoxycarbonyl alkyl groups. Examples of the group include methoxyethoxycarbonylethyl group, ethoxyethoxycarbonylethyl group, and butoxyethoxycarbonylethyl group.

Among the monoazo dyes represented by the general formula [I], particularly preferred are, for example, X and Y are a chlorine atom, Zl is a hydrogen atom, R1 is a lower alkyl group or a lower acyloxyalkyl group, and R2 is a Examples include compounds represented by a lower acyloxyalkyl group. In addition, the general formula [
Among the monoazo dyes represented by II], particularly preferred are those in which Z2 is a hydrogen atom, R3 is a lower alkyl group,
Examples include compounds in which R4 is a benzoyloxyethyl group, -C2H40°COC3H6Cl, or a phenoxyethoxycarbonylalkyl group.

The benzothiazole monoazo dyes represented by the above general formulas [I] and [II] are each represented by the following general formula [III]
or [IV] (wherein X and Y are the same as defined above) An amine represented by the following formula [V] or [VI] (wherein, Zl, R1 and R2 are respectively, is diazotized by a conventional method) Each is the same as the above definition) (wherein 72, R3 and R4 are each the same as the above definition) It can be produced by coupling with an aniline represented by the following formula.

Examples of the polyester/cellulose composite fiber used in the present invention include polyester fibers made of polyethylene terephthalate, a polycondensate of terephthalic acid and 1,4-bis-(hydroxymethyl)cyclohexane, etc.
Examples include composite fibers with cellulose fibers made of cotton, viscose rayon, cuproammonium rayon, hemp, and the like. Among these, composite fibers that can produce particularly remarkable effects when the dyeing method of the present invention is applied include blends and blends of polyethylene terephthalate fibers and cotton. The composite ratio of these fibers is usually 95:5 to 5:95 (weight ratio), preferably 8
0:20 to 20:80 (weight ratio).

When dyeing composite fibers such as those mentioned above, a so-called two-stage dyeing method is usually employed, in which polyester fibers are first dyed and then cellulose fibers are dyed.
The first invention is directed to the first step of dyeing polyester fibers.

The dyeing conditions in the dyeing process for polyester fibers are the same as those for ordinary polyester fibers, and the benzothiazole monoazo dyes represented by the general formulas [I] and [II] are used, for example, with naphthalenesulfonic acid as a dispersant. A dyeing bath is prepared in a conventional manner using a condensate of formaldehyde, a higher alcohol sulfuric ester, a higher alkylbenzene sulfonate, etc., dispersed in an aqueous medium, and the dye bath is dyed at a temperature of 110 to 140'C. Fibers can be dyed.

Composite fibers that have been dyed with polyester fibers are subjected to saw pinking and washing treatments in a conventional manner, but in the case of the present invention, since there is extremely little contamination of cellulose fibers, the washing operation is simple, and furthermore, the contamination can be reduced. A good dyed product can be obtained.

Further, in the second invention, the dyeing of the cellulose fibers performed subsequent to the dyeing of the polyester fibers is not particularly limited, and may be carried out by a conventional method using a dye for cellulose such as a direct dye or a reactive dye. can do.

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

EXAMPLES Next, the present invention will be explained in more detail by examples, but the present invention is not limited to the following examples.

Example 1 Monoazo dye represented by the following structural formula (50:50 mixture) 0.5
9, naphthalene sulfonic acid formaldehyde condensate 1
A dyeing bath was prepared by dispersing it in 3 parts of water containing 2 g of J and higher alcohol sulfate ester.

50g of polyester cloth and real cotton cloth 509 were put into this dyeing bath at the same time and dyed at 130°C for 30 minutes, then saw pink, washed with water, and dried.The polyester cloth was dyed bright red, and the light fastness of the dyed cloth was , sublimation fastness and water fastness were good. Moreover, this cotton fabric was hardly contaminated, and when judged on a gray scale, the cotton stainability was good, at grade 4 to 5.

The dye used in this example was produced as follows.

5.6- and 6,7-dichlorobenzothiazole (50
: 50 mixture>4.49 was diazotized using nitrosyl sulfuric acid in 65% sulfuric acid at 0° C. for 2 hours to produce a diazo solution.

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

Add 0 to 2 of the above diazo solution to the resulting coupling solution.
The coupling reaction was performed dropwise at °C and 3
After reacting for a period of time, the precipitated crystals were filtered, washed with water, and dried to obtain red crystals 8.07. The λmax (acetone) of this product was 522r1m.

Example 2 A dye represented by the following structural formula (isomer mixture>0.5y) was mixed with 0.57% of a naphthalene sulfonic acid-formaldehyde composite and pulverized in a paint shaker to obtain a finely divided dye. , thoroughly mixed with base glue consisting of the following composition,
Color paste '1009 was obtained.

Composition of base glue Carboxymethyl cellulose glue 30.09 Sake E
I acid 0.2g Aromatic carrier 0.3g (Sunfloren SN, manufactured by NICCA CHEMICAL CO., LTD., trade name) Water 68
．． 59 The obtained color paste was mixed with polyester-cotton blend fiber (50
: 50) Print on top, perform intermediate drying at 100'C,
Next, it was held in superheated steam at 170'C for 7 minutes to develop color, and then soaped, washed with water, and dried.
A dyed fabric with less cotton staining was obtained. In addition, the wet fastness, light fastness 17 degrees, and sublimation fastness of this dyed fabric were good.

Note that the dye used in this example was produced according to Example 1. Also, the λmax (acetone) of this dye is 52
It was 4 nm.

Next, in order to check the stainability 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 Dyeing was carried out in the same manner as in Example 1 using a monoazo dye (mixture of isomers) represented by the following structural formula, and a dyed cloth dyed in a bright bluish red color with little staining of the cotton part was obtained.

The light fastness, sublimation fastness and water fastness of the obtained dyed cloth were good, and the temperature stability and DH stability during dyeing of the above dye were also good. Note that the dye used in this example was produced according to Example 1. Further, the λmax (acetone) of this dye was 546 nm.

Next, the stainability of the cotton portion was determined in the same manner as in Example 1. The results are shown in Table 1.

Example 4 Dyeing was carried out in the same manner as in Example 1 using a modiazo dye (mixture of isomers) represented by the following structural formula, and a dyed cloth dyed in bright red with almost no staining on the cotton part was obtained.

The light fastness, sublimation fastness and water fastness of the obtained dyed cloth were good, and the temperature stability and (1) H stability during dyeing of the above dye were also good. Note that the dye used in this example was produced according to Example 1. Further, the λmax (acetone) of this dye was 521 nm.

Next, the stainability of the cotton portion was determined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 1 and 2 = 19 Dyeing was carried out in the same manner as in Example 1 using monoazo dyes other than those represented by the front claw general formulas [I] and [n], and the staining properties of the cotton fabric were determined. did. The results are also listed in Table 1.

<Evaluation method of wet fastness after polyurethane coating> (1) Polyurethane processing method After immersing in a 1% solution of Hytran F-24, 160°
Cure for 2 minutes.

(2) Washing fastness A multi-fiber was attached to a dyed cloth treated with polyurethane, and a wash R test was conducted according to the AATCC washing method No. △, and the staining of the nylon fibers of the multi-fiber was determined on a gray scale.

(3) Alkaline sweat fastness: JISL-084 dyed fabric treated with polyurethane
The test was conducted in accordance with Method 8A, except that nylon cloth and silk cloth were used as the attached cloths, and the degree of contamination of the silk cloth was determined on a gray scale.

4) Water fastness: Dyed fabric treated with polyurethane according to JISL-0846
The test was conducted in accordance with Method A, except that a silk cloth was attached instead of a nylon cloth, and the degree of contamination of the silk cloth was determined on a gray scale.

From the results in Table 1, the examples of the present invention have good cotton stain resistance and excellent wet fastness after polyurethane processing, making them extremely valuable dyes in the field of polyester/cotton blends. I understand. .

As a result, even when the obtained dyed fabric is subsequently dyed using a dye for cellulose fibers, or when dyeing is carried out at the same time using a dye for cellulose fibers if necessary, the cotton portion does not become dull. A polyester/cotton blend fabric having particularly excellent wet fastness can be obtained.

On the other hand, in the case of Comparative Examples, even though dyes that are structurally similar to those of Examples are used, if dyes with good cotton staining properties are selected, such as in Comparative Examples, the wet fastness decreases. On the other hand, if a material with increased affinity and improved wet fastness is selected for Comparative Example 2, the cotton staining property will be greatly reduced, and the practical value will be low.

Example 5 A polyester/cotton blend fabric was dyed in the same manner as in Example 1 using the monoazo dyes shown in Tables 2 and 3 below, resulting in the color tones shown in Tables 2 and 3 below. A dyed fabric having the following properties was obtained. The dyed fabric was checked for alkali sweat fastness and cotton staining property after polyurethane processing in the same manner as in Example 1. The results are shown in Tables 2 and 3.
Shown in the table.

Effects of the Invention According to the present invention, the above general formula [I] and/or [II]
Polyester/cellulose composite fibers are dyed using the benzothiazole-based monoazo dye shown in , so the polyester fibers are dyed to a red tone with high fastness, especially high wet fastness, without contaminating the cellulose fibers. can do. Therefore, according to the present invention, the washing operation of the dyed cloth becomes simple, and the subsequent dyeing of cellulose fibers does not have a decrease in brightness or other adverse effects.

Claims (2)

[Claims] (1) In a method for dyeing composite fibers consisting of polyester fibers and cellulose fibers, a benzothiazole monoazo dye represented by the following general formula [I] and/or [II] is used as the dye to dye cellulose fibers. A method for dyeing composite fibers made of polyester fibers and cellulose fibers, which is characterized by dyeing only the polyester fibers without contaminating them. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, X represents a chlorine atom or a bromine atom, Y represents a chlorine atom, a bromine atom, or a hydrogen atom, and Z^1 represents a hydrogen atom, a chlorine atom, represents 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, However, when Z^1 represents a group other than an acetylamino group, both R^1 and R^2 do not represent a lower alkyl group) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (Formula In the middle, Z^2 means the same definition as Z^1 above, and R^
3 and R^4 are each a lower alkyl group, a benzoyloxyethyl group, a lower alkyloxycarbonyloxyalkyl group, a C_4 to C_6 alkylcarbonyloxyalkyl group, -C_2H_4OCOC_3H_6Cl,
(lower alkyloxycarbonylalkyl group or phenoxyethoxycarbonylalkyl group) (2) In a method for dyeing composite fibers made of polyester fibers and cellulose fibers, benzothiazole monoazo dyes represented by the following general formulas [I] and/or [II] are used as dyes to dye cellulose fibers. A method for dyeing composite fibers made of polyester fibers and cellulose fibers, which comprises dyeing only the polyester fibers without contaminating them, and then dyeing the cellulose fibers using a dye for cellulose fibers. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, X represents a chlorine atom or a bromine atom, Y represents a chlorine atom, a bromine atom, or a hydrogen atom, and Z^1 represents a hydrogen atom, a chlorine atom, represents 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, However, when Z^1 represents a group other than an acetylamino group, both R^1 and R^2 do not represent a lower alkyl group) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (Formula In the middle, Z^2 means the same definition as Z^1 above, and R^
3 and R^4 are each a lower alkyl group, a benzoyloxyethyl group, a lower alkyloxycarbonyloxyalkyl group, a C_4 to C_6 alkylcarbonyloxyalkyl group, -C_2H_4OCOC_3H_6Cl,
(lower alkyloxycarbonylalkyl group or phenoxyethoxycarbonylalkyl group)