JPH07252786A - Method for dyeing with copper-post treating type reactive dye - Google Patents

Abstract

PURPOSE:To improve the color fastness to light and wet color fastness of cellulosic fibers dyed with a reactive dye and enable an improvement in dyeing performances such as buildup or color rendering properties. CONSTITUTION:This method for dyeing comprises dyeing cellulosic fibers with a reactive dye having a structure in which copper can be coordinated and then treating the dyed fibers with copper. Furthermore, the characteristic of this method for post-treating a dyed material comprises treating the dyed cellulosic fibers with a treating liquid containing a copper salt and a fixing agent together in the treatment thereof with the copper.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dyeing method in which a cellulose fiber or a cellulose-containing fiber material is dyed with a reactive dye and then a copper post-treatment step is added. It improves light fastness and wet fastness and enables improvement of dyeing performance such as build-up properties and color rendering properties.

[0002]

2. Description of the Related Art Reactive dyes have been frequently used for dyeing cellulose fibers and cellulose-containing fiber materials.

[0003]

When the reactive dye reacts with the hydroxyl group of cellulose and is fixed to the fiber, the fastness to wetness such as washing is extremely strong. However, unreacted dyes that did not react with cellulose, hydrolyzed dyes that reacted with water, and impurity dyes remained in the cellulose fibers dyed from the dye bath, so these dyes that did not react with cellulose were If it is not removed, the wet fastness of washing will not be strong. In order to remove the dye that has not reacted with cellulose, it is usually necessary to soap it in boiling water containing a detergent or in a state close to this, and wash it thoroughly.
In the case of dark-colored dyeing, it has often been a problem that it cannot be removed sufficiently and the fastness is poor. Further, light fastness is an important fastness item for outer garments, but in sports clothing such as golf wear and general clothing, fading troubles often occur especially in the case of light color, and improvement in light fastness is required.

In order to improve such a defect, there is a dye in which a metal is previously coordinated in the dye. However, when a metal is pre-coordinated in a dye, problems such as a decrease in solubility, a poor dyeing, a decrease in build-up property, a decrease in leveling property, and a decrease in fastness to friction occur.

[0005]

The inventor of the present invention has reached the present invention as a result of earnest research to solve the above problems. That is, the present invention is a dyeing method characterized by dyeing a cellulose fiber with a reactive dye having a structure capable of coordinating copper, and then post-treating copper. It is also possible to treat with the treatment liquid containing.

Cellulose fibers to be dyed by the reactive dye of the present invention include cotton, hemp, rayon, polynosic, cupra, purified cellulose fibers and their blends, interwoven fabrics, blends of cellulose fibers and other fibers,
Cellulose-containing fibers formed by mixed weaving, for example, polyester / cotton blend, polyester / rayon blend, acrylic / cotton blend, wool / cotton blend and the like can be mentioned.

Dyes having a structure capable of coordinating copper are usually considered to be capable of coordinating with copper such as hydroxyl or methoxy group, carboxyl group, azo group, azomethine group, etc. in the dye structure. At least two or more of any of these groups are contained, and the arrangement positions thereof are, for example, as follows.

[0008]

[Chemical 1]

The copper-containing dye in which copper is already fully coordinated during dye production is not the dye of the present invention, but the semi-copperized dye having a structure in which copper is partially coordinated during dye production is Since copper is coordinated in the copper post-treatment after dyeing, it is a target dye of the present invention as a dye having a structure capable of coordinating copper.

The reactive dye having a structure capable of coordinating copper, which is applicable in the present invention, is not limited by the reactive group in the reactive dye structure, and may be a sulfate ethyl sulfone group,
Has known reactive groups such as dichlorotriazine group, monochlorotriazine group, monofluorotriazine group, dichloropyrimidine group, trichloropyrimidine group, difluoromonochloropyrimidine group, dichloroquinoxaline group, and mononicotinic acid triazine group, and copper can be coordinated. Any reactive dye having a different structure can be applied.

A specific example of the reactive dye having a structure capable of coordinating copper is represented by the structural formula in the form of free acid.

[0012]

[Chemical 2]

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

Examples thereof include, but are not limited to:

The coordination of copper can be confirmed by analysis. For example, after the dye is developed by a paper chromatographic method and separated from free copper, the separated dye can be confirmed by analysis of the coordination of copper by atomic absorption spectrometry. Therefore, the dye having a structure capable of coordinating copper is not limited to the dye containing the group shown in the above example, and any reactive dye capable of coordinating copper can be applied. You may use these in mixture of 2 or more types. Further, it may be used as a mixture with a general reactive dye as long as the gist of the present invention is not impaired.

In the dyeing step, a known reactive dye dyeing method which is usually carried out on cellulosic fibers can be applied. For example, general dyeing in exhaustion dyeing method in which dyeing is performed under heating using an inorganic salt such as Glauber's salt and salt and an acid binder such as sodium carbonate, sodium bicarbonate, trisodium phosphate, sodium silicate, sodium hydroxide Condition is reactive dye 0.00
1-20% o. w. f. , 5 to 100 g / l of inorganic salt and 1 to 30 g / l of acid binder at a bath ratio of 1: 5 to 5
0, dyeing is carried out at a dyeing temperature of 20 to 100 ° C. for 30 to 60 minutes. More preferable dyeing conditions are, for example, in the case of a monochlorotrizidine type dip dye, the dye is 0.001 to 12%.
o. w. f. , Anhydrous Glauber's salt 30 to 60 g / l, sodium carbonate 10 to 20 g / l, and a bath ratio of 1: 5 to
40, dyeing is carried out at a dyeing temperature of 80 to 90 ° C. for 40 to 60 minutes. Further, in the pad method, a reactive dye, an acid binder,
After soaking the cellulosic fiber in a pad bath prepared by adding urea etc. for a short time, squeeze it and leave it at room temperature or warming as it is, or heat steam or dry heat for a short time Pad batch dyeing method or pad steam or pad bake continuous A dyeing method can also be applied. Furthermore, the printing method can be applied.

After dyeing, if necessary, washing with water or washing with water and soaping treatment can be carried out, as is customary for reactive dyes. . Then, the copper post-treatment is started. Alternatively, it is possible to carry out a copper post-treatment after washing with water or hot water and then carry out a soaping treatment. Washing with water or washing with hot water can be omitted when the concentration is light.

The copper post-treatment can be carried out by a known method using a copper post-treatment type direct dye. That is, the copper post-treatment type direct dye includes a method using a copper salt, a method using a copper salt and a non-copper-containing fixing agent, and a method using a copper-containing fixing agent.
The copper compound used for the copper post-treatment is not particularly limited as long as it dissolves in water to generate copper ions, but examples thereof include copper sulfate, copper acetate, and a first or second copper salt such as copper chloride. . The copper post-treatment type direct dye has a functional group in its dye structure that easily coordinates with heavy metal ions such as copper to form a stable metal complex salt and significantly reduces the solubility of the dye. Therefore, complex salt is easily formed not only in the dye solution but also in the dye dyed to the fiber, and when the metal complex salt is formed, the solubility of the dye is extremely decreased, and it is considered that the wet fastness is improved by the copper treatment. Has been. Also, the light fastness is significantly improved by the copper treatment. Such a behavior is considered to be the same as in the reactive dye having a structure capable of coordinating copper applicable in the present invention.

In order to obtain stronger wet fastness, it is desirable to carry out not only the copper post-treatment with a copper salt but also the fix treatment with a water-soluble cationic compound. As for the fix treatment, the non-copper-containing fix treatment can be performed in a separate bath after the copper treatment, or the non-copper-containing fix treatment can be performed prior to the copper treatment. The post-treatment method for the dyed product, which is treated with a treatment liquid containing together, is most preferable because it can shorten the process and is most rational. A treatment solution containing a copper salt and a fixing agent is known as a fixing agent for a dicyan-based, polyamine-based, polycation-based, etc. cellulose dye with a copper salt such as copper sulfate, copper acetate, and copper chloride and a water-soluble cationic compound. It can be obtained by mixing with the fixing agent described in 1 above to prepare a treatment liquid or by using a copper-containing fixing agent.

The post-treatment method according to the present invention may be an exhaust method at room temperature to 100 ° C., a pad method, a spray method, or the like, and can be selected depending on the form of the fiber material. For example, the applied concentration of the copper salt-containing treatment aqueous solution of the copper post-treatment with copper salt is 0.01 to 5% solution, but in the exhaust method, the bath ratio is 1: 5 to 50 and 0.5 to 3%.
o. w. f. , Pad method, spray method 1-10 g /
The range of 1 is preferable, and the treatment temperature and time are 40 in the exhaust method.
It is usually carried out at room temperature in the pad method and the spray method at ˜90 ° C. for 10-30 minutes. Further, the applied concentration of the treatment aqueous solution for the fixing treatment with the water-soluble cationic compound is 0.1 to 10% solution, but in the exhaust method, the bath ratio is 1: 5 to 50 and the concentration is 0.5 to 10.
g / l, the pad method and the spray method preferably have a range of 10 to 50 g / l, and the treatment temperature and time are 40 to 9 in the exhaust method.
It is carried out at 0 ° C. for 10 to 30 minutes, and usually at room temperature in the pad method and the spray method. Furthermore, in the case of a treatment liquid containing a copper salt and a fixing agent together, when the copper-containing fixing agent is used, the conditions for the fixing treatment with the water-soluble cationic compound are applied, and the copper salt and the non-copper-containing fixing agent are mixed. When it is used as a treatment liquid, the copper salt-containing treatment aqueous solution may be mixed with the fix treatment aqueous solution and treated under the fix treatment conditions. After the completion of the post-treatment according to the present invention, all treatments and processing applied to the dyed cellulose product can be applied.

[0029]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 1000 parts by adding water to 2 parts of the reactive dye represented by the formula (2) and 60 parts of anhydrous Glauber's salt synthesized by a known method, for example, the method described in JP-A-58-25357. Was prepared. After heating the dyeing bath to 40 ° C., 50 parts of unmercerized cotton knitted fabric was put therein, and the temperature was raised to 80 ° C. over 25 minutes while stirring. After maintaining at the same temperature for 10 minutes, 20 parts of sodium carbonate was added and the mixture was maintained at the same temperature for 50 minutes. Then, the dyed product was taken out and washed with water. The dyed product was a deep, bluish red color. This dyed product was cut into 5 pieces, and the following treatments were carried out.

(Copper post-treatment example 1) Dyeing 5 obtained in Example 1 in a bath prepared by adding water to 1.5 parts of copper sulfate to make 1000 parts
Soak 0 parts and allow 10 minutes from room temperature with stirring to
After the temperature was raised to 0 ° C. and kept at the same temperature for 20 minutes, the dyed product was taken out and washed with water, and the dyed product was put into 1000 parts of boiling water containing 2 parts of the anionic detergent and soaped for 10 minutes. Washed with water, dehydrated and dried. Copper was coordinated in the dyed product, and the hue was changed to dark Bordeaux. The dyeing fastness was excellent as shown in Table 1.

(Copper Post-treatment Example 2) Dyeing 5 obtained in Example 1 was added to a bath prepared by adding water to 1.5 parts of copper acetate to make 1000 parts.
Soak 0 parts and allow 10 minutes from room temperature with stirring to
After the temperature was raised to 0 ° C. and kept at the same temperature for 20 minutes, the dyed product was taken out and washed with water, and the dyed product was put into 1000 parts of boiling water containing 2 parts of the anionic detergent and soaped for 10 minutes. Washed with water, dehydrated and dried. Copper was coordinated in the dyed product, and the hue was changed to dark Bordeaux. The dyeing fastness was excellent as shown in Table 1.

(Copper post-treatment example 3) 50 parts of the dyed product obtained in Example 1 was immersed in a bath prepared by adding water to 1.5 parts of cupric chloride to make 1000 parts, and stirring from room temperature to 10 parts. The temperature is raised to 60 ° C. for 20 minutes and kept at the same temperature for 20 minutes, then the dyed product is taken out and washed with water, and 100 parts containing 2 parts of an anionic detergent.
The dyed product was put into 0 part of boiling water, soaped for 10 minutes, washed with water, dehydrated and dried. Copper was coordinated in the dyed product, and the hue was changed to dark Bordeaux. The dyeing fastness was excellent as shown in Table 1.

(Copper Post-Treatment Example 4) 50 parts of the dyed product obtained in Example 1 was added to 1000 parts of boiling water containing 2 parts of anionic detergent, soaped for 10 minutes, washed with water, and then rinsed with water. Water is added to 4 parts of Fix 555C (manufactured by Sanyo Kasei Co., Ltd., copper-containing polyamine-based fixing agent) to add water 1000
While stirring in a bath prepared in part, the temperature was raised from room temperature to 60 ° C. over 10 minutes and kept at the same temperature for 20 minutes, followed by washing with water, dehydration and drying. Copper was coordinated in the dyed product, and the hue was changed to dark Bordeaux. The dyeing fastness was excellent as shown in Table 1.

Comparative Example 1 A conventional method without copper post-treatment was carried out as follows. 50 parts of the dyed product obtained in Example 1 was put into 1000 parts of boiling water containing 2 parts of anionic detergent, soaped for 10 minutes, washed with water, dehydrated and dried. The dyed product is a deep, bluish red color. The dyeing fastness is shown in Table 1.

[0036]

[Table 1] Table 1 Treatment Copper post-treatment agent Light fastness Washing fastness ────────────────────────────────── -Copper post-treatment example 1 Copper sulfate 5 4-5 Copper post-treatment example 2 Copper acetate 5 4-5 Copper post-treatment example 3 Cupric chloride 5 4-5 Copper post-treatment example 4 Copper-containing polyamine-based fixative 45 5 Comparison Example 1 None 4 3

The dyeing fastness test was carried out according to the following test method. Fastness to light: JIS L 0842 (1988) Fastness to washing: JIS L 0844 (1986) A-4
Enter the contamination grade of cotton

Example 2 1000 parts by adding water to 3 parts of the reactive dye represented by the formula (1) and 60 parts of anhydrous Glauber's salt synthesized by a known method, for example, the method described in JP-A-63-199269. Was prepared. After heating the dyebath to 40 ° C., 50 parts of unmercerized cotton knitted fabric was put therein, and the temperature was raised to 90 ° C. over 30 minutes while stirring. After maintaining at the same temperature for 10 minutes, 20 parts of sodium carbonate was added and the mixture was maintained at the same temperature for 50 minutes. Then, after taking out the dyed product and washing with hot water,
The dyed product was put into 1000 parts of boiling water containing 1 part of the nonionic detergent, soaped for 10 minutes, washed with water, dehydrated and dried. The dyed product was dark blue. This dyed product was cut into 5 pieces, 4 pieces were subjected to the following treatments, and the remaining 1 piece was used as it was for a fastness test.

(Copper post-treatment example 5) Dyeing 5 obtained in Example 2 in a bath prepared by adding water to 1.5 parts of copper sulfate to make 1000 parts
Soak 0 parts and allow 10 minutes from room temperature with stirring to
After the temperature was raised to 0 ° C. and kept at the same temperature for 20 minutes, the dyed product was taken out, washed with water, dehydrated and dried. Copper is coordinated in the dyed product,
The hue became greenish dark blue. The dyeing fastness was excellent as shown in Table 2.

(Copper post-treatment example 6) Dyeing 5 obtained in Example 2 in a bath prepared by adding water to 1.5 parts of copper acetate to make 1000 parts
Soak 0 parts and allow 10 minutes from room temperature with stirring to
After the temperature was raised to 0 ° C. and kept at the same temperature for 20 minutes, the dyed product was taken out, washed with water, dehydrated and dried. Copper is coordinated in the dyed product,
The hue became greenish dark blue. The dyeing fastness was excellent as shown in Table 2.

(Copper Post-treatment Example 7) 3 parts of Kayafix CD (manufactured by Nippon Kayaku Co., polyamine fixing agent) and 1.5 parts of copper acetate were added to water to a bath prepared to obtain 1000 parts. 50 parts of the dyed product was soaked, and the temperature was raised from room temperature to 60 ° C. over 10 minutes while stirring and maintained at the same temperature for 20 minutes, after which the dyed product was taken out, washed with water, dehydrated and dried. Copper was coordinated in the dyed product, and the hue was greenish dark blue. The dyeing fastness was excellent as shown in Table 2.

Comparative Example 2 50 parts of the dyed product obtained in Example 2 was immersed in a bath prepared by adding water to 3 parts of Kayafix CD (manufactured by Nippon Kayaku Co., Ltd., polyamine fixing agent) to make 1000 parts, and stirring the mixture. Meanwhile, the temperature was raised from room temperature to 60 ° C. over 10 minutes and kept at the same temperature for 20 minutes, and then the dyed product was taken out, washed with water, dehydrated and dried. The dyed product was dark blue. The dyeing fastness is shown in Table 2.

[0043]

[Table 2] Table 2 Copper post-treatment and hot treatment Fixing agent Light resistance Washing press Color rendering ─────────────────────────────── ──── Copper post-treatment example 5 Copper sulfate 6 4-5 4-5 Small copper post-treatment example 6 Copper acetate 6 4-5 4-5 Small copper post-treatment example 7 Copper acetate and polyamine-based fixing agent mixture 54- 5 4-5 Small Comparative Example 2 Polyamine-based fixative 4-54-5 2 Large purple taste Example 2 Dyeing product None 5 3 2 Large purple taste

The dyeing fastness test was carried out according to the following test method. Fastness to light: JIS L0842 (1988) Fastness to washing: JIS L0844 (1986) A-4 No. A stain grade of cotton is described. Hot pressing fastness: JIS L0850 (19)
75) No. B-2 Described the fading grade of dried (immediately after) Color rendering: Described the hue change under the tungsten lamp irradiation for the color under the natural light of the north window.

Example 3 Activated deep blue KD-7G (reactive dye, manufactured by Shanghai No. 8 dyestuff in Shanghai, China) has the structure of the above formula (3) as a “dye application handbook” (edited by Shanghai Textile Industry Bureau). ) Pp. 353. Add 1 part of this dye and 60 parts of anhydrous Glauber's salt to water and add 1
000 parts of dyebath were prepared. After heating the dyebath to 40 ° C., 50 parts of unmercerized cotton knitted fabric was put in, and the temperature was raised to 80 ° C. over 30 minutes while stirring. 1 at the same temperature
After keeping for 0 minutes, 20 parts of sodium carbonate was added, and the temperature was kept at the same temperature for 50 minutes. Thereafter, the dyed product was taken out and washed with hot water, and then the dyed product was put into 1000 parts of boiling water containing 1 part of the nonionic detergent and subjected to soaping treatment for 10 minutes, followed by washing with water, dehydration and drying. The dyed product was blue.
This dyed product was cut into two pieces, and one of them was subjected to the following copper post-treatment to compare the light fastness.

(Copper Post-Treatment Example 8) 50 parts of the dyed product obtained in Example 3 was immersed in a bath prepared by adding water to 1.5 parts of copper sulfate to 1000 parts of water, and stirring for 20 minutes from room temperature. After the temperature was raised to 90 ° C. and kept at the same temperature for 30 minutes, the dyed product was taken out, washed with water, dehydrated and dried. Copper was coordinated in the dyed product, and the hue was greenish blue. Light fastness is grade 6,
It was a third-class improvement over the dyed product obtained in Example 3 without the copper post-treatment.

Example 4 Color index C.I. I. Reactive Yel
Low 14 (CI19036) is a reactive dye having a structure capable of coordinating copper, and is known to have the chemical structure of the above formula (10). A cotton paste was printed with 20 parts of this dye, 50 parts of urea, 280 parts of hot water, and 650 parts of medium-viscosity sodium alginate base paste.
0 parts, soda ash 200 parts, potassium carbonate 50 parts, 40 degree Baume caustic soda 50 parts, sodium silicate No. 1 product 10 parts,
Alkaline shock solution consisting of 550 parts of water at 95 ° C for 10
After padding for 2 seconds, rinse with water, desizing, soaping, rinse with water,
A yellow printing cloth was obtained after dehydration and drying. This printing cloth was cut into two pieces, and one of them was subjected to the following copper post-treatment to compare the light fastness.

(Copper Post-Treatment Example 9) 50 parts of the printing cloth obtained in Example 4 was immersed in a bath prepared by adding water to 1.5 parts of copper acetate to prepare 1000 parts of water, and stirring the mixture at room temperature for 30 minutes. After the temperature was raised to 90 ° C. and kept at the same temperature for 30 minutes, the dyed product was taken out, washed with water, dehydrated and dried. Copper was coordinated in the dyed product, and the hue became reddish yellow. Light fastness is grade 7,
It was a second-class improvement over the dyed product obtained in Example 4 without the copper post-treatment.

[0049]

Industrial Applicability The light fastness and wet fastness of a cellulose dyeing product with a reactive dye having a structure capable of coordinating copper are improved.

Claims (4)

[Claims] 1. A dyeing method, which comprises dyeing a cellulose fiber with a reactive dye having a structure capable of coordinating copper and then post-treating copper. 2. The dyeing method according to claim 1, wherein copper is post-treated with a treatment liquid containing a copper salt and a fixing agent together. 3. A cellulose characterized by treating a dyed product of cellulose fibers obtained by dyeing with a reactive dye having a structure in which copper can be arranged, with a treatment liquid containing copper salt or a copper salt and a fixing agent. Copper post-treatment method for textile dyes. 4. A dyed product of cellulose fibers obtained by the method according to claim 1, 2 or 3.