JPS6221880A - Dyeing of blended fiber material of cellulosic fiber and nitrogen-containing 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 The present invention relates to a method for dyeing a mixed fiber material of cellulosic fibers and nitrogen-containing fibers.

Conventionally, direct dyes, threne dyes, sulfur dyes, linear reactive dyes, etc. have been used for dyeing cellulose fibers, and for dyeing nitrogen-containing fibers (JU dyes, metal complex dyes, chromium mordant dyes, wool reactive dyes, etc.) have been used to dye cellulose fibers. Dyes, etc. are used.

In order to industrially dye a mixture of cellulose fibers, nitrogen-containing fibers, and rubella, the first step is to first dye the nitrogen-containing fibers in an acidic or weakly acidic bath using acid dyes or metal complex dyes. A two-bath two-stage dyeing method in which cellulose fibers are dyed and then directly dyed with a dye, or after dyeing cellulose fibers with thren dyes, sulfur dyes, line reactive dyes, etc.
A two-bath, two-step dyeing method has been carried out in which nitrogen-containing fibers are dyed with acid dyes, metal complex dyes, chromium mordant dyes, reactive dyes for wool, and the like.

However, the two-bath two-stage dyeing method using acid dyes or metal complex dyes and direct dyes has insufficient wet fastness of dyed products and it is difficult to obtain clear hues. The two-bath two-step method using reactive dyes, metal complex dyes, and chromium mordant dyes is a method that uses strong alkalis in the dyeing bath for protein m#! Problems include a decrease in the strength of chromium mordant dyes and a larger wastewater load after dyeing than other dyes, and chromium mordant dyes require a long time to dye and it is difficult to obtain clear hues as with metal complex dyes. Still, it must be improved.

Also known is a method of dyeing both cellulose fibers and nitrogen-containing fibers with reactive dyes for cellulose. However, in this case, a dyed product with a clear hue and fastness can be obtained, but the reactive dye is adsorbed to the nitrogen-containing ma through ionic bonds during dyeing of the cellulose m fiber side, which causes a decrease in fastness. A problem remained. Further, when using a reactive dye for cellulose and a reactive dye for wool, it is necessary to dye the nitrogen-containing fiber with the reactive dye for wool in an acid bath and then perform an alkali treatment for the purpose of improving fastness.

Furthermore, when a linear reactive dye having a sulfate ethyl sulfur group as a reactive group is to be used for dyeing nitrogen-containing fibers, the dye is treated with an alkali at the temperature of the rice grains, and then neutralized with an acid. The work process is extremely complicated because it is necessary to carry out dyeing in an acidic bath after carrying out alkali activation. Furthermore, when dyeing such a mixed product by mixed color dyeing, the types and number of dyes used are significantly increased, and the creation of dyeing prescriptions and dye inventory management become complicated.

Under these circumstances, the present inventors have discovered a more efficient dyeing method that is superior to any of the above-mentioned methods. The bifunctional reactive dye has excellent reactivity with nitrogen-containing fibers, exhibits high dyeability when dyed in an acidic bath, and is highly reactive with nitrogen-containing fibers under cellulose dyeing conditions in an alkaline bath. ! The present invention was completed based on the discovery that the dyeing of the A-fibers was extremely low. That is, in the present invention, when dyeing a fiber material made of a mixture of cellulose fibers and nitrogen-containing fibers, the general formula (I) [wherein is an organic dye residue having a sulfonic acid group, R1,
R2 is a hydrogen atom or an alkyl group, R2 is a phenylene group or naphthalene group which may be substituted with one or two of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom or a sulfonic acid group, and X is a halogen atom ,Y
is a group -80z CH=, 0liz or -BO+
CHz CHzYt (Yt is a group that is eliminated by alkali). ] One or more dyes selected from the dyes represented by formula (I) are used to dye nitrogen-containing fibers in an acidic bath, and then one or more dyes selected from the dyes represented by formula (I) above are dyed. Provided is a method for dyeing a mixed fiber material, which is characterized by dyeing cellulose fibers in an alkaline bath using a dye.

Mixed fibers obtained by blending, twisting, or knitting cellulose fibers such as cotton, hemp, viscose rayon, and copper ammonia viscose rayon with nitrogen-containing m-fibers such as wool, silk, and nylon by the method of the present invention. The material can be dyed with industrial advantage.

The dye represented by the general formula (I) used in the present invention is disclosed in, for example, Japanese Patent Publication No. 89-18184, Japanese Patent Publication No. 58-1
It is described in Japanese Patent Publication No. 8472, Japanese Patent Publication No. 58-55189, Japanese Patent Publication No. 48672-1987, and is well known.

According to the present invention, first, nitrogen-containing fibers are dyed using one or more of the above dyes, preferably in an acidic bath containing a leveling agent.

Examples of acids used include organic acids such as acetic acid, formic acid, and citric acid, salts that exhibit acidity at high temperatures such as ammonium acetate and ammonium sulfate, and inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid.

The pH of the dye bath is preferably in the range of 8.0 to 6.5.

As a leveling agent, the following formula, (OHz CLiCLi20) RN"-C2Els, Cz EIs so? (C
EI 2 CH20) n H [wherein, 几represents an alkyl group having 12 to 18 carbon atoms,
m and n represent positive numbers, and the sum thereof is 2-20. ] The amphoteric ionic surfactants shown are effective in terms of level dyeing and dyeing properties.

After dyeing the nitrogen-containing fibers, the mixed fiber material 1 is taken out and washed with water, or without being taken out, 1 m or more of the dye represented by the general formula (I) is used, preferably in an alkaline bath containing an inorganic salt. Performs cellulose-based miscellaneous dyeing,
Finish by soaping if necessary and fixing if necessary.

The alkalis used include alkali metal hydroxides, alkali metal scrap carbonates, tribasic sodium phosphates, tribasic potassium phosphates, alkali acetates, alkali oxalates, alkali perphosphates and organic bases such as triethanolamine. , tertiary amines such as diethyl-2-phenol, and the like.

Examples of the soaping agent include anionic surfactants and nonionic surfactants such as sodium alkylbenzenesulfonate and polyoxyethylene alkyl phenyl ether.

Dyes and cellulose mI# used for dyeing nitrogen-containing fibers
The dye used for dyeing may be the same or different, but preferably the hue is the same, and more preferably the same dye is used.

A specific example of the dyeing method according to the present invention is listed below.

First, a mixed fiber material is placed in a dye bath containing a reactive dye represented by the general formula (I), a zwitterionic surfactant, and an acid.
The dyed product is poured at 0 to 50°C, gradually raised to 80 to 100°C, and treated for 30 to 60 minutes, after which the dyed product is taken out and washed with water. Next, it is poured into another dye bath containing the reactive dye represented by the general formula (I) and an inorganic salt such as mirabilite and common salt at 20 to 50°C,
After treatment for 5-80 minutes, add alkali and heat at 50-80℃.
After treatment at that temperature for 40 to 120 minutes, the dyed product is taken out and washed with water. Next, the dyed product is placed in a bath containing an anionic surfactant or a nonionic surfactant and the temperature is raised to 85 to 100°C, and after treatment at that temperature for 5 to 10 minutes, the dyed product is taken out and washed. If necessary, fix with a fixing agent, then wash with water and dry.

According to the method of the present invention, cellulosic fibers and nitrogen-containing m
Mixed fiber materials consisting of fibers can be dyed in a uniform hue or each fiber can be dyed in different hues, fast and economically.

The present invention is characterized in that the reactive dye of the general formula (I) used is well dyed on the nitrogen-containing fibers of the mixed Iall# material in an acid bath,
Almost no dyeing to the other cellulose fiber,
This method takes advantage of the fact that the reactive dye dyes cellulose fibers better in an alkaline bath containing an inorganic salt, but dyes nitrogen-containing fibers only to the extent of staining. When using a conventional monofunctional cellulose fiber reactive dye having a sulfate ethyl sulfo group as a reactive group for dyeing nitrogen-containing fibers, tertiary phosphorus is added to the dye bath before dyeing in an acidic bath. So-called alkali activation, in which heat treatment is performed by adding an alkali such as acid soda, is required, and dyeing of nitrogen-containing fibers is promoted even in an acid bath. If so, there is no need for alkali activation, and even if the dye is directly dyed in an acid bath, a strong dyed product with high density can be obtained. Furthermore, when attempting to dye cellulose fibers of a mixed A string material consisting of cellulose fibers and nitrogen-containing complex ml in an alkaline bath using conventional reactive dyes for cellulose, the nitrogen-containing fibers are more likely to be contaminated than the cellulose am. There was a major problem in that cellulose fibers could not be dyed sufficiently deep, but the method of the present invention solves that problem and allows easy fast dyeing of both nitrogen-containing a-fibers and cellulose fibers. That's what makes it so special.

Regarding the dyeing process, conventional dyeing processes using monofunctional reactive dyes often result in a cellulose color, and in this case, it is essential to remove unfixed dye by soaping after dyeing cellulose fibers. If soaping is omitted, the undyed dye adhering to the fibers and the dye hydrolyzed with alkali will flow into the dye bath in the next dyeing process for nitrogen-containing fibers and re-contaminate the dye, resulting in fluctuations in density and hue. The resulting dyeing becomes unstable and the fastness is poor. Furthermore, if the nitrogen-containing fibers are not subjected to alkali activation treatment prior to dyeing, the final soaping is essential as the dyeing of the nitrogen-containing fibers will be incomplete, so soaping will be carried out twice in the middle and at the end. It becomes necessary.

On the other hand, according to the dyeing process of the present invention, the dyeing process on the nitrogen-containing fibers is good, the amount of residual bath is extremely small, and the contamination of the cellulose fibers is also extremely low, so that the dyeing process can be carried out before proceeding to the next dyeing of the cellulose fibers. Soaping is not necessary; just a simple wash with water to remove the acid is sufficient. Therefore, the method of the present invention not only streamlines the dyeing process by requiring fewer soaping steps than the conventional dyeing process, but also results in less damage to the fibers due to soaping (thus, a higher quality product is obtained).

Examples are shown below, where C indicates parts by weight.

Example 1 ++l C%I
1000 parts of CQ water (0.2 parts of reactive dye represented by formula (1) and 1.0 part of reactive dye represented by formula (2))
0.1 part of the reactive dye represented by formula (3) is dissolved, and Sumibon Wum (product of Sumitomo Chemical Co., Ltd., amphoteric surfactant) is dissolved in this.
1.8 parts and 2 parts of glacial acetic acid were added and kept at 50°C. A wool/rayon (65/85) intertwisted yarn was inserted into this, and the temperature was raised to 100° C. in 40 minutes, and the wool side was dyed at this temperature for 80 minutes. After that, take out the dyed product and hold it at 60℃.
Washed with water. Next, 0 parts of the dye of formula (1) was added to 1000 parts of water.
．． 1 part, 0.6 part of dye of formula (2), and 0.6 part of dye of formula (3).
The wool/rayon intertwisted yarn with the wool side dyed was placed in a bath containing 50 parts of anhydrous sodium sulfate and 50 parts of anhydrous sodium sulfate and kept at 30° C., and treated for 20 minutes. Thereafter, 20 parts of soda ash was added to the dye bath, and the temperature was gradually raised to 60° C. over 80 minutes, and the rayon side was dyed at this temperature for 60 minutes. Next, the dyed product was taken out and washed with water, and 2 parts of Monogen Powder (manufactured by Dai-Kogyo Seiyaku Co., Ltd., anionic surfactant) was dissolved in 1000 parts of water.
The dyed product was placed in a bath at 0.degree. C. and treated for 5 minutes, then taken out, washed with water, dehydrated, and dried to finish. As a result, a uniform and strong red dyed product was obtained for both wool and rayon.

Comparative Example 1 100 parts of water 410. I, No, Acjd Yellow
w 11 y acid dye 0.1 part and C, 1, No, mu a
0.7 parts of acidic dye of id Red 249 and C01,
No, Muaid Blue 129 acid dye 0.02
1 part and 2 parts of glacial acetic acid were added to it to make a 50°C dye bath, and 100 parts of wool/rayon (65/85) intertwisted yarn was added thereto.
Then, the same treatment as in Example 1 was carried out to dye the wool side. After washing the dyed product in hot water, the rayon side was dyed in the same manner as in Example 1, and a red dyed product was obtained, but the washing fastness was significantly inferior to that in Example 12. Regarding the types and number of dyes used, in Example 1 there were only eight reactive dyes, whereas in the comparative example a total of six dyes, eight acidic dyes and eight reactive dyes, were used.

Table 1 Washing fastness (A-4) Example 2 0, 5 &
iS was dissolved, 0.5 part of sulfuric acid and 1 part of glacial acetic acid were added thereto, and the mixture was maintained at 50°C. Here wool/cotton (50/6
0) 100 parts of the interlaced knit were put in, the temperature was raised to 100° C. in 40 minutes, and the wool side was dyed at this temperature for 80 minutes. Thereafter, the dyed product was taken out and washed with 60°C water.

Next (1.5 parts of the dye of formula (1) and 50 parts of anhydrous sodium sulfate were dissolved in 1000 parts of this water, and the above wool/cotton mixture was dissolved in a bath kept at 80°C.
A dyed cloth with one knit wool side dyed was inserted and treated for 20 minutes. After that, 20 parts of soda ash was added to the dye bath and 80 parts of soda ash was added to the dye bath.
The temperature was gradually raised to 60° C. in minutes, and the cotton side was dyed at this temperature for 60 minutes.

Next, it was washed with water, soaped in the same manner as in Example 1, washed with water, dehydrated, and dried to finish.

As a result, a uniform and strong golden yellow dyed product was obtained for both wool and cotton.

Comparative Example 2 1000 parts of water 1c C, I, No, Reaot
Dissolve 0.5 part of iye Yel low76 reactive dye (reactive dye having one sulfate ether sulfone group as a reactive group), and add 0.5 part of Sumibon Wum to this.
1 part and 1 part of glacial acetic acid were added and kept at 50°C. wool here/
Cotton (50150) mixed knit io.

Then, the same treatment as in Example 2 was carried out to dye the wool side. After that, as in Example 2, the formula (
Dye the line side using 1.5 parts of the reactive dye from 1),
Finished by washing and soaping. As a result, the dyed product was noticeably lighter and flickering on the wool side than on the line side G.

Comparative Example 8 Reactive dye used in Comparative Example 2 in water too much
Dissolve 0.5 part of ive Yellow 76, add 0.25 part of crystalline 8th sodium phosphate thereto, raise the temperature to 85°C, treat for 5 minutes, perform alkali activation, and then heat to 50°C.
Cool to , add 1 part of glacial acetic acid and 9.5 parts of Sumibon WA,
100 parts of a wool/cotton (50150) interlaced knit were put in and treated in the same manner as in Example 2 to dye the wool side. Next, the same treatment as in Example 2 was carried out using 1.5 parts of the reactive dye of formula (1) to dye the line side.As a result, uniform and strong golden yellow dyed products were obtained for both wool and cotton. However, compared to Example 2, the dyeing operation was significantly more complicated.

Comparative Example 4 Reactive dye kacti used in Comparative Example 2 in 1000 parts of water
Dissolve 0.5 parts of ve Yellow 76, add 5 parts of Sumibon WA□ and 1 part of glacial acetic acid, bring the temperature to 50°C, and add 100 parts of wool/cotton (50150) interlaced knit to it to obtain Example 2. The wool side was dyed using the same process as above. Next+cReactive Y6110W
The same treatment as in Example 2 was carried out using 1.6 parts of 76 to dye the line side. As a result, both wool and cotton are uniform.

A golden yellow dyed product was obtained, but the density was significantly lower than that of Example 2.

Example 3 0.1 part of the reactive dye represented by formula (1), 0.2 part of the reactive dye represented by formula (2), and 0.5 part of the reactive dye represented by the formula were dissolved in 1000 parts of water. Nisu Shibabon W A Q,
g parts and 1 part of glacial acetic acid were added and kept at 50°C. 100 parts of wool/cotton (40/60) blended yarn was put into this, the temperature was raised to 100'C in 40 minutes, and the upper side was dyed at this temperature for 80 minutes. The dyebath was then cooled to 60° C. over a period of 20 to 80 minutes. During this time, 1.5 parts of soda ash was added to the dye bath at 80°C or lower to neutralize it.
．． 5 parts, 0.8 parts of the reactive dye represented by formula (5), and 0.8 parts of the reactive dye represented by formula (5);
1.6 parts of the dye shown in 6) was dissolved in 10 parts of warm water and added to the dye bath. Furthermore, 50 parts of anhydrous sodium sulfate was added to the dye bath ζ and after the temperature reached 60°C, 20 parts of soda ash was added to the dye bath over 5 to 10 minutes, and the cotton side was dyed at 60°C for 60 minutes. Thereafter, the dyed product was taken out, washed with water, soaped in the same manner as in Example 1.2, washed with water, dehydrated, and dried to finish. As a result, a uniform and strong dark blue dyed product was obtained for both wool and cotton.

Comparative Example 5 Reactive dye C,1,No,Raac having one sulfatoethylsulfone group as a reactive group in 1000 parts of water
tiva Yellow 76 ヲ1 Reactive dye C, 1, No, Reactive Re
d 1 part of 22 and 0.1 part of a reactive dye having the same reactive group. N
o.

Wool/cotton (40%
/60) 100 parts of the blended yarn was introduced and treated for 20 minutes. After that, 20 parts of soda ash was added to the dye bath and 6 parts of soda ash was added in 80 minutes.
The temperature was gradually raised to 0° C., and the cotton side was dyed at this temperature for 60 minutes.

Next, the dyed product was taken out and washed with water.The dyed product was placed in a 95°C bath containing 2 parts of monodane powder dissolved in too much water and treated for 5 minutes, and then taken out and washed with water. Next, add the reactive dye Reaotive Yellow 7 to 1000 parts of water.
0.2 parts of 5 and 11active Red 22
Dissolve 0.7 parts of O, 2 parts and 0.7 parts of Reaotjve Blue19, add 1.1 parts of Sumipon W and 1 part of glacial acetic acid to make a 60°C dye bath, and dye the width side first. The object was placed in the container, the temperature was raised to 100° C. over 40 minutes, and the upper side was dyed at that temperature for 80 minutes. Next, the dyed product was taken out and placed in a 95° C. bath containing 2 parts of monodane powder dissolved in 1000 parts of water, treated for 6 minutes, taken out, washed with water, dehydrated, and dried to finish. The result was a dull dark blue dyeing in which the wool was darker than the cotton. As a result of measuring the tensile strength of the dyed yarn, the strength of the dyed yarn of Example 8 was almost equivalent to that of undyed white yarn, whereas the strength of the dyed yarn of Comparative Example 5 was reduced by about 10%. Further, when comparing the dyeing steps, in the case of Example 3, the number of steps was 1/2 that of Comparative Example 5, and the length of the total dyeing time was significantly shortened.

Table 2 Note) Tensile strength measuring device: 8TItOGRAPHM Strength of 100 wool/cotton (40/60) blended undyed yarn 0.29 Kf1; S
``ノ5 Compensation vs. courage f Continued i'+ti +1: , li (spontaneous) Akira [
1160; 1: August 211 +, "fl-' Yama Secretary Uga Michibu 11 role 1 '11 ('lu) Life Otsushi Hitatsu・-'-□Akir
++ ++ 11'1 Application No. 8 (Patent No. 8 filed on July 17, 1985)) 211 Ming No. 8 Method for dyeing mixed anchor fiber material of cellulose fibers and nitrogen-containing fibers 3 111 ``Relationship with each case to be ordered Patent applicant address 115 Kitahama 5th, Yamanaka-ku, Osaka Name (
209) Suminoi Chemical 1'7J Co., Ltd. CEO Akane Mori
Ei Who 4 Attorney (1- Address: 5J, Kitahama, Higashi-ku, Osaka City) 15 Sumitomo Chemical Company, Ltd. Name: Patent Attorney (8597) Mitsuru Moroishi, 1+1-(shi-
・, -2J-'3404 °-11, (]t1.', ノ, ν] ■v ++ 1+ 19J r1 Column 6 of the detailed explanation of the invention in the specification, page 7 of the description of the contents of the amendment On line 18, (CHg CH20) □H” [ Above

Claims (1)

[Claims] When dyeing fiber materials mixed with cellulose fibers and nitrogen-containing fibers, general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, D represents a sulfonic acid group. organic dye residue with R_1
, R_2 is a hydrogen atom or an alkyl group, A is a phenylene group or a naphthalene group which may be substituted with one or two of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom or a sulfonic acid group, and X is a halogen Atom, Y is group -SO_2CH=CH_2 or -SO_2C
H_2CH_2Y_1 (Y_1 is a group that is eliminated by an alkali). ] One or more dyes selected from the dyes represented by formula (I) are used to dye nitrogen-containing fibers in an acidic bath, and then one or more dyes selected from the dyes represented by the above general formula (I) are dyed. A method for dyeing mixed fiber materials, which comprises dyeing cellulose fibers in an alkaline bath using a dye.