JPH0718096B2 - Dyeing method of mixed fiber material of cellulose fiber and nitrogen-containing fiber - Google Patents

Description

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

Conventionally, direct dyes, slene dyes, sulfur dyes, reactive dyes for cotton, etc. are used for dyeing cellulose fibers, and acid dyes, metal complex dyes, chromium mordant dyes, reactive dyes for wool are used for dyeing nitrogen-containing fibers. Etc. are used.

As a method for industrially dyeing a mixed material of a cellulosic fiber and a nitrogen-containing fiber, generally, an acid dye or a metal complex salt dye is first used to dye the nitrogen-containing fiber in an acidic or weakly acidic bath. Next, a two-bath two-step dyeing method in which cellulosic fibers are directly dyed, or after the cellulosic fibers are dyed with a slene dye, a sulfur dye, a reactive dye for cotton, etc., the nitrogen-containing fibers are acid dyes or metal complex salts. A two-bath two-step dyeing method of dyeing with a dye, a chromium mordant dye, a reactive dye for wool, and the like is performed.

However, the two-bath two-step dyeing method using an acid dye or a metal complex salt dye and a direct dye is insufficient in wet dregs of the dyed product, and it is difficult to obtain a clear hue, and a slene for improving the dye, a sulfur dye, The two-bath two-stage method using reactive dyes for cotton, metal complex dyes, and chromium mordant dyes is a case of slene and sulfur dyes. In addition, chromium mordant dyes require a long time for dyeing and it is difficult to obtain a clear hue as in the case of metal complex dyes. Also known is a method of dyeing both cellulose fibers and nitrogen-containing fibers with a reactive dye for cellulose. However, in this case, although a dyed product with a clear hue and a prison is obtained, the reactive dye is adsorbed to the nitrogen-containing fiber by an ionic bond during the dyeing of the cellulose fiber side, which causes a drop in the prudential degree. A big problem remained. When a reactive dye for cellulose and a reactive dye for wool are used, it is necessary to dye the nitrogen-containing fiber with the reactive dye for wool in an acid bath and then subject it to alkali treatment for the purpose of improving the verticality. Further, when a reactive dye for cotton having a sulfoethyl sulfone group as a reactive group is to be used for dyeing a nitrogen-containing fiber, the dye is alkali-treated in the first bath and then neutralized with an acid, so-called dye alkali. After activation, it is necessary to use an acidic bath for dyeing, which makes the working process extremely complicated. Further, in the case of performing mixed color dyeing by dyeing such a mixed product, the types and number of dyes used are remarkably increased, and preparation of dyeing prescriptions and dye inventory management become complicated.

Under these circumstances, the present inventors have made earnest studies to find an efficient dyeing method superior to any of the above methods, and as a result, have a vinyl sulfone type reactive group and a halogenotriazinyl group in one molecule. The bifunctional reactive dye has excellent reactivity to nitrogen-containing fibers and shows high dyeing property in dyeing in an acidic bath, and it becomes a nitrogen-containing fiber under the cellulose dyeing conditions in an alkaline bath. The present invention has been completed by finding that the dyeing of No. 2 is extremely small. That is, the present invention provides a dye of the general formula (I) when dyeing a mixed fiber material of a cellulosic fiber and a nitrogen-containing fiber. [Wherein D is an organic dye residue having a sulfonic acid group, R ₁ and R ₂
Are hydrogen atoms or alkyl groups, A is an alkyl group,
An alkoxy group, an aryloxy group, a phenylene group or a naphthalene group which may be substituted with one or two of a halogen atom or a sulfonic acid group, X is a halogen atom, Y is a group —SO ₂ CH═CH _2, or — SO ₂ CH ₂ CH ₂ Y ₁ (Y ₁ is a group capable of leaving by an alkali) is represented. ] The nitrogen-containing fiber is dyed in an acidic bath with one or more dyes selected from the dyes represented by the following formula, and then one or more dyes selected from the dyes represented by the general formula (I) Provided is a method for dyeing a mixed fiber material, which comprises dyeing a cellulosic fiber in an alkaline bath with a dye.

By the method of the present invention, a blended fiber material obtained by blending, twisting or knitting cellulosic fibers such as cotton, hemp, viscose rayon, copper ammonia viscose rayon, etc. and nitrogen-containing fibers such as wool, silk and nylon. Can be dyed industrially advantageously.

Examples of the dye represented by the general formula (I) used in the present invention include, for example, JP-B-39-18184, JP-B-58-18472, JP-B-58-55189, and JP-B-58-48672. Etc., and is known.

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

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

The pH of the dyebath is preferably in the range of 3.0 to 6.5.

As a leveling agent, the following formula, [In the formula, R represents an alkyl group having a carbon number of 12 to 18, m and n represent a positive number, and the sum thereof is 2 to 20. ] The zwitterionic surfactant represented by is effective in leveling and dyeing.

After dyeing the nitrogen-containing fiber, the mixed fiber material is taken out, washed with water or not taken out, and one or more kinds of the dyes represented by the general formula (I) are used, preferably in an alkaline bath containing an inorganic salt. Dyes cellulosic fibers,
If necessary, soaping treatment and, if necessary, fixing treatment are performed.

Examples of the alkali to be used include alkali metal hydroxide, alkali metal carbonate, sodium triphosphate, potassium triphosphate, alkali acetate, alkali borate, alkali perborate and organic bases such as triethanolamine and diethylaminophenol. Examples include tertiary amines.

Examples of the soaping agent include anionic and nonionic surfactants such as sodium alkylbenzene sulfonate and polyoxyethylene alkylphenyl ether.

The dye used for dyeing the nitrogen-containing fiber and the dye used for dyeing the cellulose fiber may be the same or different,
Dyes having the same hue, and more preferably the same hue are preferably used.

An example of a specific example of the dyeing method according to the present invention is given below.

First, the mixed fiber material is placed in a dye bath containing the reactive dye represented by the general formula (I), a zwitterionic surfactant and an acid.
Hold at ~ 50 ° C, gradually raise to 80 ~ 100 ° C, 30 ~ 60
After the treatment for a minute, the dyed product is taken out and washed with water. Next, the reaction dye represented by the general formula (I) is placed in another dyeing bath containing an inorganic salt such as Glauber's salt and salt at 20 to 50 ° C., treated for 5 to 30 minutes and then alkali is added to 50 to 80 ° C. The temperature is gradually raised to 40 ° C. for 120 to 120 minutes, and 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, heated to 85 to 100 ° C., treated at that temperature for 5 to 10 minutes, and then the dyed product is taken out and washed with hot water. If necessary, a fixing treatment is performed with a fixing agent, followed by washing with water and drying.

According to the method of the present invention, it is possible to dye a mixed fiber material composed of a cellulosic fiber and a nitrogen-containing fiber in a uniform hue, or in a different hue for each fiber, in a prison and economically.

The present invention provides that the reactive dye of the general formula (I) used is well dyed to the nitrogen-containing fiber of the mixed fiber material in the acid bath and hardly dyed to the other cellulosic fiber, and the reactive dye. However, in the alkaline bath containing an inorganic salt, the property that the cellulose-based fiber is dyed well and the nitrogen-containing fiber is dyed only to the extent of contamination is applied. When a conventional reactive dye for so-called monofunctional cellulose fiber having a sulfatoethylsulfone group as a reactive group is used for dyeing a nitrogen-containing fiber, the dye bath may be dyed with sodium phosphite trioxide or the like before dyeing with an acid bath. It is necessary to perform so-called alkali activation in which an alkali is added and heat treatment is carried out, whereby dyeing to nitrogen-containing fibers is promoted even in an acid bath,
With the dye represented by the general formula (1), alkali activation is not necessary, and a dyed product having a high density and high consistency can be obtained even when dyeing as it is in an acid bath. In addition, when an attempt is made to dye a cellulosic fiber, which is a mixed fiber material composed of a cellulosic fiber and a nitrogen-containing fiber with a conventional reactive dye for cellulosics, in an alkaline bath, the contamination of the cellulosic fiber is larger than that of the cellulosic fiber. There was a problem that the fiber cannot be dyed in a sufficiently dark color, but in the case of the method of the present invention, that point is also solved, and both nitrogen-containing fiber and cellulosic fiber can be easily dyed in the vertical direction. It has its characteristics. Looking at the dyeing process, in the conventional dyeing process using a monofunctional reactive dye, a case where a nitrogen-containing fiber dye is used in combination to dye the cellulose fiber in a sufficiently dark color In this case, it is essential to remove unfixed dye by soaping after dyeing the cellulosic fiber. If the soaping is omitted, the undyed dye adhering to the fiber or the dye hydrolyzed with alkali will flow out to the dyeing bath in the next dyeing process of the nitrogen-containing fiber and will be recontaminated. And the dyeing becomes unstable, and the prison degree becomes poor. If the alkali activation treatment is not performed prior to dyeing the nitrogen-containing fiber, the last soaping is indispensable because the dyeing on the nitrogen-containing fiber is incomplete. Will be needed. On the other hand, according to the dyeing process of the present invention, the dyeing to the nitrogen-containing fiber is good, the residual bath is extremely small, and the contamination to the cellulosic fiber is extremely small. The soaping is unnecessary and only a simple washing with water is needed to remove the acid. Therefore, according to the method of the present invention, since the number of soaping steps is smaller than that of the conventional dyeing process, the dyeing step can be rationalized, and the damage to the fiber due to soaping is less, so that a higher quality product can be obtained.

Examples are shown below, where parts represent parts by weight.

Example 1 0.2 parts of the reactive dye represented by the formula (1), 1.0 part of the reactive dye represented by the formula (2) and 0.1 part of the reactive dye represented by the formula (3) are dissolved in 1000 parts of water, and Sumipon WA (Otomo) Chemicals product, amphoteric surfactant) 1.3 parts and glacial acetic acid 2 parts 5
It was kept at 0 ° C. To wool / rayon (65/35) mixed yarn 10
0 part was rolled in and the temperature was raised to 100 ° C. in 40 minutes, and the wool side was dyed at this temperature for 30 minutes. Thereafter, the dyed product was taken out and washed with water at 60 ° C. Next, 0.1 part of the dye of the formula (1), 0.6 part of the dye of the formula (2), 0.03 part of the dye of the formula (3) and 50 parts of anhydrous Glauber's salt are dissolved in 1000 parts of water, and 50 parts of anhydrous sodium sulfate is dissolved. / A yarn dyed on the wool side of rayon twisted yarn was rolled in and treated for 20 minutes. After that, add 20 parts of soda ash to the dyebath and keep at 60 ℃ for 30 minutes.
The temperature was gradually raised to 60 ° C., and the rayon side was dyed at this temperature for 60 minutes. Next, the dyed product is taken out and washed with water, and the dyed product is placed in a bath at 95 ° C in which 2 parts of monogen powder (Daiichi Kogyo Seiyaku Co., anionic surfactant) is dissolved in 1000 parts of water, treated for 5 minutes, and then taken out and washed with water. Dehydrated, dried and finished. As a result, a dyed product in red, which was uniform in both wool and rayon and was in a prison, was obtained.

Comparative Example 1 0.1 part of acid dye of CI No. Acid Yellow 110 was added to 1000 parts of water.
CINo.Acid Red 249 acid dye 0.7 parts and CINo.Acid Bl
ue 129 acid dye 0.02 parts was dissolved and glacial acetic acid 2 parts was added to this to make 50 ° C dyeing bath, where wool / rayon (65/3
5) 100 parts of the twisted yarn was put in and the same treatment as in Example 1 was performed to dye the wool side. When the dyed product was washed with hot water and dyed on the rayon side in the same manner as in Example 1, a red dyed product was obtained, but the washability was significantly inferior to that in Example 1. In addition, as for the type and number of dyes used for dyeing, in Example 1, only 3 reactive dyes were used, whereas in Comparative Example, 3 acidic dyes and 3 reactive dyes were used, for a total of 6 items.

Example 2 0.5 part of the reactive dye represented by the formula (1) was dissolved in 1000 parts of water, 0.5 part of Sumipon WA and 1 part of glacial acetic acid were added, and the mixture was heated to 50 ° C.
Kept at. 100 parts of a wool / cotton (50/50) knitted knit was placed therein, the temperature was raised to 100 ° C. in 40 minutes, and the wool side was dyed at this temperature for 30 minutes. Thereafter, the dyed product was taken out and washed with water at 60 ° C. Next, 1.5 parts of the dye of the formula (1) and 50 parts of anhydrous Glauber's salt are dissolved in 1000 parts of water, and the dyed cloth dyeing the wool side of the above wool / cotton knit is dyed in a bath kept at 30 ° C. for 20 minutes. Processed. After that, add 20 parts of soda ash to the dyebath and keep at 60 ℃ for 30 minutes.
The cotton side was dyed for 60 minutes at this temperature.

Next, it was washed with water and subjected to the same soaping as in Example 1, followed by washing with water, dehydration and drying to finish. As a result, a dyed product which was uniform in both wool and cotton and had a prison-like color was obtained.

Comparative Example 2 0.5 part of a reactive dye of CI No. Reactive Yellow 76 (a reactive dye having 1 sulfatoethyl sulfone group as a reactive group) was dissolved in 1000 parts of water, and 0.5 part of Sumipon WA and 1 part of glacial acetic acid were dissolved in the solution. The temperature was maintained at 50 ° C. To wool / cotton (50
/ 50) 100 parts of a knitted knit was put in and the same treatment as in Example 2 was carried out to dye the wool side. Thereafter, as in Example 2, the cotton side was dyed with 1.5 parts of the reactive dye of the formula (1), washed with water and soaped to finish. As a result, a dyed product in which the wool side was markedly flickering as compared with the cotton side was obtained.

Comparative Example 3 Reactive Yell reactive dye used in Comparative Example 2 in 1000 parts of water
ow 76 0.5 part was dissolved and crystallized sodium tertiary phosphate 0.2
After adding 5 parts, the temperature was raised to 85 ° C., treated for 5 minutes to carry out alkali activation, and then cooled to 50 ° C., 1 part glacial acetic acid and Sumipon WA.
0.5 part was added, and 100 parts of a wool / cotton (50/50) interlaced knit was rolled 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 the formula (1) to dye the cotton side. As a result, a dyed product having a uniform golden color on both wool and cotton was obtained, but the dyeing operation was remarkably complicated as compared with Example 2.

Comparative Example 4 Reactive Yello reactive dye used in Comparative Example 2 in 1000 parts of water
w 76 0.5 part was dissolved, 0.5 parts Sumipon WA and 1 part glacial acetic acid were added to this to obtain 50 ° C., and 100 parts of wool / cotton (50/50) knitted knit was cast into the same as in Example 2. After processing, the wool side was dyed. Then, the same treatment as in Example 2 was carried out using 1.5 parts of Reactive Yellow 76 to dye the cotton side. As a result, a uniform golden dyed product was obtained for both wool and cotton, but the density was remarkably lower than that of the dyed product of Example 2.

Example 3 In 1000 parts of water, 0.1 part of the reactive dye represented by formula (1), 0.2 part of the reactive dye represented by formula (2) and formula (4). Dissolve 0.5 parts of the reactive dye shown in
0.8 parts and 1 part of glacial acetic acid were added and the mixture was kept at 50 ° C. Wool here /
100 parts of cotton (40/60) blended yarn was put in, heated to 100 ° C. in 40 minutes, and dyed on the wool side at this temperature for 30 minutes. Then a dye bath
Cooled to 60 ° C in 20-30 minutes. Meanwhile soda ash 1.5
Of the reactive dye of the formula (1) and the formula (5) after neutralization by adding 1 part of the dye to a dye bath at 80 ° C or lower. 0.8 parts of the reactive dye represented by the formula (6) 1.6 parts of the dye shown by was dissolved in 10 parts of warm water and added to the bath. Furthermore, after adding 50 parts of anhydrous sodium sulfate to the dyeing bath to reach 60 ° C, 20 parts of soda ash are added to the dyeing bath in 5 to 10 minutes, and at 60 ° C.
The cotton side was dyed for 60 minutes. Thereafter, the dyed product was taken out, washed with water, subjected to the same soaping as in Examples 1 and 2, and then washed with water, dehydrated and dried to finish. As a result, wool,
A dark blue dyed product which was uniform and was in a jail with both cotton was obtained.

Comparative Example 5 Reactive dye CI No. Reactive Yellow 76 which has 1 part of a sulfate ethyl sulfone group as a reactive group in 1000 parts of water.
CI No. Reactive Re which has the same reactive group as 1 part
Reactive dye CI No. Reactiv which has the same reactive group as 1 part of d 22
2 parts of eBlue 19 and 50 parts of anhydrous Glauber's salt were dissolved and 100 parts of a wool / cotton (40/60) blended yarn were put into a bath kept at 30 ° C. and treated for 20 minutes. After that, add 20 parts of soda ash to the dye bath, and in 30 minutes
The temperature was gradually raised to 60 ° C and the cotton side was dyed at this temperature for 60 minutes. Next, the dyed product is taken out and washed with water, and the dyed product is put in a bath at 95 ° C in which 2 parts of monogen powder are dissolved in 1000 parts of water.
After processing for 1 minute, it was taken out and washed with water. Next, to 1000 parts of water, 0.2 parts of the reactive dye Reactive Yellow 76 and Reactive Red
0.2 parts of 22 and 0.7 parts of Reactive Blue 19 are dissolved, 1.1 parts of Sumipon WA and 1 part of glacial acetic acid are added to this to make a 50 ° C. dyeing bath,
Put the dyed material on the cotton side here for 10 minutes in 40 minutes.
The temperature was raised to 0 ° C and the wool side was dyed at that temperature for 30 minutes. Next, the dyed product was taken out, and the dyed product was put in a bath at 95 ° C. in which 2 parts of monogen powder was dissolved in 1000 parts of water, treated for 5 minutes, taken out, washed with water, dehydrated and dried to finish. as a result,
A dark blue dyed product in which the wool is more fluffy than cotton is obtained. As a result of measuring the tensile strength of the dyed yarn, while the dyed yarn of Example 3 has almost the same strength as the undyed white yarn,
The strength of the dyed yarn of Comparative Example 5 was reduced by about 10%. Further, comparing the dyeing steps, in the case of Example 3, 1/2 of Comparative Example 5
And the total dyeing time was remarkably shortened.

Comparative Example 6 CI Reactive Yellow 84 reactive dye (reactive dye having two monochlorotriazines as reactive groups) in 1000 parts of water.
Five parts were dissolved, 0.5 parts Sumipon WA and 1 part glacial acetic acid were added thereto, and the mixture was kept at 50 ° C. 100 parts of a wool / cotton (50/50) knitted knit fabric was placed therein, and treated in the same manner as in Example 2 to dye the wool side. Next CI Reactive Yellow 84
The same treatment as in Example 2 was carried out using 1.5 parts to dye the cotton side. As a result, a uniform golden dyed product was obtained for both wool and cotton, but the density was remarkably lower than that of the dyed product of Example 2.

Claims (1)

[Claims] 1. When dyeing a mixed fiber material of a cellulose fiber and a nitrogen-containing fiber, the compound of the general formula (I) [Wherein D is an organic dye residue having a sulfonic acid group, R ₁ and R ₂
Are hydrogen atoms or alkyl groups, A is an alkyl group,
An alkoxy group, an aryloxy group, a phenylene group or a naphthalene group which may be substituted with one or two of a halogen atom or a sulfonic acid group, X is a halogen atom, Y is a group —SO ₂ CH═CH _2, or — SO ₂ CH ₂ CH ₂ Y ₁ (Y ₁ is a group capable of leaving by an alkali) is represented. ] Nitrogen-containing fibers are dyed in an acid bath with one or more dyes selected from the following, and then one or more dyes selected from the dyes represented by the general formula (I) A method for dyeing a mixed fiber material, which comprises dyeing a cellulosic fiber in an alkaline bath using a dye.