JPS59199877A - Dyeing of blended fibe material - 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 cellulose fibers and nitrogen-containing fibers.

Traditionally, direct dyes, reactive dyes, vat dyes, sulfur dyes, etc. have been used to dye cellulose fibers, and acid dyes, metal-containing complex dyes, chromium mordant dyes, reactive dyes, etc. have been used to dye nitrogen-containing fibers. However, because the dyeing conditions for these dyes are different for each fiber, the dyeing of mixed materials of cellulose fibers and nitrogen-containing fibers is processed in separate baths, which requires a long time and a large amount of energy. was.

To industrially dye a mixed material of cellulose fibers and nitrogen-containing fibers, the first step is to first dye the nitrogen-containing fibers in an acidic or weakly acidic bath using acid dyes or metal-containing complex dyes. Next, cellulose fibers are dyed with a direct dye in a two-bath two-stage dyeing method, or cellulose fibers are dyed with thren dyes, sulfur dyes, etc., and nitrogen-containing fibers are dyed with acid dyes, metal-containing complex dyes, or chromium. A two-bath two-step dyeing method in which dyeing is carried out using mordant dyes, etc. Furthermore, adjusting the dyeing conditions using a two-step dyeing method that uses a reactive dye and distributing the reactive dye to cellulose fibers and nitrogen-containing fibers, or resist dyeing. Dyeing methods are used in which dyeing is controlled by using auxiliary agents or by pre-treatment.

The dyeing methods mentioned above using direct dyes, acid dyes, or metal-containing complex dyes have poor wet fastness of dyed products;
An improved method using slenium and sulfur dyes, metal-containing complex dyes, and chromium mordant dyes causes a decrease in protein strength due to strong alkalis during dyeing with slenium and sulfur, and the wastewater load after dyeing is greater than with other dyes. This is problematic and cannot be said to be the best method. The last method using reactive dyes is complicated because the dyeing temperature and the amount of dye bath pH 1 auxiliary agent used are different depending on the reactive group of the reactive dye.
Further, there are problems such as color fading when dyes having different distribution ratios to the composite fibers are mixed and dyed. Furthermore, when using a dye resist aid, there is also the problem of reduced light resistance. Therefore, in the case of the two-bath, two-stage method, a considerable amount of time and energy are required for one dyeing process, and in the case of the two-bath, two-stage method, there are many technical problems.

Under these circumstances, the present inventors conducted intensive studies to find a dyeing method superior to any of the above methods, and found that an alkaline dye containing an inorganic salt was dyed using a reactive dye having two or more different reactive groups. First, the cellulose fibers are dyed in a bath, and after washing with water, the reactive dyes that are not fixed on the cellulose fibers are removed.During the so-called soaping process, a metal-containing complex dye is injected into the soaping bath along with a soaping agent, and at the same time as the soaping process, nitrogen-containing dyes are injected into the bath. The present inventors have completed the present invention by discovering that a method for dyeing fibers can be carried out industrially advantageously and provides dyed products with extremely excellent fastness.

That is, in dyeing a mixed fiber material of cellulose fibers and nitrogen-containing fibers, the present invention is directed to dyeing the cellulose fibers using a reactive dye having two or more different reactive groups, and then dyeing the cellulose fibers with metal-containing fibers during soaping treatment. Provided is a method for dyeing mixed fiber materials, which is characterized by dyeing nitrogen-containing fibers using a complex dye.

Reactive dyes having two or more different reactive groups used in the method of the present invention include those having a sulfatoethylsulfone group and a monochlorotriazine group in one dye molecule;
Those having a monochlorotriazine group and a dichloropyrimidine group, those having a monochlorotriazine group and a monofluorotriazine group, those having a monofluorotriazine group and a sulfatoethylsulfone group, those having a monochlorotriazine group and a difluoro-monochloropyrimidine group , sulfatoethyl sulfone,! Examples include dyes with one sulfatoethyl sulfone group and two monochlorotriazine groups, and dyes with two sulfatoethylsulfone groups and two monochlorotriazine groups.
488, Special Publication No. 89-18184, Special Publication No. 8B-202
40, JP 1988-2023F JP 52-746
．． 19, JP-A-55-12187, JP-A-52-102
885, JP-A-54-72226, JP-A-54-788
28, JP-A-55-39672, JP-A-56-9085
9, JP-A-57-57754, etc., is already known.

Among these reactive dyes, reactive dyes represented by the following general formula (1) or ('') are preferably used.

[In the formula, the organic dye residue having a sulfonic acid group, R1
t R2# "3 is each a hydrogen atom or an alkyl group,
Person may be substituted with one or two of alkyl group, alkoxy group, aryloxy group, halogen atom or sulfonic acid group, phenylene group or naphthalene group, X is halogen atom, Y is group -8O□CH=CH2 or , -80
2CH2CH2Yl (Yl is a group that is eliminated by an alkali), and 2 is a halogen atom; an amino group; a mono- or dialkylamino group that may be substituted with a hydroxy group, a carboxy group, or a sulfonic acid group; a morpholino group: a halogen atom, lower alkyl Anilino, N which may be substituted with a group, a lower alkoxy group, a carboxy group or a sulfo group
-Methyanilino or naphthylamino group; alkoxy group optionally substituted with lower alkoxy group; phenoxy group; alkylthio group optionally substituted with hydroxy group; or phenylthio group. ] Also, the metal-containing complex salt dye preferably used in the method of the present invention is one in which two molecules of the organic dye having an azo group are chromium,
A 1:2 type metal complex dye formed by chelating with one metal such as cobalt, nickel, copper, etc., C01, AcidY
yellow 116.0. I, Ac1d Red
215, c, ■.

Commercially available metal-containing complex dyes such as Ac1d Blue 229 can be mentioned.

The alkalis used in the method of the present invention include alkali metal hydroxides, alkali metal carbonates, tribasic sodium phosphates, tribasic potassium phosphates, alkali acetates, alkali permates, alkali perphosphates and organic bases. Examples include tertiary amines such as triethanolamine and diethylaminophenol.

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

The dyeing method according to the present invention involves blending, twisting, or knitting cellulose fibers such as cotton, hemp, viscose rayon, and copper ammonia viscose rayon with nitrogen-containing fibers such as nylon, wool, and silk. The blended fiber material has the formula (I)
Alternatively, it is poured into a dye bath containing the reactive dye shown in (I) and inorganic salts such as mirabilite and salt at 20 to 50°C, treated for 5 to 30 minutes, then an alkali is added and the temperature is gradually raised to 50 to 80°C. After heating and treating at that temperature for 40 to 120 minutes, the dyed product is taken out and washed with water. Next, in another bath containing an anionic surfactant or a nonionic surfactant and a metal-containing complex dye,
8. Place the dyed material at 20-50°C for 10-30 minutes.
After raising the temperature to 0 to 100°C and treating at that temperature for 10 to 40 minutes, the dyed product is taken out and washed on site. If necessary, fix with a nylon fix agent, wash with water, and dry to finish dyeing.

According to this method, a mixed fiber material consisting of cellulosic fibers and nitrogen-containing fibers can be dyed to a uniform hue, or each fiber can be dyed to a different hue, fast, quickly, and economically. The reason for this is that the reactive dye of formula (I) or (II) used in the present invention dyes cellulose fibers in the mixed fiber material better in an alkaline bath containing an inorganic salt;
This product takes advantage of the properties of the metal-containing complex dye, which hardly dyes the other nitrogen-containing fiber, and which dyes the nitrogen-containing fiber well in a neutral or alkaline bath containing a soaping agent, and does not stain the cellulose fiber. In this method, the soaping process, which is essential for washing off unreacted reactive dyes in conventional dyeing of cellulose fibers with reactive dyes, is utilized for dyeing nitrogen-containing fibers. Therefore, the result is the same as if the soaping process for reactive dyes was omitted or the separate bath dyeing of nitrogen-containing fibers was omitted, and the advantage is that resources such as energy and water can be saved and time can be shortened.

Examples are shown below, in which parts represent parts by weight.

Example 1 50 parts of Glauber's salt of formula (I) was dissolved in 1000 parts of water and maintained at 30'C. Here the front is cotton,
Fifty parts of a cross-knit (50150) knit fabric with a nylon backing is hollowed out and treated for 20 minutes.

After that, 20 parts of soda ash was added to the dyebath, and it was dyed at 60 parts in 3 minutes.
The temperature is gradually raised to ℃ and the cotton side is dyed at this temperature for 60 minutes. Next, the dyed product was taken out, washed with water, and mixed with 1000 parts of water, 2 parts of Monogen Paw Goo (anionic surfactant, manufactured by Dai-Kogyo Co., Ltd.) and C0I, Ac1d Yellow 11.
The dyed product was placed in a 50°C bath in which 0.27 parts of the metal-containing complex dye No. 6 was dissolved, and the temperature was raised to 100°C in 25 minutes.
After processing for a minute, remove and wash with water.

Next, in 1000 parts of water, 1 part of Nylox 700 (product of Ichisha Yushi Kogyo Co., Ltd., nylon fix agent) and 0.5 parts of glacial acetic acid.
The dyed fabric was placed in a 60"C bath containing 100% of the dyed material, treated for 10 minutes, and then taken out, washed with water, and dried to finish. As a result, a uniform and solid golden yellow dyed fabric was obtained on both the front and back sides.

Example 2 2.2 parts of a reactive dye with two reactive groups represented by formula (2), 0.2 parts of a reactive dye with two reactive groups represented by formula (1), and 50 parts of anhydrous sodium sulfate were dissolved in 1000 parts of water. Keep it ao'c. Fifty parts of a rayon 85/nylon 15 interlaced knit fabric was inserted into this and treated for 20 minutes. Thereafter, 20 parts of soda ash was added and the temperature was raised to 6°C over 30 minutes, and the rayon side was dyed at this temperature for 60 minutes. Next, the dyed product was taken out, washed with water, and mixed with 1000 parts of water, 2 parts of Monogen Powder (anionic surfactant, manufactured by Dai-Kogyo Co., Ltd.) and C, I, Ac1d Red 215.
The dyed product was placed in a 50'Q bath in which 0.42 parts of metal-containing complex dye was dissolved, and the temperature was raised to 100' (E) for 25 minutes.
After processing for 0 minutes, take out and wash with water. Next, the same nylon fix treatment as in Example 1) was performed, followed by washing with water and drying. As a result, a uniform and strong red dyeing was obtained.

Example 3 1.2 parts of a reactive dye with 2 reactive groups represented by formula (3) in 1000 parts of water, 0.15 parts of a reactive dye with 2 reactive groups represented by formula (1), and 0.15 parts of a reactive dye with 2 reactive groups represented by formula (2) 04 parts of a reactive dye with 2 reactive groups and 50 parts of anhydrous sodium sulfate were dissolved and maintained at ao'c. 20 parts of a blended cloth of 85 hemp/15 nylon was inserted into this and treated for 20 minutes. Thereafter, 20 parts of soda ash was added in the same manner as in Example 1, and the hemp side was dyed at 60°C for 60 minutes, then washed with water, and monogen powder (Dai-Kogyo Seiyaku product, anionic surfactant) was added to 1000 parts of water.
Part 2 and O, I.

Ac1d Blue 229 metal-containing complex dye 0.
Part 12, Example 2 (7) C6I, Ac1d Re
The sample is treated in the same manner as in Example 1 at 100° C. for 10 minutes in a bath in which 0.015 part of the metal-containing complex dye d215 is dissolved, followed by nylon fixing, washing with water, and drying.

As a result, a uniform and strong dark blue dyed product was obtained.

Example 4 1.8 parts of the dye represented by formula (4) and 50 parts of anhydrous sodium sulfate were added to 100 parts of water.
A dye bath was prepared at 30°C. 50 parts of cotton/nylon (85/15) mixed knit fabric was put into this bath and treated for 20 minutes, then 20 parts of soda ash was added and 30 parts of
The temperature was raised to 60° C. for 60 minutes, and the cotton side was dyed at this temperature for 60 minutes. 0.5 parts of metal-containing complex salt dye shown by Betsu Ni C, I, Ac1d Red 215, 2 parts of Mosogen powder (anionic surfactant: Dai-Kogyo Seiyaku Co., Ltd. product) and 100 parts of water.
Dissolve in 0 parts and adjust the bath to 50°C. The above-mentioned interwoven knit dyed on the line side was put into this bath and 1
The temperature was raised to 00°C, treated for 10 minutes, and then taken out and washed with water. Next, the material was treated with Nanolon Fix under the same conditions as in Example 1), washed with water, and dried. As a result, a uniform and firm red material was obtained.

Comparative Example I Using the reactive dye (1) with two reactive groups shown in Example 1, the line side was dyed in the same manner as in Example 1 on 50 pieces of interlaced knit with cotton on the front side and nylon (50150) on the back side. After that, the dyed product was taken out, washed with water, and washed at 100°01 in the same manner as in Example 1 in a bath containing 2 parts of monodan powder dissolved in 1000 parts of water.
Process (soap) for 0 minutes. Thereafter, the dyed product was placed in a bath at 50°C in which 0.27 parts of O, I, Ac1d Yellow 116 metal-containing complex dye and 2 parts of ammonium sulfate were dissolved in 1000 parts of water, and 2 parts were heated to 100°C for 6 minutes. Raise the temperature, perform nylon fix treatment for 10 minutes, wash with water and dry. As a result, a dyed product having the same density, hue and fastness as Example 1 was obtained. However, the dyeing time was 35 minutes longer for one soaping treatment than in Example 1, and more water and energy were required for one soaping treatment.

Comparative Example 2 The rayon side of 50 parts of interlaced knit of rayon 85/nylon 15 was dyed in the same manner as in Example 2 using the reactive dye (2) having two reactive groups.The dyed product was taken out, washed with water, and 2 parts of Dan powder and C01, Ac1d
The dyed product was placed in a 50°C bath containing 0.42 parts of Red 118 acid dye dissolved in 1000 parts of water, treated at 100°C for 10 minutes in the same manner as in Example 2, and then treated with a nylon fix and washed with water and dried. I finished it. As a result, the rayon side was dark, but the nylon side was extremely light, resulting in a dyed product with flickering as a whole.

Comparative Example 8 C0I, Reactive Blue in 1000 parts of water
64 parts of e19 reactive dye and C, I, Reactive
0.7 part of Orange 116 reactive dye is dissolved together with 50 parts of anhydrous sodium sulfate and kept at 30°C. 50 parts of a hemp 85/nylon 15 blend fabric was put into this, and the hemp side was dyed in the same manner as in Example 8.The dyed material was then taken out and washed with water, containing the same metal-containing complex dye and monogen powder as in Example 3. After treatment in a bath in the same manner as in Example 3, a nylon fix treatment is performed to finish. As a result, the nylon side was dark, but the hemp side was extremely light, resulting in a light dyed material with flickering as a whole.

Claims (1)

[Claims] ■) When dyeing a mixed fiber material of cellulose fibers and nitrogen-containing fibers, after dyeing the cellulose fibers using a reactive dye having two or more different types of reactive groups, during soaping treatment. A method for dyeing mixed fiber materials, characterized by dyeing nitrogen-containing fibers using a metal-containing complex dye. 2) A reactive dye having two or more different reactive groups is represented by the general formula (or can be expressed by the formula) N, , NR. [In the formula, the organic dye residue having a sulfonic acid group, R1
p R2e R3 are each a hydrogen atom or an alkyl group,
A 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, X is a halogen atom, and Y is a group -8O□C ! 1EI=cH2 or -5o2an20)I2Y. (Yl is a group that is eliminated by an alkali), and 2 is a halogen atom; an amino group; a mono- or dialkylamino group that may be substituted with a hydroxy group, a carboxy group, or a sulfo group; a morpholino group; a halogen atom, a lower alkyl group,
Anilino, N-methylanilino or naphthyl 7E/ group which may be substituted with a lower alkoxy group, carboxy group or sulfo group; alkoxy group which may be substituted with an i-class alkoxy group; phenoxy group; or a phenylthio group. ] Claim 1 is a dye represented by
The staining method described in section. 3) The metal-containing complex salt dye is an l:2 type metal-containing complex salt dye obtained by chelating two molecules of an organic dye having an azo group with one metal such as chromium, cobalt, nickel, copper, etc. Claim 1 Staining method described. 4) The dyeing method according to claim 1, wherein the nitrogen-containing fiber is a polyamide synthetic fiber.