JPH06108382A - Improvement of wet color fastness - Google Patents

Abstract

PURPOSE:To give an excellent wet color fastness without reducing other color fastness by treating a dyed material composed of a cellulose-based fiber dyed with a direct dye or a reactive dye with a specified polymer. CONSTITUTION:A cellulose-based fiber material dyed with a direct dye or a reactive dye is treated in a bath composed of an alkaline liquid containing (A) a polymer composed of a repeating monomer unit represented by the formula (X is a halogen; Y is an organic acid or an inorganic acid) and (B) a polymer composed of the repeating monomer unit represented in the above-mentioned (A) and another repeating monomer units such as anallylic and an acrylic repeating monomer units (a preferable example; diallyldimethyl-ammonium chloride) derived from a monomer copolymerizable with a monomer deriving the above-mentioned repeating monomer unit so as to improve the wet color fastness. In addition, the polymer represented by (A) is obtained by polymerizing a salt a reaction product between diallylamine and an epihalohydrin.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to a method for improving the wet fastness of dyed cellulosic fiber materials.

2. Description of the Related Art Reactive dyes and direct dyes are mainly used for dyeing cellulosic fiber materials. The reactive dye is a dye that is fixed by the formation of a covalent bond with the cellulose fiber, and the unfixed dyestuff is removed from the fiber by sufficient washing after dyeing, whereby excellent wet fastness can be obtained. However, under the industrial dyeing conditions, it is impossible to completely remove the unfixed dye, and the use of the wet fastness improver is indispensable. Direct dyes are inexpensive and are often used because they can be dyed by a relatively simple process, but they have poor wet fastness and, like reactive dyes,
The use of wet fastness improvers has become essential.
Examples of the wet fastness improver include dicyandiamide-formalin condensate, dicyandiamide-polyethylene polyamine condensate, dimethylamine-epichlorohydrin polymer (JP-B-43-243), diallylamine derivative-based polymer (JP-B-43-18165, JP-A-43-18165). 53-7017
8), dimethylaminoethyl (meth) acrylate derivative-based polymer (JP-A-57-112480), alkyldiallylamine polymer-epichlorohydrin quaternary compound (JP-A-62-299589), alkyldiallylamine-epichlorohydrin quaternary compound (JP-A-62-299589). JP-A-4-2144
79) and the like are publicly known. The dicyandiamide-formalin condensate and the dicyandiamide-polyethylenepolyamine condensate have a relatively excellent effect of improving the wet fastness, but the treatment discoloration is large, and the light fastness and the chlorine fastness are largely reduced. Dimethylamine-epichlorohydrin polymer, diallylamine derivative-based polymer or dimethylaminoethyl (meth) acrylate derivative-based polymer has little discoloration due to treatment and little deterioration in light fastness and chlorine fastness, but has an effect of improving wet fastness. It is smaller than the former two and cannot be used as a wet fastness improver for direct dyes. The alkyl diallyl amine polymer-epichlorohydrin quaternary compound has an excellent effect of improving the wet fastness, but since it is composed of a quaternary ammonium salt, the chlorine fastness is largely reduced. Unlike other wet fastness improvers, alkyldiallylamine-epichlorohydrin quaternary compounds utilize monomers rather than polymers, so the processing method is limited to the cold batch-up method and requires special processing equipment. In addition to this, there is a drawback that the form of material that can be used is limited to cloth foil, and it cannot be processed in the form of cotton, thread and the like.

SUMMARY OF THE INVENTION An object of the present invention is to provide a treatment method for imparting excellent wet fastness to dyed cellulosic fiber materials without lowering other fastness to dyeing. is there. That is, the present invention provides a dyed cellulosic fiber material with (a) the general formula (1)

[Chemical 2] [Wherein X represents a halogen atom, Y represents an organic acid or an inorganic acid], and (b) a repeating monomer unit represented by the above general formula (1); The present invention relates to a method for improving wet fastness, which comprises treating a monomer that is a monomer unit with a copolymer that is copolymerizable with another monomer unit. According to the study of the present inventors, when a dyed cellulosic fiber material is treated by the method of the present invention, excellent wet fastness can be imparted to the fiber material, and further, discoloration of the fiber material by the treatment and chlorine resistance. It has been found that the reduction in fastness and lightfastness can be minimized. Examples of the organic acid represented by Y in the general formula (1) include acetic acid and formic acid, and examples of the inorganic acid include hydrochloric acid and sulfuric acid. The polymer shown in (a) above can be obtained by polymerizing a salt of the reaction product of diallylamine and epihalohydrin. Examples of epihalohydrin to be reacted with diallylamine include epichlorohydrin, epiiodohydrin, epipromohydrin and the like, and epichlorohydrin is particularly preferable. Epihalohydrin is preferably used in an amount of 0.5 to 1.5 mol, particularly 1 to 1.3 mol, based on 1 mol of diallylamine. In the reaction of diallylamine with epihalohydrin, 20
The reaction is preferably carried out in the temperature range of -60 ° C, particularly in the temperature range of 25-35 ° C. For the polymerization of the salt of the reaction product of diallylamine and epihalohydrin, an ordinary aqueous solution radical polymerization method can be used. For example, a salt of a reaction product of diallylamine and epichlorohydrin is added to a polymerization initiator such as ammonium persulfate, hydrogen peroxide, benzoyl peroxide, and t-butylhydrogen in an aqueous solvent such as water at a reaction temperature of 60 to 90 ° C. Polymerization may be performed in the presence of peroxide, azobisbutyronitrile, azobis (2-aminodipropane) hydrochloride or the like. The polymer of the present invention thus obtained has a molecular weight of 3,000.
Although it is set to about 500,000, a suitable one as a wet fastness improver has a molecular weight of about 10,000 to 100,000. Representative examples of the other copolymerizable monomer unit in the copolymer shown in (b) above include an allylic monomer unit and an acrylic monomer unit. Examples of the allyl monomer unit and the acrylic monomer unit include diallyldimethylammonium chloride, diallylamine, organic acid or inorganic acid salt of diallylamine, acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylic acid or methacrylic acid alkali metal or ammonium salt. Examples thereof include lower alkyl esters of acrylic acid or methacrylic acid, tertiary or quaternary amino-substituted lower alkyl esters, tertiary or quaternary amino- and hydroxy-substituted lower alkyl esters, and the like. Of these monomer units, the most preferred is diallyldimethylammonium chloride. The conditions for producing these copolymers may be the same as those for the polymer shown in (a) above. The proportion of the salt of the reaction product of diallylamine and epihalohydrin in the copolymer is 5 mol%.
The above is enough. Examples of fibers to which the treatment method of the present invention can be applied include natural cellulose fibers such as cotton and hemp, and regenerated cellulose fibers such as viscose rayon and cuprammonium rayon. The fiber material includes the above natural cellulose fibers and / or regenerated cellulose fibers, and may include fibers other than these as long as they are dyed by a conventional method using a known direct dye or reactive dye. Absent. The form of the fiber material treated by the treatment method of the present invention may be cotton, thread, cheese, cloth, product or the like. When applying the treatment method of the present invention to a fiber material, it is desirable to adopt an exhaust treatment method. As the processing device, a standard dyeing device such as a cheese dyeing machine, a Jigger dyeing machine, a Wins dyeing machine, a jet dyeing machine, or a paddle dyeing machine can be used. In the treatment method of the present invention, it is desirable to use the above polymer in combination with an alkali. Examples of the alkali include sodium hydroxide,
Potassium hydroxide and the like can be mentioned, and it is particularly preferable to use sodium hydroxide, and a 25 to 30% (W / W) aqueous sodium hydroxide solution is used in an amount of 1 to 10 g / l, preferably 2 to 4 g / l. be able to. The alkali may be added at the same time as the polymer of the general formula (1), but it is added after the treatment with the above polymer at 40 to 60 ° C. for 10 to 20 minutes, and then at the same temperature for 10 to 20 minutes. It is desirable to perform the processing of. After completion of the treatment, washing with water may be repeated and, if necessary, a neutralization treatment using acetic acid, formic acid or the like may be performed.

EXAMPLES The features of the present invention will be further clarified by giving examples and comparative examples, but the present invention is not limited to the following examples. The parts and% in the examples are parts by weight and% by weight, unless otherwise specified.

[Synthesis Example 1] Synthesis of diallylamine-epichlorohydrin adduct 230 g of diallylamine and 7 g of water were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and the mixture was stirred and uniformly dissolved, and then heated. And set the temperature to 28
It was raised to ℃. To this mixture, 222 g of epichlorohydrin was added dropwise from a dropping funnel over about 30 minutes. After the dropping was completed, the temperature was kept at 28 to 30 ° C. for 10 hours. After the reaction,
Water (223 g) and hydrochloric acid (35%) (250 g) were added to give a diallylamine-epichlorohydrin adduct (hereinafter DAA-EC).
An aqueous solution of hydrochloride (abbreviated as H) was obtained.

[Synthesis Example 2] DAA-E obtained in Synthesis Example 1 was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
An aqueous solution of 200 g of CH hydrochloride and an aqueous solution of diallyldimethylammonium chloride (hereinafter abbreviated as DADMAC) (6
0%) 100 g and water 150 g were added, and the internal temperature was raised to 70 ° C. Under stirring, 20 g of ammonium persulfate aqueous solution (25%) was added dropwise using a dropping funnel over 2 hours.
After the dropping was completed, the reaction was continued for 3 hours to obtain a viscous pale yellow liquid. Excess acetone was added to 50 g of the obtained reaction mixture, and the precipitate was separated by filtration and dried in vacuum to give 15 g of a pale yellow powder.
Got The yield was 88%. G of the obtained polymer
The molecular weight determined by PC was 35,000.

Synthesis Example 3 DAA-E obtained in Synthesis Example 1 in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
250 g of CH hydrochloride aqueous solution and DADMAC aqueous solution (60
%) 50 g and water 150 g, and the internal temperature was raised to 70 ° C. Under stirring, 20 g of ammonium persulfate aqueous solution (25%) was added dropwise using a dropping funnel over 2 hours. After the dropping was completed, the reaction was continued for 3 hours to obtain a viscous pale yellow liquid. Excess acetone was added to 50 g of the obtained reaction mixture, and the precipitate was separated by filtration and vacuum dried to obtain 14 g of a pale yellow powder.
The yield was 85%. The molecular weight of the obtained polymer determined by GPC was 36,000.

[Synthesis Example 4] DAA-E obtained in Synthesis Example 1 was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
Add 300g of CH aqueous solution of hydrochloric acid and 150g of water.
The temperature was raised to 0 ° C. Under stirring, 20 g of ammonium persulfate aqueous solution (25%) was added dropwise using a dropping funnel over 2 hours. After the dropping was completed, the reaction was continued for 3 hours to obtain a viscous pale yellow liquid. Excess acetone was added to 50 g of the obtained reaction mixture, and the precipitate was separated by filtration and vacuum dried to obtain 13 g of a pale yellow powder. The yield was 82%. The polymer obtained had a molecular weight of 38,000 as determined by GPC.

Examples 1 to 3 Dyeing cloths (Samples A to F) dyed under the following conditions were tested using the polymers obtained in Synthesis Examples 2 to 4, respectively. Sample A A cotton knitted scouring cloth (100% cotton) was dyed (“Kayer”).
us Supra Yellow RL "manufactured by Nippon Kayaku Co., Ltd.) 1% owf and 10 g / l of anhydrous Glauber's salt were dyed at a bath ratio of 1:20 at 90 ° C. for 60 minutes, washed with water and dried. Sample B Cotton knitted scouring cloth ( 100% cotton) dye (“Kayarus Supra Red BWS”)
(Manufactured by Nippon Kayaku Co., Ltd.) 1% owf, anhydrous glauber's salt 10 g / l, dyeing with a bath ratio of 1:20 at 90 ° C. for 60 minutes, washing with water,
Dried. Sample C Cotton knit scouring cloth (100% cotton) dyed
us Supra Blue 4BL / C "manufactured by Nippon Kayaku Co., Ltd.) 1% owf, 10 g / l of anhydrous Glauber's salt were dyed at a bath ratio of 1:20 at 90 ° C for 60 minutes, washed with water and dried. Sample D Cotton knitting Cloth (100% cotton) dyed ("Cibac
ron Scarlet F3G "manufactured by Ciba Geigy)
5% owf, anhydrous sodium sulfate 80g / l, soda ash 20g /
1 was used to dye at a bath ratio of 1:20 at 80 ° C. for 60 minutes, repeatedly washed with water and washed with hot water, and then dried. Sample E Cotton knitting scouring cloth (100% cotton)
on Blue HERD "(ICI)) 0.
1% owf, anhydrous sodium sulfate 15g / l, soda ash 10g / l
Was dyed at a bath ratio of 1:20 at 80 ° C. for 30 minutes, repeatedly washed with water and washed with hot water, and then dried. Sample F Cotton knitted scouring cloth (100% cotton) was dyed ("Remaz"
ol Turquoise Blue G "Hoechst) 0.1% owf, anhydrous Glauber's salt 15g / l, soda ash 10g / l were used, dyeing was carried out at a bath ratio of 1:20 at 60 ° C for 30 minutes, and washing with water and washing with water were repeated. After that, it was dried.

Example 1 Samples A to F were dipped under the following conditions, and the treated cloths were treated with an acetic acid solution (0.3 cc /
It was immersed in l), neutralized with acid, washed with water, and then air dried. Synthesis Example 1 Polymer (solid content) 1% owf sodium hydroxide aqueous solution (30%) 3 g / l Treatment temperature / time 40 ° C. × 30 minutes (sodium hydroxide aqueous solution was added midway after treatment at 40 ° C. × 10 minutes) Bath ratio 1:20

[Example 2] Samples A to F were immersed in the following conditions, and the treated cloth was treated with an acetic acid solution (0.3 cc /
It was immersed in l), neutralized with acid, washed with water, and then air dried. Synthesis Example 2 Polymer (solid content) 1% owf sodium hydroxide aqueous solution (30%) 3 g / l Treatment temperature / time 40 ° C. × 30 minutes (sodium hydroxide aqueous solution was added midway after treatment at 40 ° C. × 10 minutes) Bath ratio 1:20

[Example 3] Samples A to F were dipped under the following conditions, and the treated cloth was treated with an acetic acid solution (0.3 cc /
It was immersed in l), neutralized with acid, washed with water, and then air dried. Synthesis Example 3 Polymer (solid content) 1% owf sodium hydroxide aqueous solution (30%) 3 g / l Treatment temperature / time 40 ° C. × 30 minutes (sodium hydroxide aqueous solution was added midway after treatment at 40 ° C. × 10 minutes) Bath ratio 1:20

[Comparative Example 1] Samples A to F were dipped under the following conditions, and the treated cloth was treated with an acetic acid solution (0.3 cc /
It was immersed in l), neutralized with acid, washed with water, and then air dried. Dicyandiamide-diethylenetriamine condensate (solid content) 2% oWf Treatment temperature / time 60 ° C. × 30 minutes Bath ratio 1:20

[Comparative Example 2] Samples A to F were dipped under the following conditions, and the treated cloth was treated with an acetic acid solution (0.3 cc /
It was immersed in l), neutralized with acid, washed with water, and then air dried. Diallyldimethylammonium chloride polymer (solid content) 2% owf Treatment temperature / time 60 ° C x 30 minutes Bath ratio 1:20

【Evaluation test】

[Washing test] The washing test was carried out based on the JISL-0844 A-2 test. For Samples AD, unprocessed cloth,
As the washing fastness of the treated cloths obtained in Examples 1 to 3 and Comparative Examples 1 to 2, contamination of the applied cloth (gold width) is shown in Table 1.

[Chlorine fastness test] The test was carried out based on the JIS L-0884 weak test. For samples C, E and F,
Table 2 shows the chlorine resistance of the unprocessed cloth and the treated cloths obtained in Examples 1 to 3 and Comparative Examples 1 and 2.

[Light fastness] JISL-0842 was irradiated at 63 ° C for 20 hours. For Samples C, E and F, Table 3 shows the light fastnesses of the untreated fabrics and the treated fabrics obtained in Examples 1 to 3 and Comparative Examples 1 and 2. The numbers in Tables 1 to 3 indicate series.

[Table 1]

[Table 2]

[Table 3]

Claims (3)

[Claims] (A) A dyed cellulosic fiber material is represented by the general formula (1): [Wherein X represents a halogen atom, Y represents an organic acid or an inorganic acid], and (b) a repeating monomer unit represented by the above general formula (1); A method for improving wet fastness, which comprises treating a monomer which is a monomer unit with a copolymer which is copolymerizable with another monomer unit. 2. The other copolymerizable monomer unit is at least one kind selected from the group consisting of an allylic monomer unit and an acrylic monomer unit. the method of. 3. Process according to claim 1, characterized in that it is carried out in an alkaline bath.