JP3360124B2 - Chlorine fastness improver for dyed cellulosic fiber products and processing method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for improving the fastness to chlorine of cellulosic textile products.

2. Description of the Related Art Dyed cellulosic fiber products, especially products dyed with reactive dyes and direct dyes, can be discolored by active chlorine such as chlorine in tap water and chlorine for disinfection in pool water. It is known that improvement in the fastness to chlorine of these textile products is required. Conventionally, as a method for improving the above-mentioned fastness to chlorine, for example, a method of treating a resin with thiourea or a thiourea derivative (Japanese Patent Laid-Open Nos. 50-58374 and 62-104983).
Nos. 104986 and 63-309681-30968
No. 2), a method of treating with a resin and urea or a guanidine compound (Japanese Patent Publication No. 57-29593, etc.), a method of treating with a diamine and / or tannic acid (JP-A-56-9)
Nos. 6971, 57-143584 and 57-154
No. 475, No. 58-115183, etc.) and a method of treating with an allylamine-based polymer (JP-A-58-31185).
No. 63-182485, JP-A 1-272887
No. 2-80681) and a method of treating with a polymer obtained by condensing a polyethylene polyamine and epihalohydrin (JP-A-55-152879 and JP-A-55-15288).
Nos. 0 and 55-152881), but no satisfactory chlorine fastness has been obtained by any of the methods.
In addition, when using a method of treating a resin and thiourea, tannic acid (and diamines), or a resin and a guanidine compound to treat a dyed cellulose fiber product, discoloration of the fiber product occurs, Furthermore, the fastness to sweat and sunlight of the textile product is reduced. Furthermore, when a method of treating with a polymer obtained by condensing epihalohydrin with diamines or polyethylene polyamine is used, the effect of further improving the fastness to chlorine is lower than other methods, and the method of treating with an allylamine-based polymer is used. When treated, the fastness to sweat and sunlight of the textile product decreases. In addition, in the method of treating with a resin and thiourea or a resin and a guanidine-based compound, the treatment method is limited to a pad method, a spray method, and a coat method, and is the most common treatment method. It has a drawback that it is not possible to employ an exhaustion method that allows processing regardless of the shape of the material, such as a knitted fabric. As described above, each of the conventional processing methods has its own problems, and at present, it has not yet satisfied the market requirements. The present inventor has studied to solve the above-mentioned problems, and treated a dyed cellulose fiber product with a semicarbazide compound or a resin and a semicarbazide compound (Japanese Patent Application No. 2-326584). The treated cellulosic fiber product with a hydrazide compound or a resin and a hydrazide compound (Japanese Patent Application No. Hei 3-2).
64288), without discoloration of the dyed cellulosic fiber product and deterioration of the fastness to sweat and sunlight.
It has been found that the fiber product can be given excellent chlorine fastness and excellent durability fastness. However, in this case, although an excellent effect of improving the durability and chlorine fastness is obtained, the processing method is limited to the pad method, the spray method, and the coating method, and has a disadvantage that the processing cannot be performed using the exhaustion method. Had. In order to eliminate this drawback, the present inventor has further studied and completed the present invention.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for imparting an excellent chlorine fastness to a dyed cellulosic fiber product without reducing the fastness to sweat and sunlight. To provide. That is, the present invention is carboxymethyl Roh hydrazide or general formula (1)

Embedded image Wherein X is an alkylene group having 1 to 18 carbon atoms or a general formula

Embedded image Is shown. The present invention relates to a method for improving the fastness to chlorine of a dyed cellulosic fiber product, which comprises a polymer produced by condensation of 0.5 to 4 mol of epihalohydrin with respect to 1 mol of the hydrazide compound represented by the formula (1). According to the study of the present inventor, when a dyed cellulosic fiber product is treated with the polymer of the present invention, an exhaustion method capable of treating any material, such as cotton, yarn and knitted fabric, is used. It has been found that it can be employed as a treatment method and can impart excellent chlorine fastness to textiles, and that the treatment does not cause a decrease in fastness to sweat and sunlight. Preferred specific examples of the compound represented by the general formula (1) include adipic dihydrazide, sebacic dihydrazide, dodecane diacid dihydrazide, phthalic dihydrazide, and isophthalic dihydrazide. The polymer of the present invention is obtained by mixing one or more of the above-mentioned hydrazide-based compounds and epihalohydrin in water or an organic solvent, and then as an alkali agent as a catalyst, for example, potassium hydroxide, sodium hydroxide, in the presence of lithium hydroxide, It can be obtained by heating in the range of 30 to 100 ° C. When the polymer of the present invention is obtained from the hydrazide compound and epihalohydrin, the molar ratio can be 1: 0.5 to 4, but is preferably 1: 1 to 1.9. The amount of the alkali agent to be used may be 0.5 to 1.5 mol per 1 mol of epihalohydrin, but may be 0.5 to 1.5 mol.
It is particularly preferred that the amount be 8 to 1.1 mol. The amount of the polymer used in the present invention is 0.1 to 5%, preferably about 0.2 to 2%, based on the fiber. In the present invention, if necessary, known surfactants, dispersants, organic solvents, and the like used in the art may be appropriately used in combination. In addition, a fixing agent for improving wet fastness, a softening agent for adjusting feeling, and the like may be used in combination. Examples of the 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 copper ammonia rayon. The fiber products include the above-mentioned natural cellulose fibers and / or regenerated cellulose fibers, as long as they are dyed by a known method. Fibers other than these may be included. In applying the treatment method of the present invention to textiles, there is no particular limitation, and conventionally known methods can be appropriately used.
For example, in the immersion method, a bath ratio of 1: 5 to 1: 100,
The treatment can be performed under conditions such as a treatment temperature of 50 to 60 ° C. and a treatment time of 10 to 30 minutes.

EXAMPLES Examples and comparative examples are given below.
While the features of the present invention will be more clear, the present invention is not limited to the following examples.

Synthesis Example 1 Carbonohydrazide (CD) was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
H) 300 g (3.3 mol) and 3066 g of water were added, stirred and uniformly dissolved, and then heated to raise the temperature to 30 ° C. To this mixture, 390 g (4.2 mol) of epichlorohydrin was dropped from the dropping funnel over about 1 hour. 30 minutes after completion of the dropwise addition, 164 g of sodium hydroxide
(4.1 mol). After charging, the internal temperature is 80 ℃
And reacted for 5 hours. After completion of the reaction, 10 g of the reaction mixture was applied to a dialysis membrane ("Dialasis membrane 3").
The solution was dialyzed using 6 "Wako Pure Chemical Industries, Ltd. and the content was dried under reduced pressure to obtain 1.2 g of a pale yellow polymer of the present invention (yield 9).
0%)

Synthesis Example 2 Carbonohydrazide (CD) was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
H) 300 g (3.3 mol) and 3564 g of water were added, stirred and uniformly dissolved, and then heated to raise the temperature to 30 ° C. To this mixture, 510 g (5.5 mol) of epichlorohydrin was dropped from the dropping funnel over about 1 hour. 30 minutes after completion of the dropwise addition, 164 g of sodium hydroxide
(4.1 mol). After charging, the internal temperature is 80 ℃
And reacted for 5 hours. After completion of the reaction, 10 g of the reaction mixture was applied to a dialysis membrane ("Dialasis membrane 3").
The solution was dialyzed using 6 "Wako Pure Chemical Industries, Ltd. and the content was dried under reduced pressure to obtain 1.2 g of a pale yellow polymer of the present invention (yield 9).
0%)

Synthesis Example 3 Adipic dihydrazide (A) was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
DH) 300 g (1.7 mol) and water 3528 g
After stirring to dissolve uniformly, the mixture was heated to raise the temperature to 40 ° C. To this mixture, 271 g (2.9 mol) of epichlorohydrin was added dropwise from a dropping funnel over about 1 hour. 30 minutes after the completion of dropping, 112 g of sodium hydroxide
(2.8 moles). After charging is completed, internal temperature is 90 ℃
And reacted for 9 hours. After completion of the reaction, 10 g of the reaction mixture was applied to a dialysis membrane ("Dialasis membrane 3").
The solution was dialyzed using 6 "Wako Pure Chemical Industries, Ltd. and the contents were dried under reduced pressure to obtain 0.9 g of a pale yellow polymer of the present invention (yield: 8).
5%)

Examples 1 to 3 Using the polymers of the present invention obtained in Synthesis Examples 1 to 3, dyed fabrics (samples A to E) were dyed under the following conditions. still,
Hereinafter, “%” indicates “% by weight” unless otherwise specified. Sample A A cotton knit scouring cloth (100% cotton) was dyed (“Proci
on Blue HEGN "ICI company) 0.0
5% owf, anhydrous sodium sulfate 15 g / l, soda ash 15 g / l
And dyeing at a bath ratio of 1:20 at 80 ° C. for 60 minutes, washing with water and washing with hot water were repeated, and then dried. Sample B Cotton knitted scouring cloth (100% cotton) was dyed (“Proci
on Yellow HE4R (manufactured by ICI) 0.
65% owf, dye ("Procion Red HE
7B "ICI" 0.1% owf, dye ("P
rocionBlue HERD "manufactured by ICI Company)
0.25% owf, anhydrous sodium sulfate 15 g / l, soda ash 1
Using 5 g / l, dyeing was carried out at a bath ratio of 1:20 at 80 ° C. for 60 minutes, washed repeatedly with water and hot water, and dried. Sample C A cotton knit scouring cloth (100% cotton) is dyed (“Suif
ix Supra Yellow 3RF 150
% “Sumitomo Chemical Co., Ltd.” 0.43% owf, dye (“Su
mifix Supra Brilliant Red
3BF 150% "Sumitomo Chemical Co., Ltd." 0.07% ow
f, dye ("Sumifix SupraBlue B
RF 150% “Sumitomo Chemical Co., Ltd.) 0.17% owf,
Using 15 g / l of anhydrous sodium sulfate and 15 g / l of soda ash, dyeing was performed at 60 ° C. × 60 minutes at a bath ratio of 1:20, washing with water and washing with hot water were repeated, and then drying. Sample D A cotton knit scouring cloth (100% cotton) was dyed (“Proci
on Red HE7B "manufactured by ICI company) 0.05
% Owf, anhydrous glaucoma 15 g / l, soda ash 15 g / l, dyeing at 80 ° C. × 60 minutes at a bath ratio of 1:20, washing with water,
After repeated hot water washing, it was dried. Sample E A cotton knit scouring cloth (100% cotton) was dyed (“Remaz
ol Turquoise Blue G (manufactured by Hoechst Co.) 0.05% owf, 15 g / l of anhydrous sodium sulfate and 15 g / l of soda ash were dyed at a bath ratio of 1:20 at 60 ° C. for 60 minutes, and washing with water and washing with hot water were repeated. After that, it was dried.

Example 1 Samples A, B, C, D and E were immersed under the following conditions, washed with water and air-dried. Treatment bath: Synthesis example 1 Polymer (solid content) 1% owf Treatment temperature / time: 60 ° C. × 20 minutes Bath ratio 1:20

Example 2 Samples A, B, C, D and E were immersed under the following conditions, washed with water and air-dried. Treatment bath: Synthesis example 2 Polymer (solid content) 1% owf Treatment temperature / time: 60 ° C. × 20 minutes Bath ratio 1:20

Example 3 Samples A, B, C, D and E were immersed under the following conditions, washed with water and air-dried. Treatment bath: Synthesis example 3 Polymer (solid content) 1% owf Treatment temperature / time: 60 ° C. × 20 minutes Bath ratio 1:20

Comparative Example 1 Samples A, B, C, D and E were immersed under the following conditions, washed with water and air-dried. Treatment bath: polyallylamine (solid content) 1% owf Treatment temperature / time: 60 ° C. × 20 minutes Bath ratio 1:20

Comparative Example 2 Samples A, B, C, D and E were immersed under the following conditions, washed with water and air-dried. Treatment bath: tallow alkylpropylene diamine 1% owf acetic acid 1% owf Treatment temperature / time: 60 ° C. × 20 minutes Bath ratio 1:20

【Evaluation test】

[Cleanness fastness 1] Unprocessed cloth according to JISL-0884 weak test (effective chlorine concentration 10 ppm), Example 1
-3 and the treated fabrics obtained in Comparative Examples 1 and 2 were evaluated for chlorine fastness. Table 1 shows the results.

[Chlorine fastness 2] Put a test cloth in a home washing machine, pass tap water at a flow rate of 6 l / min, wash with stirring for 1 hour, untreated cloth, Examples 1-3 and Comparative Examples The treated cloths obtained in 1 and 2 were evaluated for chlorine fastness. Table 2 shows the results.

[Sweat Sunlight Robustness] The untreated cloth, the treated cloths obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were immersed in a treatment liquid (sweat liquid) having the following composition at a bath ratio of 1:50 for 30 minutes, and then mangled. After squeezing (aperture ratio 100%), the results of evaluating the fastness to sweat and sunlight (63 ° C. × 10 hours) with a fadeometer are shown in Table 3. The numbers in Tables 1 to 3 indicate series.

[Table 1]

[Table 2]

[Table 3]

Claims (2)

(57) [Claims] (1) a carbonohydrazide or a general formula: [Wherein X is an alkylene group having 1 to 18 carbon atoms or a general formula: Is shown. A chlorine-resistant fastness improver for dyed cellulosic fiber products, comprising a polymer produced by condensation of 0.5 to 4 mol of epihalohydrin with respect to 1 mol of the hydrazide compound represented by the formula (1). 2. A method for improving the fastness to chlorine of cellulosic textile products, comprising treating the dyed product with the agent for improving fastness to chlorine according to claim 1.