JP2003278080A - Method for treating protein fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To impart shrink-resistance to a protein fiber product at a low temperature without carrying out treatment by ozone or plasma without using a chlorine-based oxidizing agent, an enzyme or a resin and without removing scale of animal hair such as wool. <P>SOLUTION: The method for treating the protein fiber product comprises impregnating a protein fiber product into a first aqueous solution containing 0.5-3 wt.% ammonium salt and having pH 5.0-8.5, treating the protein fiber product for 20-60 min at 30-60°C, impregnating the protein fiber product treated with the first aqueous solution into a second aqueous solution having pH 3-9 and containing 6-12 wt.% shape-stabilizing agent and 0.1-12 wt.% first protein, drying the impregnated protein fiber product at 100-130°C for 1-10 min, impregnating the protein fiber product treated with the second aqueous solution into a third aqueous solution having pH 1-3 and containing 0.5-2.0 wt.% organic acid and 0.1-1.2 wt.% second protein and treating the treated protein fiber product at 15-35°C for 10-60 min and impregnating the protein fiber product treated with the third aqueous solution into a fourth aqueous solution having pH 7.5-9.5 and containing 0.1-1.5 wt.% alkali agent and treating the treated protein fiber product at 30-50°C for 10-60 min. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for treating protein fiber products such as wool. More specifically, it relates to a treatment method for imparting shrink resistance and dimensional stability to water-based washing to a protein fiber product.

[0002]

2. Description of the Related Art At present, the following methods are known as shrink-proofing methods for industrialized natural protein fiber products. A method for removing scales of animal hair fibers using a chlorine-based oxidizing agent,
A method of imparting shrinkage resistance to animal hair fibers by removing scales of animal hair fibers using proteases such as protease, and coating the protein fiber surface with resin processing using polyurethane etc. Deterioration treatment method, plasma treatment of animal hair fibers under reduced pressure to make the surface of animal hair fibers hydrophilic and improve affinity with various anti-shrinking agents, oxidize and remove animal hair fiber scales using ozone Method.

[0003]

However, the above method has a risk of fatally damaging the fiber body, and there is a possibility that the ozone layer is destroyed or the environment is destroyed by the generation of dioxins. Since it is likely to cause worker health problems, there is a need for immediate development of alternative methods. The above method has a problem that a high weight loss rate cannot be obtained because the reactivity of the enzyme with respect to the animal hair fiber is low, a very long time is required for the enzyme treatment, and the strength is remarkably reduced. When treated by the above method, there is a problem that the texture of the protein fiber product becomes hard and the hue thereof changes. Further, the above method is difficult to put into practical use because it has to undergo a treatment step under reduced pressure, requires a long time for depressurization, and requires a closed space for depressurization treatment. There's a problem. Further, the above method is likely to cause damage to the fiber body and decrease in strength, as in the above method. The object of the present invention is to provide a chlorine-based oxidant, an enzyme,
It is to provide a treatment method for imparting shrinkage resistance to a protein fiber product at a low temperature without using a resin, without removing scales of animal hair fibers such as wool, and without performing treatment with ozone or plasma. .

[0004]

The invention according to claim 1 is
PH 5.0-containing 0.5 to 3 wt% ammonium salt
30-60 by impregnating the first aqueous solution of 8.5 with the protein fiber product
A step of treating at 60 ° C. for 20 to 60 minutes, and a second aqueous solution having a pH of 3 to 9 and containing 6 to 12% by weight of a morphological stabilizer and 0.1 to 12% by weight of the first protein. A step of impregnating the protein fiber article, a step of drying the protein fiber article impregnated with the second aqueous solution at 100 to 130 ° C., 0.5
~ 2.0 wt% organic acid and 0.1-1.2 wt% second
A step of impregnating the dried protein fiber product in a third aqueous solution of pH 1 to 3 containing protein and treating at 15 to 35 ° C. for 10 to 60 minutes; and pH 7 containing 0.1 to 1.5% by weight of an alkaline agent. 10 to 6 at 30 to 50 ° C. by impregnating the fourth aqueous solution of 0.5 to 9.5 with the protein fiber product treated with the third aqueous solution
A treatment method for a protein fiber product, which comprises a treatment for 0 minutes.

According to the method of claim 1, when treated with the first aqueous solution, the epicuticle on the surface of the protein fiber, which is originally hydrophobic, is hydrophilized. When treated with the second aqueous solution,
Disulfide bond cleavage and recombination occur, followed by the first
The epicuticle etched with the aqueous solution is repaired, and the texture of the protein fiber product is improved by adding the first protein. Further, when treated with the third aqueous solution, the protein fiber product is provided with anti-setting property, and the second protein coats the scale of the protein fiber product to reduce the tingling sensation and improve the hygroscopicity. As a result, due to the synergistic effect of the treatment with the first aqueous solution to the third aqueous solution, the scale on the surface of the protein fiber product is less likely to rise, and the shrink resistance of the protein fiber product is improved. Finally, when treated with the fourth aqueous solution, the protein fiber product that has been acidified by the treatment with the third aqueous solution is neutralized with the alkaline agent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The protein fibers constituting the protein fiber product of the present invention are animal hair fibers such as wool, cashmere, alpaca, angora and mohair, or silk fibers obtained from cocoons such as domestic silkworms and wild silkworms. Protein fiber products include loose fibers, tops, threads, woven fabrics, knitted fabrics, non-woven fabrics and the like made from these fibers. The protein fiber product of the present invention does not need to be 100% protein fiber, but may be mixed or blended with other fibers such as cellulose fiber such as cotton fiber and hemp fiber, and chemical fiber such as rayon, acetate, nylon, polyester and acrylic. Includes woven and mixed knitted textiles. In this case, it contains at least 10% by weight of protein fibers. The first aqueous solution of the present invention is 0.5 to 3% by weight,
PH 5.0-8.5, preferably pH 7.5-8.5, containing preferably 0.8-1.5% by weight ammonium salt.
Is an aqueous solution of. If the amount of the ammonium salt is less than 0.5% by weight, the effect of modifying the epicuticle cannot be sufficiently achieved.
When it exceeds the weight%, the chemical becomes excessive. Examples of ammonium salts include ammonium hydrogen carbonate, ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate, monoammonium phosphate, diammonium phosphate, and triammonium phosphate. These are used alone or in combination. The first aqueous solution is impregnated with a protein fiber product for 30-
The treatment is carried out at 60 ° C., preferably 35 to 50 ° C. for 20 to 60 minutes, preferably 20 to 45 minutes. When the treatment temperature and the treatment time exceed the upper limit, the treatment becomes uneven, and when the treatment temperature and the treatment time are below the lower limit, the treatment becomes insufficient.

The second aqueous solution of the present invention contains 6 to 12% by weight,
Preferably 6-10 wt% morphological stabilizer and 0.1-1
It is an aqueous solution containing 2% by weight, preferably 5-10% by weight, of the first protein and having a pH of 3-9, preferably 7.5-8.5. If the amount of the morphological stabilizer is less than 6% by weight, the morphology of the protein fiber product is not stabilized, and if it exceeds 12% by weight, the protein fiber becomes brittle. Examples of the morphological stabilizer include sodium hydrogen sulfite, ammonium thioglycolate, monoethanolamine bisulfite, phosphorous acid, thiourea dioxide and the like. These are used alone or in combination. If the amount of the first protein is less than 0.1% by weight, defects such as poor repair and poor texture will occur, and if it exceeds 12% by weight, the amount of chemicals will be excessive. Examples of the first protein include silk fibroin, animal hair keratin, animal hair keratose and the like.
After impregnating the second aqueous solution with the protein fiber product treated with the first aqueous solution, 100-130 ° C., preferably 110-13
Dry at 0 ° C. for 1-10 minutes, preferably 3-10 minutes. When the treatment temperature and the treatment time exceed the upper limit, the texture of the protein fiber becomes poor, and when the treatment temperature and the treatment time are below the lower limit, the chemical reaction becomes insufficient.

The third aqueous solution of the present invention contains 0.5 to 2.0% by weight, preferably 0.5 to 1.0% by weight of an organic acid and 0.1% by weight.
1 to 1.2% by weight, preferably 0.2 to 0.8% by weight of the second protein, pH 1 to 3, preferably pH 1.
It is an aqueous solution of 8 to 2.5. 0.5% by weight of the above organic acid
If it is less than 1.2%, the set will be defective, and if it exceeds 1.2% by weight, unreacted chemicals will remain. Examples of the organic acid include maleic acid, maleic anhydride, tetrathionic acid and the like.
These are used alone or in combination. If the second protein is less than 0.1% by weight, pilling occurs, and if it exceeds 1.2% by weight, unreacted chemicals remain. Examples of the second protein include silk fibroin, animal hair keratin, animal hair keratose and the like. The second protein and the first protein may be the same. The protein fiber product treated with the second aqueous solution is impregnated with the third aqueous solution and treated at 15 to 35 ° C., preferably 20 to 30 ° C. for 10 to 60 minutes, preferably 20 to 45 minutes. If the treatment temperature and treatment time exceed the upper limit, the fibers will be damaged, and if the treatment temperature and the treatment time are below the lower limit, the chemical reaction will be insufficient.

The fourth aqueous solution of the present invention contains 0.1 to 1.5% by weight, preferably 0.1 to 0.5% by weight of an alkaline agent and has a pH of 7.5 to 9.5, preferably 9 to 9. It is an aqueous solution of 0.5. If the alkaline agent is less than 0.1% by weight, the neutralization reaction is not sufficient, and if it exceeds 1.5% by weight, the protein fiber becomes brittle. As an alkaline agent, ammonia water,
Examples include sodium hydrogen carbonate and disodium hydrogen phosphate. These are used alone or in combination. The fourth aqueous solution is impregnated with a protein fiber product and treated at 30 to 50 ° C, preferably 35 to 45 ° C for 10 to 60 minutes, preferably 10 to 30 minutes. If the treatment temperature and the treatment time exceed the upper limit, the texture of the protein fiber will be poor, and if it is less than the lower limit, the neutralization will be insufficient.

[0010]

EXAMPLES Next, examples of the present invention will be described together with comparative examples. <Example 1> Worsted yarn-dyed shirt fabric (80% wool, 20 lamb)
%) Was prepared. Permeation cleaning scouring agent (Tuyak Corporation 21-
DF-10) p containing 0.5% by weight and 10 g / l (1.0% by weight) of ammonium hydrogencarbonate, which is an ammonium salt.
Impregnate the above-mentioned shirt cloth with the first aqueous solution of H8.0 at 40 ° C.
For 30 minutes. Next, 12% by weight of sodium bisulfite which is a morphological stabilizer, 10% by weight of silk fibroin (CS-TC of Daiwa Chemical Co., Ltd.) which is the first protein, and special amino-modified silicone (ST-B of Yamato Chemical Co., Ltd.) 5 % By weight and permeation washing scouring agent (Tuyak Corporation 21-DF-1
0) A second aqueous solution containing 0.5% by weight and having a pH of 8.4 at 20 ° C. was prepared, and the second aqueous solution was impregnated with the second aqueous solution for 0.2 minutes in a state where the shirt cloth treated with the first aqueous solution was spread. The liquid was drained at and dried at 110 ° C. for 5 minutes. Next, maleic anhydride 6g / l (0.6% by weight), which is an organic acid, and keratose solution (Nippon Textile Industry Cooperative Association Proticute FCL) 5 ml / l (0.5% by weight), which is the second protein, are infiltrated. Cleaning and scouring agent (Tuyak Corporation 21-DF-1
0) The above-mentioned shirt cloth was impregnated with a third aqueous solution containing 0.5% by weight and having a pH of 1.8, and treated at 25 ° C for 30 minutes. 2g / l (0.2wt%) of ammonia water, which is an alkaline agent
Impregnate the above-mentioned shirt cloth with a fourth aqueous solution containing
It was processed for 0 minutes.

<Example 2> The same worsted yarn-dyed shirt fabric as in Example 1 was prepared, and the same first aqueous solution as in Example 1 was impregnated with the above-mentioned shirt fabric in the same manner as in Example 1 for treatment. Then 10% by weight of ammonium thioglycolate, which is a morphological stabilizer
And the first protein, silk fibroin (Daiwa Chemical Co., Ltd.)
20 ° C. containing 10% by weight of CS-TC), 5% by weight of special amino-modified silicone (ST-B of Yamato Chemical Co., Ltd.) and 0.5% by weight of osmotic cleaning and refining agent (21-DF-10 of Tayak Co., Ltd.) Prepare a second aqueous solution having a pH of 8.4, impregnate the second aqueous solution with the second aqueous solution for 0.2 minutes with the shirt cloth treated with the first aqueous solution spread, then drain with a mangle and dry at 110 ° C for 5 minutes. did. Next, the same third aqueous solution as in Example 1 was impregnated with the above-mentioned shirt fabric in the same manner as in Example 1 for treatment. Further, the same shirt solution as in Example 1 was impregnated with the same fourth aqueous solution as in Example 1 for treatment.

<Example 3> The same worsted yarn-dyed shirt fabric as in Example 1 was prepared. Permeation cleaning scouring agent (Tuyak Corporation 21-
DF-10) 0.5 wt% and ammonium sulfate 10 g / l (1 wt%) which is an ammonium salt, pH 5.4
The above-mentioned shirt cloth was impregnated with the first aqueous solution of, and treated at 40 ° C. for 30 minutes. Then, the same second aqueous solution as in Example 1 was prepared, and the shirt cloth treated with the first aqueous solution containing ammonium sulfate was impregnated with the second aqueous solution as in Example 1, then drained and dried. Next, 5 g / l (0.5% by weight) of tetrathionic acid, which is an organic acid, and 5 ml / l (0.5% by weight) of keratose solution (Nippon Textile Industry Cooperative Co., Ltd. Proticute FCL), which is a second protein, and permeation washing. The above-mentioned shirt cloth was impregnated with a third aqueous solution containing 0.5% by weight of a scouring agent (Tuyak Co., Ltd. 21-DF-10) and having a pH of 1.8.
It was treated at 5 ° C. for 30 minutes. Further, the same shirt solution as in Example 1 was impregnated with the same fourth aqueous solution as in Example 1 for treatment.

<Example 4> The same worsted yarn-dyed shirt fabric as in Example 1 was prepared. The same treatment as in Example 1 was performed except that the treatment of the first aqueous solution was performed at 30 ° C. for 20 minutes.

Comparative Example 1 The same worsted yarn-dyed shirt fabric as in Example 1 was prepared. In Example 1, the same second aqueous solution as Example 1 except that the treatment with the first aqueous solution was not performed,
The shirt cloth was treated in the same manner as in Example 1 using the aqueous solution and the fourth aqueous solution.

Comparative Example 2 The same worsted yarn-dyed shirt fabric as in Example 1 was prepared. In Example 1, the same first aqueous solution as Example 1 except that the treatment with the second aqueous solution was not performed.
The shirt cloth was treated in the same manner as in Example 1 using the aqueous solution and the fourth aqueous solution.

<Example 5> Botany surge dyeing (100% wool) after carding was prepared. Penetrating cleaning scouring agent
21-DF-10) (0.5% by weight) and 15 g / l (1.5% by weight) of ammonium hydrogencarbonate, which is an ammonium salt, were impregnated with the above botany surge into a first aqueous solution having a pH of 8.0, and 40 It was treated at 30 ° C. for 30 minutes. Next, 8% by weight of phosphorous acid which is a morphological stabilizer and 10% by weight of silk fibroin (CS-TC, Daiwa Chemical Co., Ltd.) which is the first protein.
And special amino-modified silicone (ST-B, Daiwa Chemical Co., Ltd.)
5% by weight and permeation washing scouring agent (Tuyak Co., Ltd. 21-DF-
10) A second aqueous solution containing 0.5% by weight and having a pH of 8.4 at 20 ° C. was prepared, and the second aqueous solution was impregnated with the second aqueous solution for 0.2 minutes while spreading the Botany surge treated with the first aqueous solution. The liquid was drained at and dried at 110 ° C. for 5 minutes. Next, maleic anhydride 6g / l (0.6% by weight), which is an organic acid, and keratose solution (Nippon Textile Industry Cooperative, Proticute FCL) 5ml / l, which is a second protein.
(0.5% by weight) and permeation washing scouring agent (Tuyak Co., Ltd. 21
-DF-10) A third aqueous solution containing 0.5% by weight of pH 1.8 was impregnated with the above Botany surge, and treated at 25 ° C for 30 minutes. Ammonia water, which is an alkaline agent, 2 g / l
A fourth aqueous solution containing (0.2% by weight) was impregnated with the above Botany surge and treated at 40 ° C. for 30 minutes.

<Example 6> The same worsted dyed Botany surge as in Example 5 was prepared. Penetration cleaning scouring agent (Tuyak Corporation)
21-DF-10) 0.5% by weight and ammonium carbonate 10 g / l (1.0% by weight), which is an ammonium salt, were impregnated with the above-mentioned Botany surge in a first aqueous solution having a pH of 8.0, and the solution was immersed at 40 ° C. for 30 minutes. Processed. Next, 10% by weight of thiourea dioxide, which is a morphological stabilizer, and 10% by weight of silk fibroin (CS-TC, Daiwa Chemical Co., Ltd.), which is the first protein.
And special amino-modified silicone (ST-B, Daiwa Chemical Co., Ltd.)
5% by weight and permeation washing scouring agent (Tuyak Co., Ltd. 21-DF-
10) A second aqueous solution containing 0.5% by weight and having a pH of 8.4 at 20 ° C. was prepared, and the second aqueous solution was impregnated with the second aqueous solution for 0.2 minutes while spreading the Botany surge treated with the first aqueous solution. The liquid was drained at and dried at 110 ° C. for 5 minutes. Next, maleic acid 8 g / l (0.8% by weight), which is an organic acid, and keratose solution (Nippon Textile Industry Cooperative, Proticute FCL), which is a second protein, 5 ml / l (0.
5% by weight) and permeation cleaning scouring agent (Tuyak Co., Ltd. 21-DF
-10) A third aqueous solution containing 0.5% by weight and having a pH of 1.8 was impregnated with the above Botany surge, and treated at 25 ° C. for 30 minutes. Further, 2 g / l of ammonia water (0.
The fourth aqueous solution containing 2% by weight) was impregnated with the above botany surge and treated at 40 ° C. for 30 minutes.

Example 7 The same worsted dyed Botany surge as in Example 5 was prepared. Penetration cleaning scouring agent (Tuyak Corporation)
21-DF-10) 0.5% by weight and ammonium sulfate 15 g / l (1.5% by weight), which is an ammonium salt, were impregnated with the above botany surge in a first aqueous solution having a pH of 5.4 and treated at 40 ° C. for 30 minutes. did. Next, 8% by weight of phosphite which is a morphological stabilizer, 10% by weight of silk fibroin (CS-TC of Daiwa Chemical Co., Ltd.) which is the first protein, and special amino-modified silicone (ST-B of Yamato Chemical Co., Ltd.) 5 weight%
And osmotic cleaning scouring agent (Tuyak Corporation 21-DF-10)
A second aqueous solution containing 0.5% by weight and having a pH of 8.4 at 20 ° C. was prepared, and after the botany surge treated with the first aqueous solution was spread, the second aqueous solution was impregnated with the second aqueous solution for 0.2 minutes, and then removed with a mangle. The solution was dried and dried at 110 ° C. for 5 minutes. Then, with an organic acid, maleic anhydride 6 g / l (0.6% by weight) and a second
Keratose solution (Nippon Textile Industry Cooperative, Proticute FCL) 5 ml / l (0.5% by weight) which is a protein, and a permeation washing scouring agent (Tweak 21-DF-1)
0) A third aqueous solution containing 0.5% by weight and having a pH of 1.8 was impregnated with the above Botany surge and treated at 25 ° C. for 30 minutes.
1 g / l of sodium hydrogencarbonate, which is an alkaline agent
A fourth aqueous solution containing (0.1% by weight) was impregnated with the above Botany surge and treated at 40 ° C. for 30 minutes.

<Example 8> The same carded post-dyeing Botany surge as in Example 5 was prepared. Penetration cleaning scouring agent (Tuyak Corporation)
21-DF-10) 0.5% by weight and 15 g / l (1.5% by weight) of ammonium hydrogencarbonate, which is an ammonium salt, were impregnated with the above-mentioned botany surge in a first aqueous solution having a pH of 8.0, and the mixture was stored at 40 ° C. for 30 minutes. Processed for a minute. Next, 8% by weight of ammonium thioglycolate, which is a morphological stabilizer, and silk fibroin, which is the first protein (CS-T, manufactured by Daiwa Chemical Co., Ltd.).
C) 10% by weight and special amino-modified silicone (Daiwa Chemical
5% by weight of ST-B Co., Ltd. and osmotic cleaning scouring agent (Tuyak)
21-DF-10) 0.5% by weight at 20 ° C.
A second aqueous solution of H8.4 was prepared, and a botany surge treated with the first aqueous solution was spread on the second aqueous solution in a state of being spread.
After impregnating for 2 minutes, it was drained with mangle and dried at 110 ° C. for 5 minutes. Next, tetragionic acid, an organic acid, 6 g / l
(0.6% by weight) and the second protein keratose solution (Nippon Textile Industry Cooperative, Proticute FC
L) pH containing 5 ml / l (0.5% by weight) and 0.5% by weight of osmotic cleaning and refining agent (Tuyak Co., Ltd. 21-DF-10)
Impregnating the third aqueous solution of 1.8 with the above botany surge,
It was treated at 5 ° C. for 30 minutes. Further, the fourth aqueous solution containing 2 g / l (0.2% by weight) of aqueous ammonia as an alkaline agent was impregnated with the above Botany surge and treated at 40 ° C. for 30 minutes.

<Comparative Example 3> The same worsted dyed Botany surge as in Example 5 was prepared. In Example 5, the same second aqueous solution, the third aqueous solution, and the fourth aqueous solution as in Example 5 were used to treat the Botany surge in the same manner as in Example 5, except that the treatment with the first aqueous solution was not performed.

<Comparative Example 4> The same worsted dyed Botany surge as in Example 5 was prepared. In the same manner as in Example 5, the Botany surge was treated by using the same first aqueous solution, third aqueous solution, and fourth aqueous solution as in Example 5, except that the second aqueous solution was not used.

Example 9 Wool-dyed Tweed (wool 82)
%, Nylon 6%, acrylic 10%, urethane 2%) were prepared. Permeation cleaning scouring agent (Tuyak Corporation 21-DF-
10) pH 8. containing 0.5% by weight and 10 g / l (1.0% by weight) ammonium bisulfate, which is an ammonium salt.
Impregnate the above tweed into a first aqueous solution of
Processed for a minute. Next, 8% by weight of sodium bisulfite which is a morphological stabilizer, 10% by weight of silk fibroin (CS-TC of Daiwa Chemical Co., Ltd.) which is the first protein, and special amino-modified silicone (ST-B of Yamato Chemical Co., Ltd.) 5 % By weight and 0.5% permeation washing scouring agent (Tuyak Corporation 21-DF-10)
A second aqueous solution containing 20% by weight and having a pH of 8.4 at 20 ° C. was prepared, and the second aqueous solution was impregnated with the second aqueous solution for 0.2 minutes in a spread state. Dry at 5 ° C for 5 minutes. Next, maleic acid 10 g / l (1% by weight) which is an organic acid, and keratose solution (Nippon Textile Industry Cooperative Association Proticute FCL) 8 ml / l (0.8% by weight) which is a second protein, and a permeation washing scouring agent. (Tuyak Corporation 21-DF-10) 0.5% by weight
The above tweed was impregnated in a third aqueous solution having a pH of 1.8 and was treated at 25 ° C. for 30 minutes. Furthermore, the above-mentioned tweed was impregnated with a fourth aqueous solution containing 2 g / l (0.2% by weight) of ammonia water as an alkaline agent, and treated at 40 ° C. for 30 minutes.

<Example 10> The same woolen-dyed tweed as in Example 9 was prepared. Penetration cleaning refining agent (Tuyak Corporation 21
-DF-10) The first aqueous solution having a pH of 8.0 containing 0.5% by weight of ammonium bicarbonate and 10 g / l (1.0% by weight) of ammonium hydrogen carbonate was impregnated with the above tweed, and 40
It was treated at 30 ° C. for 30 minutes. Then, 8% by weight of monoethanolamine bisulfite which is a morphological stabilizer and silk fibroin which is the first protein (CS-T of Daiwa Chemical Co., Ltd.)
C) 10% by weight and special amino-modified silicone (Daiwa Chemical
5% by weight of ST-B Co., Ltd. and osmotic cleaning scouring agent (Tuyak)
21-DF-10) 0.5% by weight at 20 ° C.
Prepare a second aqueous solution of H8.4, impregnate the second aqueous solution for 0.2 minutes with the tweed treated with the first aqueous solution containing ammonium hydrogen carbonate spread, and then deliquoring with mangle to remove the liquid at 110 ° C. And dried for 5 minutes. Next, the same third aqueous solution as in Example 9 was impregnated with the above tweed and treated in the same manner as in Example 9. Further, the same fourth aqueous solution as in Example 9 was impregnated with the above tweed and treated in the same manner as in Example 9.

<Example 11> The same woolen-dyed tweed as in Example 9 was prepared. Penetration cleaning refining agent (Tuyak Corporation 21
-DF-10) pH containing 0.5% by weight and 10 g / l (1.0% by weight) of ammonium salt which is an ammonium salt.
The above tweed was impregnated with a first aqueous solution of 8.0 and treated at 40 ° C. for 30 minutes. Next, 8% by weight of thiourea dioxide which is a morphological stabilizer, 10% by weight of silk fibroin (CS-TC of Daiwa Chemical Co., Ltd.) which is the first protein, and special amino-modified silicone (ST-B of Yamato Chemical Co., Ltd.) 5 A second aqueous solution having a pH of 8.4 at 20 ° C. containing 0.5% by weight of a permeation washing scouring agent (Tuyak 21-DF-10) is prepared.
The tweed treated with the ammonium carbonate first aqueous solution was spread and impregnated with the second aqueous solution for 0.2 minutes, drained with mangle, and dried at 110 ° C. for 5 minutes. Next, the same third aqueous solution as in Example 9 was impregnated with the above tweed and treated in the same manner as in Example 9. Further, the same fourth aqueous solution as in Example 9 was impregnated with the above tweed and treated in the same manner as in Example 9.

<Example 12> The same woolen yarn-dyed tweed as in Example 9 was prepared. The same first aqueous solution as in Example 10 was impregnated with the above tweed and treated in the same manner as in Example 10. Then, the same second aqueous solution as in Example 10 was impregnated with tweed treated with the first aqueous solution as in Example 10, then drained and dried. Next, 10 g of tetrathioic acid, which is an organic acid,
1 (1% by weight) and the second protein, keratose solution (Nippon Textile Industry Cooperative, Proticute FCL)
A pH of 1. containing 8 ml / l (0.8% by weight) and 0.5% by weight of a osmotic washing and refining agent (Tuyak Corporation 21-DF-10).
Impregnate the above-mentioned tweed into the third aqueous solution of 8 at
Processed for a minute. Further, the above-mentioned tweed was impregnated with a fourth aqueous solution containing 1 g / l (0.1% by weight) of sodium hydrogen carbonate as an alkaline agent, and treated at 40 ° C. for 30 minutes.

Comparative Example 5 The same woolen-dyed tweed as in Example 9 was prepared. In Example 9, the same second aqueous solution, third Example as in Example 9 except that the treatment with the first aqueous solution was not performed.
The tweed was treated in the same manner as in Example 9 using the aqueous solution and the fourth aqueous solution.

Comparative Example 6 The same woolen-dyed tweed as in Example 9 was prepared. In Example 9, the same first aqueous solution, Example 3 as Example 9 except that the treatment with the second aqueous solution was not performed.
The tweed was treated in the same manner as in Example 9 using the aqueous solution and the fourth aqueous solution.

<Evaluation 1> For the fabrics treated in Examples 1 to 12 and the fabrics treated in Comparative Examples 1 to 6, wool mark test method No. 31 (for examining the washing performance of wool fiber products) was used. It was evaluated by WM TM31). In this test method, a fabric sample of size 500 x 500 mm is sampled, the edges of the sample are protected against fraying, marks are given at predetermined locations, and then washed in a washing machine with warm water at 40 ° C ± 3 ° C. . After three cycles of washing, it was dried and the total dimensional change rate was calculated by the following formula (1). The results are shown in Table 1. Total dimensional change rate (%) = [(FM-OM) / OM] x 100 (1) where FM is the measured value after felting and OM is the original length.

As is clear from Table 1, the shrinkage ratios of the fabrics of Comparative Examples 1 to 6 which were not treated with the first or second aqueous solution among the first to fourth aqueous solutions had a shrinkage rate of -32.0% to-. 44.
While it was as large as 0%, the shrinkage percentages of the fabrics of Examples 1 to 12 treated with the first to fourth aqueous solutions were -2.6% to-.
It was as small as 0.5%.

[0030]

[Table 1]

<Evaluation 2> The hygroscopicity of each of the fabrics treated in Example 1 and Comparative Example 1 was evaluated by the following method. That is, these fabrics are at 20 ° C and relative humidity of 65%.
After being left for 24 hours in the atmosphere, the absolute dry weight was measured. Next, these fabrics were left to stand under an atmosphere of 20 ° C. and a relative humidity of 90% for 24 hours to absorb moisture, and then the weight after moisture absorption was measured. The water content after moisture absorption was determined by the following formula (2). Moisture content after moisture absorption = [((weight after moisture absorption)-(absolute dry weight)) / (absolute dry weight)] × 100 (2) The results are shown in Table 2.

As is clear from Table 2, of the first to fourth aqueous solutions, the water content after moisture absorption of the fabric of Comparative Example 1 which was not treated with the first aqueous solution was as small as 6.0%. It was found that the fabric of Example 1 treated with the first to fourth aqueous solutions had a high moisture content after moisture absorption of 9.2% and had a high hygroscopic property.

[0033]

[Table 2]

<Evaluation 3> Examples 1 to 3 and Comparative Examples 1 to 3
The easiness of drying (drying property) of each of the fabrics treated with 1. was evaluated by the following method. That is, these fabrics were allowed to stand for 24 hours in an atmosphere of 20 ° C. and a relative humidity of 65%, and then the absolute dry weight was measured. Then, these fabrics were dipped in warm water at 40 ° C for 30 minutes and mangled (nip pressure 4 Kg / cm
Dehydrated in ² ) and weighed immediately after dehydration. 20 more
The fabric was weighed after being left for 10 minutes and after being left for 30 minutes in an atmosphere of ℃ and 65% relative humidity.
The results are shown in Table 3. As is clear from Table 3, the first
~ Of the fourth aqueous solution, immediately after dehydration of the fabrics of Comparative Examples 1 to 3 not treated with the first aqueous solution or the second aqueous solution, 10 minutes later,
Immediately after the dehydration of the fabrics of Examples 1 to 3 treated with the first to fourth aqueous solutions, the weights after 10 minutes and after 30 minutes were all smaller than the weight after 30 minutes, in other words, the weight. It was found that the decrease was fast and that it was easy to dry (excellent in drying property).

[0035]

[Table 3]

[0036]

As described above, according to the treatment method of the present invention, since the step of removing the scale of the protein fiber is not included, the protein fiber product can be obtained without damaging the protein fiber and without resin processing. Since shrink resistance can be imparted, a protein fiber product that is friendly to humans and the environment can be obtained without impairing the original advantages of protein fiber. When the protein fiber product for outerwear is subjected to the treatment of the present invention, the protein fiber product has good hygroscopicity and is easily dried. When the protein fiber product for innerwear is subjected to the treatment of the present invention, the protein fiber product is easy to absorb sweat, has a soft touch, and loses the tingling sensation of the conventional protein fiber product represented by wool.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06M 15/00 D06M 3/06 Z // D06M 101: 12 3/10 Z F term (reference) 4L031 AA04 AA05 AB01 AB32 AB33 BA16 BA17 BA33 BA34 DA20 4L033 AA03 AB01 AB05 AB06 AC01 AC15 BA19 CA08

Claims (7)

[Claims] 1. A step of impregnating a protein fiber product in a first aqueous solution containing 0.5 to 3% by weight of an ammonium salt and having a pH of 5.0 to 8.5 and treating at 30 to 60 ° C. for 20 to 60 minutes, Impregnating a second aqueous solution having a pH of 3 to 9 containing 6 to 12% by weight of a morphological stabilizer and 0.1 to 12% by weight of a first protein with the protein fiber product treated with the first aqueous solution; 2 100-130 protein fiber product impregnated with aqueous solution
Step of drying at ℃, 0.5-2.0 wt% organic acid and 0.1-1.2 wt%
10 to 6 at 15 to 35 ° C. by impregnating the dried protein fiber product into a third aqueous solution of pH 1 to 3 containing the second protein of
A step of treating for 0 minutes, and a pH of 7.5 containing 0.1 to 1.5% by weight of an alkaline agent.
9. A method for treating a protein fiber product, comprising the step of impregnating the fourth aqueous solution of 9.5 with the protein fiber product treated with the third aqueous solution and treating at 30 to 50 ° C. for 10 to 60 minutes. 2. The treatment method according to claim 1, wherein the ammonium salt contains at least one of ammonium hydrogen carbonate, ammonium carbonate, ammonium hydrogen sulfate, ammonium sulfate, monoammonium phosphate, diammonium phosphate and triammonium phosphate. 3. The morphological stabilizer is sodium hydrogen sulfite,
The treatment method according to claim 1, comprising at least one of ammonium thioglycolate, monoethanolamine bisulfite, phosphorous acid, and thiourea dioxide. 4. The treatment method according to claim 1, wherein the first protein contains at least one of silk fibroin, animal hair keratin, and animal hair keratose. 5. The treatment method according to claim 1, wherein the organic acid contains at least one of maleic acid, maleic anhydride and tetrathioic acid. 6. The treatment method according to claim 1, wherein the second protein contains at least one of silk fibroin, animal hair keratin, and animal hair keratose. 7. The treatment method according to claim 1, wherein the alkaline agent contains at least one of aqueous ammonia, sodium hydrogen carbonate and disodium hydrogen phosphate.