KR102129971B1 - Method for manufacturing processed fiber and method for inhibiting damage to processed fiber, animal fiber, and method for processing animal fiber - Google Patents

Abstract

The present invention, even when the animal fiber is bleached and / or dyed, the unique texture and light resistance of the fiber is maintained, the manufacturing method of the processed fiber capable of realizing the desired color and the processing fiber, animal fiber damage control Methods and methods of processing animal fibers are provided.
In a method of manufacturing processed fibers by bleaching and/or dyeing animal fibers, it is a method of manufacturing processed fibers including a step of immersing the fibers in a hydrolyzed keratin solution.

Description

Method for manufacturing processed fiber and method for inhibiting damage to processed fiber, animal fiber, and method for processing animal fiber

The present invention relates to a method for manufacturing bleached and/or dyed processed fibers, and to a method for inhibiting damage to processed fibers, animal fibers, and processing methods for animal fibers.

In textile products using animal fibers, texture and color are important factors in determining product value. The texture of the animal fibers is expressed as "soft", "smooth", or "silky", and the state in which the fibers are collected and not subjected to chemical treatment other than refining is the most excellent in texture. Is considered. In addition, although the color is dyed according to the purpose, when a vivid color from white or ultra light blue to light blue is required, it is necessary to bleach the fiber before dyeing. Therefore, conventionally, oxidation bleaching using hydrogen peroxide or reduction bleaching using hydrosulfite or sodium hydrogen sulfite has been performed. However, in these bleaching, a long period of heating and an alkali agent are required, and the fibers are damaged, which causes the softness of the animal fibers and the deterioration of a unique texture such as silkiness.

Therefore, development of a bleaching method that obtains sufficient whiteness without causing texture degradation has been attempted. For example, a bleaching agent containing a polycarboxylic acid-based polymer and an amine-based compound (Patent Document 1), or a method of treating hydroxyalkylphosphine and its derivatives with an alkaline protease (Patent Document 2) Is proposed. However, it cannot be said that it is sufficient in suppressing the deterioration of texture or in light resistance.

In addition, as a method of improving light resistance to animal fibers, for example, a method using an ultraviolet absorber (Patent Document 3), a method of imparting lower phosphoric acid and lower phosphate (patent document 4), and a method of imparting a fluorescent whitening agent ( Patent documents 5) and the like have been proposed. However, the effect is not necessarily sufficient, and the texture is harmed or the safety of the human body is concerned.

On the other hand, a method of binding a protein derived from an animal to an animal fiber and imparting properties of the protein derived from the animal to the fiber has been conventionally proposed (Patent Documents 6 to 8). For example, by using sericin in combination with a dichlorotriazine-based compound to impart durability and form stability (Patent Document 6), in fixing treatment of a shape formed on a cloth of animal protein fiber, the cloth is a collagen protein derivative And fibroin protein solution or keratin soluble solution, thereby maintaining texture and thickness (Patent Document 7), by immersing the protein fiber product in the presence of a water-soluble aqueous protein solution and a crosslinking agent. It has been reported to improve the properties of textile products and to enrich protein fiber products (Patent Document 8).

However, it has not been known until now that keratin hydrolyzate has an effect of suppressing degradation of texture and light resistance of animal fibers caused by bleaching or dyeing treatment.

: Japanese Patent Application Publication No. 2005-146442 : Japanese Patent Application Publication No. 11-172580 : Publication of Japanese Patent Laid-Open No. 2-242970 : Japanese Patent Laid-Open No. 5-156573 : Publication of Japanese Patent Publication No. 2001-518919 : Japanese Patent Application Publication No. 2004-44055 : Japanese Patent Application Publication No. 1-280074 : Japanese Patent Application Laid-open No. 6-341058

The present invention, even when the animal fiber is bleached and / or dyed, the unique texture and light resistance of the fiber is maintained, the manufacturing method of the processed fiber capable of realizing the desired color and the processing fiber, animal fiber damage control It relates to providing a method and a method for processing animal fibers.

The present inventors have conducted extensive studies in view of the above problems, and as a result, in any process in the case of bleaching and/or dyeing animal fibers, the fibers are immersed in a hydrolyzed keratin solution. The damage was suppressed, and it was found that it is possible to manufacture a processed fiber that realizes a desired color while maintaining the texture and light resistance inherent to the animal fiber.

That is, the present invention relates to the following 1) to 10).

1) In a method of manufacturing processed fibers by bleaching and/or dyeing animal fibers, a method of manufacturing processed fibers including a step of immersing the fibers in a hydrolyzed keratin solution.

2) The method of 1), wherein the hydrolyzed keratin solution is a hydrolyzed keratin solution having a concentration of 0.01 to 1% by mass.

3) The method of 1) or 2) in which the step of immersing in the hydrolyzed keratin solution is performed before and after the bleaching and/or dyeing process.

4) The method of any one of 1) to 3), wherein the hydrolyzed keratin is hydrolyzed keratin derived from wool or wool.

5) The method of any one of 1) to 4), wherein the hydrolyzed keratin is a hydrolyzed keratin having a number average molecular weight of 10,000 to 130.

6) Animal fiber is wool, cashmere, mohair, camel hair, llama, alpaca, vicuna, angora, mink and Method of any one of 1) to 5) selected from one or more of silk.

7) The method of any one of 1) to 6) in which the animal fibers are spun yarn.

8) In the bleaching and/or dyeing treatment of animal fibers, a method for inhibiting damage to the fibers comprising the step of immersing the fibers in a hydrolyzed keratin solution.

9) As a method for processing animal fibers, a method comprising immersing the fibers in a hydrolyzed keratin solution before or after bleaching and/or dyeing treatment.

10) Processed fiber produced by any one of 1) to 7).

According to the manufacturing method of the processed fiber of the present invention, the method for inhibiting damage to the animal fiber and the method for processing the animal fiber, it is possible to suppress or repair the fiber damage caused when the animal fiber is bleached and/or dyed. It is possible to manufacture a processed fiber that maintains strength and light resistance without damaging the unique texture it possesses. In addition, since the method of the present invention uses a hydrolyzate of keratin protein derived from nature, it can be carried out without fear of having a great adverse effect on the human body or the environment.

1 is SDS-PAGE of hydrolyzed keratin.
2 is a photograph of the fiber surface before and after dyeing methylene blue.
3 is an ATR-FTIR spectrum of Examples 5 to 7 and Comparative Example 3.
4 is an ATR-FTIR spectrum of Examples 11 to 12 and Comparative Example 3.
5 is a photograph of the fiber surface before and after dyeing methylene blue.

The manufacturing method of the processed fiber of the present invention is a method of manufacturing a processed fiber by bleaching and/or dyeing animal fibers, and includes a step of immersing the fiber in a hydrolyzed keratin solution.

Animal fibers in the present invention, which can be used for spinning (紡績), the form may be any of short fibers, long fibers, spun yarn, knitted fabrics, felts, and also clothing, bedding, cushions, plush toys, etc. It may be a textile product.

Here, as animal fibers, for example, wool, cashmere, mohair, camel hair, llama, alpaca, vicuna, angora ), mink, silk, and the like. These animal fibers may be used alone or in combination of two or more.

The processed fiber of the present invention is obtained by bleaching and/or dyeing the above animal fibers, and thus includes bleached fiber, dyed fiber, bleached and dyed fiber.

In the present invention, the bleaching treatment is a treatment performed to improve the whiteness of animal fibers, for example, using an aqueous solution containing hydrogen peroxide and a surfactant, an aqueous solution containing hydrogen peroxide and sodium silicate, and the like. . In addition, the dyeing treatment is not particularly limited, a liquid flow method, a jigger process, a beam process, a cold pad batch process, a pad steam process, a pad Since a pad roll process, a continuous method, etc. can be used, the dye and dyeing method used may be appropriately selected according to the type of animal fibers.

In the present invention, as the hydrolyzed keratin, there may be mentioned a hydrolyzate obtained by decomposing keratin-containing raw materials or keratin extracted under reducing conditions from the raw materials using acids, alkalis, peroxides, enzymes, and the like, and all methods are known. (For example, Japanese Patent Application Publication No. 2005-247692, Japanese Patent Application Publication No. 2006-124341, Japanese Patent Application Publication No. 2008-247925, Japanese Patent Application Publication No. Hei 6-116300 See). Among these, a hydrolyzate using alkali or peroxide is preferred.

The molecular weight of such hydrolyzed keratin is, in terms of sorption to fibers and permeability, the number average molecular weight measured by gel filtration analysis is preferably 10,000 or less, more preferably 8,000 or less , More preferably 5,000 or less, more preferably 3,000 or less, more preferably 2,000 or less, also preferably 130 or more, more preferably 150 or more, more preferably 200 or more, more preferably 300 or more to be. In addition, it is preferably 10,000 to 130, more preferably 8,000 to 130, more preferably 5,000 to 130, more preferably 3,000 to 150, further preferably 2,000 to 200, and still more preferably 2,000 to 300.

In hydrolysis using alkali or peroxide, the keratin-containing raw material can be decomposed as it is.

For alkali hydrolysis, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali earth metal hydroxides such as calcium hydroxide, and alkalis such as ammonia can be used, and usually 0.1 to 0.8 mol/L, preferably 0.2 to 0.5 It is preferable to treat the keratin-containing raw material at a concentration of mol/L, usually 20 to 120°C, preferably 0.1 to 72 hours.

In addition, hydrolysis using oxidized peroxide (oxidative hydrolysis) is carried out using peroxides such as hydrogen peroxide, formic acid and acetic acid peroxide, usually at a concentration of 1 to 10%, preferably 3 to 8%, usually at room temperature to 100 It is preferable to treat the keratin-containing raw material at ℃, preferably 30 minutes to 48 hours.

Further, such a hydrolyzate can be used as a derivative of hydrolyzed keratin by cationization, silylation, acylation or alkyl cationization, if necessary, and these derivatives can be used as long as the effects of the present invention are exhibited.

Examples of keratin-containing raw materials include hairs such as algae, sheep, horses, pigs, alpaca, mohair, angora, and cashmere. Among them, wool or wool obtained from birds is preferable, and wool It is more preferable to use. Also, for example, ducks, goose, call duck, dometic duck, European duck, Peking duck, such as chicken, quail, turkey, etc. ), any of down, feather, and small feather obtained from a water tank such as an Eider duck can be used, but in particular, a wool of a tank is preferable. Do.

Suitable hydrolyzed keratin in the present invention includes hydrolyzed keratin derived from wool or wool, more preferably hydrolyzed keratin derived from wool, and more preferably alkali hydrolyzed from wool. Degraded keratin or oxidative hydrolyzed keratin.

As a solution of hydrolyzed keratin, a solution of water and ethanol may be mentioned, but it is preferably an aqueous solution.

In the hydrolyzed keratin solution, in the range that does not impair its effect, lipid components such as chelating agents, metal salts, ceramides, fatty acid esters, citric acid, organic acids such as ascorbic acid, nonionic surfactants, cationic surfactants, Various surfactants such as amphoteric surfactants, higher alcohols, lower alcohols, animal and vegetable oils, silicone oils, natural polysaccharides, animal and vegetable extracts, and hydrolyzates derived from animal and vegetable products, derivatives thereof, pH adjusting agents, and preservatives can be appropriately combined.

The concentration of hydrolyzed keratin in the hydrolyzed keratin solution increases the protective and restorative action of animal fibers, and the texture of the hydrolyzed keratin as the sorption amount of the fiber increases. From the viewpoint of suppressing the decrease of, the content is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and also preferably 1% by mass % Or less, more preferably 0.7% by mass or less, and still more preferably 0.5% by mass or less. Moreover, it is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.7% by mass, more preferably 0.05 to 0.7% by mass or more, and still more preferably 0.1 to 0.5% by mass.

Immersion of the animal fibers in the hydrolyzed keratin solution suppresses the deterioration of the protective and restoring effects on the animal fibers due to heat deterioration or reduction of the penetration force, and thus the animal fibers are usually 30 to 80 in the hydrolyzed keratin solution. It is preferable to immerse for 20 to 60 minutes at ℃, and more preferably for 30 to 60 minutes at 40 to 60°C.

The immersion of the animal fibers in the hydrolyzed keratin solution may be performed as a pretreatment step before the bleaching step and/or dyeing step, or as a post treatment step after the bleaching step and/or dyeing step, and may be pretreated. It is more preferable to perform both a process and a post-treatment process. For example, in the case where the dyeing treatment is continued after the bleaching treatment, it is preferable to perform two times before the bleaching process and after the dyeing process, or before the bleaching process, after the bleaching process (before the dyeing process) and three times after the dyeing process.

In the thus obtained processed fiber of the present invention, fiber damage caused when bleaching or dyeing is suppressed or repaired. That is, in the processed fiber of the present invention, the unique texture of the animal fiber (e.g., hand touch) is maintained without being damaged by bleaching or dyeing, and strength and light resistance are not deteriorated. Without being maintained.

Therefore, in the bleaching and/or dyeing treatment of animal fibers, a method including the step of immersing the fibers in a hydrolyzed keratin solution may be a method for inhibiting damage to the fibers in the bleaching and/or dyeing treatment. In addition, before or after bleaching and/or dyeing treatment of animal fibers, a method including a step of immersing the fibers in a hydrolyzed keratin solution may be a processing method for suppressing damage to the fibers.

Such a method for inhibiting damage to an animal fiber and a method for processing the animal fiber are useful for protecting the animal fiber from bleaching and/or dyeing treatment and maintaining the texture or light resistance of the fiber.

In addition, in the present invention, "texture" refers to a feeling of texture when a person touches an object, such as a feeling of touch, a feeling of wearing, or the like when touched by hand, and the unique texture of animal fibers has "softness", " It means smoothness, "silkiness", "voidness", "softness", "elasticity", and "softness".

In addition, light resistance means resistance to light deterioration (yellowing or fading of fibers).

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples.

<Evaluation method>

1. Dyeing (light-resistant) fastness test method (染色(耐光) 堅牢度 試驗法)

The color fastness of the fibers (light resistance) was measured according to JIS L 0842 third exposure method. The higher the grade obtained by this test indicates that the fastness is higher.

2. Fiber damage test method: alkali solubility method

The alkali solubility of the fiber was measured according to JIS L 1081 alkali solubility method. The smaller the value obtained by this test, the less damage the fiber shows.

3. Fiber damage test method: coloring method (methylene blue method)

The degree of damage to the fibers was determined according to the JIS L 1081 coloring method (methylene blue method). Since the fibers without damage are light blue, and those with damage are deep blue, the degree of damage is determined by the color concentration.

4. ATR-FTIR test method

The ATR-FTIR spectrum of the fibers was recorded using a PerkinElmer Spectrum One FTIR spectrophotometer (PerkinElmer, Inc.) attached with Universal ATR Sampling Accessory. It was performed under the conditions of 16 times of integration, 4cm ^{-1 of} resolution and 4000 to 400cm ^-1 . A peak attributed to sulfonic acid is obtained at 1040 cm ^-1 in the obtained spectrum. This sulfonic acid is derived from cystine contained in the fiber, and when the cystine is excessively oxidized, it is cleaved and converted into sulfonic acid. Therefore, the lower the peak of 1040 cm ^-1 indicates that the content of sulfonic acid is small, and that the excess oxidation of the fiber by the bleaching step is suppressed.

5. Elasticity test of yarn

Tensile strength and elongation of the single yarn were measured according to the JIS L 1095 general spinning yarn test method.

6. Panelist evaluation (Sensory evaluation)

Panelist evaluation of specimens was conducted. Twenty-five panelists who had many opportunities to evaluate cashmere fibers for work, touched the specimens arbitrarily, evaluated them by the following criteria for the touch when they were touched by hand, and averaged them.

Evaluation standard

5: Very good

4: Good

3: slightly good

2: Bad

1: Very bad

7. Electrophoresis

SDS-PAGE electrophoresis was carried out using a precast gel (Ato Corporation, e-PAGEL manufactured by ATTO CORPORATION). The dyeing was done by Coomassie Brilliant Blue, and the bleaching was made with 10% acetic acid.

8. Gel filtration chromatography

Gel filtration column: Showa Denko K.K. products, AsahipakGF-510HQ, AsahipakGF-310HQ

Mobile phase: CH ₃ CN/H ₂ O (45/55) + 0.1% trifluoroacetic acid (TFA)

Flow rate: 0.5ml/min

Column temperature: 40℃

UV detection conditions: 215nm

Standard samples: catalase (Mw 230,000), aldolase (Mw 158,000), bovine serum albumin (BSA) (Mw 68,000), ovalbumin (OVA) (Mw 45,000), chymotrypsinogen A (Mw 25,000), cytochrome C (Mw 12,500), Insulin (Mw 5,808), Bacitracin (Mw 1,400), Gly-Gly-Gly-Gly-Gly-Gly (Mw 360.3), Gly-Pro-Ala (Mw 243), Phe (Mw 165)

Preparation Example 1: Preparation of solubilized (non-hydrolysis) keratin derived from wool

To 10 g of wool, 300 mL of an 8M urea solution (pH9.5) containing 0.05M Tris and 0.1M dithiothreitol was added and stirred at 4°C for 24 hours. Thereafter, 7.5 g of sodium sulfite and 18 g of sodium tetrathionate were added, followed by stirring at 4° C. for 24 hours. After removing the lysate by centrifugation, it was adjusted to pH5.2 with hydrochloric acid to prepare solubilized keratin derived from wool without hydrolysis.

Preparation Example 2: Preparation of solubilized (non-hydrolysis) keratin derived from wool

A solubilized keratin derived from wool was prepared by treating in the same manner as in Production Example 1, except that the wool was changed to wool.

Preparation Example 3: Preparation of oxidative hydrolysis keratin derived from wool

10 g of wool was immersed in hydrogen peroxide water, and reacted for 3 hours. Thereafter, ammonia was added to hydrolyze. Residual hydrogen peroxide and undegraded products were removed to prepare oxidative hydrolysis keratin derived from wool.

Preparation Example 4: Preparation of oxidative hydrolysis keratin derived from wool

Oxidative hydrolysis keratin derived from wool was prepared by treating in the same manner as in Production Example 3, except that the wool was changed to wool.

Preparation Example 5 Preparation of alkaline hydrolyzed keratin derived from wool

100 g of 1.3% sodium hydroxide was added to 10 g of wool and reacted at 120° C. for 20 minutes. After cooling to room temperature, it was lowered to pH 4 by hydrochloric acid and left overnight. After removing the un-degraded product by centrifugation, the pH was adjusted to 5.6 with sodium hydroxide to prepare alkali hydrolyzed keratin derived from wool.

Preparation Example 6: Preparation of alkaline hydrolyzed keratin derived from wool

Alkali-hydrolyzed keratin derived from wool was prepared by treating in the same manner as in Production Example 5, except that the wool was changed to wool.

The results of molecular weight analysis by SDS-PAGE of keratin prepared in Preparation Examples 1 to 6 are shown in FIG. 1. In solubilized keratin derived from wool and wool, a band having a molecular weight of 10,000 or more was confirmed, but in hydrolyzed keratin derived from wool and wool, only a band having a molecular weight of 10,000 or less was confirmed. From this, it can be seen that the solubilized keratin derived from wool and wool contains keratin molecules having a molecular weight of 10,000 or more, and the hydrolyzed keratin derived from wool and wool contains only keratin molecules having a molecular weight of 10,000 or less.

In addition, the results of molecular weight measurement by gel filtration molecular weight analysis of keratin prepared in Preparation Examples 3 to 6 are shown in Table 1. It can be seen that, regardless of the origin of the keratin-containing raw material and the method of hydrolysis, keratin molecules having a number average molecular weight of around 1000 are included.

Examples 1 to 4 and Comparative Examples 1 to 2 (keratin treatment before and after bleaching)

(Example 1)

Cashmere hair was immersed in a 0.1% aqueous solution of oxidatively hydrolyzed keratin derived from the wool produced in Preparation Example 4 at a temperature of 40°C for 60 minutes, and pretreated. Subsequently, the solution added with 20 cc/L of 35% hydrogen peroxide was immersed at a liquid ratio of 1:20 and bleached at 60°C for 1 hour. After bleaching, it was immersed in a 0.1% hydrolyzed keratin solution at a liquid ratio of 1:20 and a temperature of 40°C for 60 minutes, followed by post-treatment. After sufficiently washed with water, it was dried to prepare hairs treated with oxidative hydrolysis keratin derived from rain.

(Example 2)

Processed in the same manner as in Example 1, except that the oxidative hydrolyzed keratin derived from the wool was replaced with the alkali hydrolyzed keratin derived from the wool produced in Production Example 6, to prepare a hair treated with alkali hydrolyzed keratin derived from the wool. Did.

(Example 3)

Processed in the same manner as in Example 1, except that the oxidative hydrolyzed keratin derived from the wool was changed to the oxidative hydrolyzed keratin derived from the wool prepared in Production Example 3, to prepare a hair treated with oxidative hydrolyzed keratin derived from the wool. Did.

(Example 4)

Processed in the same manner as in Example 1, except that the oxidative hydrolyzed keratin derived from the wool was changed to the alkali hydrolyzed keratin derived from the wool prepared in Production Example 5, to prepare a hair treated with alkali hydrolyzed keratin derived from the wool. Did.

(Comparative Example 1)

The same procedure as in Example 1 was carried out except that the oxidative hydrolyzed keratin derived from the wool was changed to the solubilized keratin derived from the wool prepared in Production Example 1 to prepare a hair treated with solubilized keratin derived from the wool.

(Comparative Example 2)

The same procedure as in Example 1 was carried out except that the oxidative hydrolyzed keratin derived from the hair was replaced with the solubilized keratin derived from the hair produced in Production Example 2, to prepare a hair treated with the solubilized keratin derived from the wool.

(result)

Table 2 shows the fiber damage test results and panelist evaluation (touch when touched) of Examples 1 to 4 and Comparative Examples 1 and 2, respectively. Compared to Comparative Examples 1 and 2 not treated with hydrolyzed keratin, in Examples 1 to 4 treated with hydrolyzed keratin, fiber damage due to bleaching was suppressed and deterioration of the unique texture of cashmere fibers was suppressed. You can see.

Fig. 2 shows photographs of fibers 1 and 4 before and after Comparative Examples 1 and 2 and untreated methylene blue dyeing. Since there is no damage to the fiber in light blue color, and the damage is in deep blue, it is possible to evaluate the fiber damage by the color concentration. In Fig. 2, Comparative Examples 1-2 are markedly darker than untreated. Examples 1 to 4 are lighter colored than Comparative Examples 1 to 2, and in particular, Examples 1 to 2 are colored to the same extent as untreated. From this, it can be seen that Examples 1 to 4 also inhibit fiber damage due to bleaching, as in the alkali solubility method, in the evaluation by the methylene blue dyeing method.

From the results of evaluating the degree of fiber damage and the feel when touched by hand, it can be seen that keratin having a high effect of suppressing fiber damage due to bleaching is hydrolyzed keratin having an average molecular weight of 10,000 or less.

Examples 5-7 and Comparative Example 3 (keratin treatment before bleaching)

(Example 5)

Cashmere hairs having different origins from those used in Example 1 were immersed in an oxidative hydrolysis keratin solution derived from 0.5% wool for 30 minutes at a liquid ratio of 1:20 at a temperature of 40° C. and pretreated. Thereafter, the solution added with 20 cc/L of 35% hydrogen peroxide was immersed at a liquid ratio of 1:20, and bleached at 60°C for 1 hour. After sufficiently washed with water, it was dried to prepare hairs treated with hydrolyzed keratin.

(Example 6)

The same treatment as in Example 5 was carried out except that the oxidative hydrolyzed keratin solution originating from the wool was immersed at 60°C to prepare a hair treated with hydrolyzed keratin.

(Example 7)

The same treatment as in Example 5 was carried out except that the oxidative hydrolyzed keratin solution derived from the wool was immersed at 80°C to prepare a hair treated with hydrolyzed keratin.

(Comparative Example 3)

The same cashmere hair as that used in Example 5 was immersed in a solution to which 20 cc/L of 35% hydrogen peroxide was added at a liquid ratio of 1:20, and bleached at 60°C for 1 hour. After washing with water sufficiently, the hair was not treated with keratin to prepare a hair.

(result)

1) Table 3 shows the fiber damage test results of the untreated mothers and Examples 5 to 7 and Comparative Example 3. As compared with Comparative Example 3, it was found that in Examples 5 to 7, the fiber damage degree was lowered, and fiber damage due to bleaching was suppressed.

2) ATR-FTIR spectra of untreated parent, Examples 5 to 7 and Comparative Example 3 are shown in FIG. 3. Since all the untreated, but can see the peak attributable to the acid from 1040cm ^-1, for example, it is carried out 5 to 7 and Comparative Example 3, can view the peak attributable to the acid from 1040cm ^-1, which is taking place over-oxidation by the bleach Suggests that However, Examples 5 to 7 have a weak peak intensity of 1040 cm ^-1 compared to Comparative Example 3, which suggests that excessive oxidation by bleaching is suppressed.

Example 8 (Keratin treatment after bleaching)

(Example 8)

The bleached cashmere hair was immersed in an oxidative hydrolysis keratin solution derived from 0.1% of wool for 60 minutes at a liquid ratio of 1:20 and a temperature of 40°C. After washing with water sufficiently, the hair treated with hydrolyzed keratin was produced.

(result)

Table 8 shows the fiber damage and light fastness of Example 8 and bleached cashmere wool. In Example 8, the fiber damage level was lower than that of the bleached cashmere wool, which suggests that the fiber damage was recovered. In addition, the light fastness is increased, which suggests that the light fastness is increased.

Examples 9 to 10 (keratin treatment after bleaching and dyeing)

(Example 9)

The bleached and dyed cashmere hair was immersed in an oxidative hydrolysis keratin solution derived from 0.5% wool for 20 minutes at a liquid ratio of 1:20 and a temperature of 60°C. After sufficiently washed with water, it was dried to prepare hairs treated with hydrolyzed keratin.

(Example 10)

The same treatment as in Example 7 was carried out except that the oxidative hydrolyzed keratin solution derived from the wool was immersed at 80°C to prepare a hair treated with hydrolyzed keratin.

(result)

Tables 9 and 10 show the light fastness properties of bleached and dyed cashmere wool. Examples 9 and 10 have high light fastness.

Examples 11-12 (keratin treatment before and after bleaching)

(Example 11)

The same cashmere hair as used in Example 5 was immersed in an oxidative hydrolysis keratin solution derived from 0.1% of wool at a liquid ratio of 1:20 at a temperature of 40° C. for 60 minutes, and pretreated. Thereafter, the solution added with 20 cc/L of 35% hydrogen peroxide was immersed at a liquid ratio of 1:20, and bleached at 60°C for 1 hour. After bleaching, the solution was immersed in an oxidative hydrolysis keratin solution derived from 0.1% of wool at a liquid ratio of 1:20 at a temperature of 40° C. for 60 minutes, followed by post-treatment. After sufficiently washed with water, it was dried to prepare hairs pre- and post-treated with hydrolyzed keratin.

(Example 12)

The same treatment as in Example 9 was carried out except that the oxidative hydrolyzed keratin solution derived from the wool was immersed at 30°C to prepare a hair treated with hydrolyzed keratin.

(result)

1) Table 6 shows the results of the fiber damage test and panelist evaluation of the untreated mothers, Examples 11 to 12 and Comparative Example 3. In Examples 11 to 12, compared with Comparative Example 3, the degree of fiber damage was lowered. In addition, light fastness is also increasing. In the evaluation of the touch when touched by the panelist, it can be seen that in Examples 11 and 12, the decrease in the touch was suppressed. Therefore, while maintaining the unique texture and light resistance of the fibers, it was possible to obtain an excellent quality animal fiber spun yarn.

2) The untreated parent, the ATR-FTIR spectra of Examples 11 to 12 and Comparative Example 3 are shown in Fig. 4. Peaks attributed to sulfonic acid cannot be seen at 1040 cm ^-1 in untreated hair, but peaks attributed to sulfonic acid at 1040 cm ^-1 can be seen in Examples ¹¹ to 12 and Comparative Example 3, which causes overoxidation by bleaching. Suggests that However, Examples 11 to 12 have a weak peak intensity of 1040 cm ^-1 compared to Comparative Example 3, which suggests that excessive oxidation by bleaching is suppressed.

Examples 13-14 (keratin treatment before and after bleaching and dyeing)

(Example 13)

The same cashmere hair as used in Example 5 was immersed in an oxidative hydrolysis keratin solution derived from 0.1% of wool at a liquid ratio of 1:20 at a temperature of 80°C for 30 minutes, and pretreated. Thereafter, the solution added with 20 cc/L of 35% hydrogen peroxide was immersed at a liquid ratio of 1:20, and bleached at 60°C for 1 hour. After bleaching, it was dyed using 0.03% acid dye. The cashmere hair after bleaching and dyeing was immersed in an oxidative hydrolysis keratin solution derived from 0.1% of wool at a liquid ratio of 1:20 at a temperature of 80°C for 30 minutes, followed by post-treatment. After sufficiently washed with water, it was dried to prepare hairs pre- and post-treated with hydrolyzed keratin.

(Example 14)

The same treatment as in Example 13 was carried out except that the solution was immersed in an oxidative hydrolysis keratin solution derived from 0.5% of wool to prepare a hair treated with hydrolysis keratin.

(Comparative Example 4)

The same cashmere hair as that used in Example 5 was immersed in a solution to which 20 cc/L of 35% hydrogen peroxide was added at a liquid ratio of 1:20, and bleached at 60°C for 1 hour. After bleaching, it was dyed using 0.03% acid dye. After washing with water sufficiently, the hair was not treated with keratin to prepare a hair.

(result)

Table 7 shows the fiber damage and light fastness of Examples 13, 14 and Comparative Example 4. In comparison with Comparative Example 4, Examples 13 and 14 showed a decrease in fiber damage, which suggests that fiber damage is suppressed. In addition, the light fastness is increased, which suggests that the light fastness is increased.

Example 15, Comparative Example 5 (Keratin treatment before and after bleaching <spun yarn>)

(Example 15)

The wool yarn after spinning was immersed in an oxidative hydrolysis keratin solution derived from 0.1% of wool at a liquid ratio of 1:20 at a temperature of 40° C. for 60 minutes, and pretreated. Thereafter, the solution added with 20 cc/L of 35% hydrogen peroxide was immersed at a liquid ratio of 1:20, and bleached at 60°C for 1 hour. After bleaching, the solution was immersed in an oxidative hydrolysis keratin solution derived from 0.1% of wool at a liquid ratio of 1:20 at a temperature of 40° C. for 60 minutes, followed by post-treatment. After washing with water sufficiently, a wool spun yarn treated with hydrolyzed keratin was produced.

(Comparative Example 5)

After spinning, the wool yarn was immersed in a solution to which 20 cc/L of 35% hydrogen peroxide was added at a liquid ratio of 1:20, and bleached at 60°C for 1 hour. After sufficiently washed and dried, a bleached wool spun yarn was produced.

(result)

Table 8 shows the strength and elongation of yarns of yarns, Example 15 and Comparative Example 5. Compared with Comparative Example 5, in Example 15, since the value close to the yarn before bleaching was found, it was found that there was little change in physical properties of the yarn due to bleaching.

Examples 16-20 and Comparative Examples 6-10 (keratin treatment before and after bleaching <spun yarn>)

(Example 16)

The same procedure as in Example 15 was carried out except that the wool yarn was changed to cashmere yarn, thereby producing a cashmere spun yarn treated with hydrolyzed keratin.

(Example 17)

The same procedure as in Example 15 was performed except that the wool yarn was changed to a silk yarn, and a silk spun yarn treated with hydrolyzed keratin was produced.

(Example 18)

An alpaca spun yarn treated with hydrolyzed keratin was produced in the same manner as in Example 15, except that the wool yarn was changed to alpacasa.

(Example 19)

The same procedure as in Example 15 was carried out except that the wool yarn was changed to a 80% wool, 20% wool blended yarn, and a mixed spun yarn treated with hydrolyzed keratin was produced.

(Example 20)

The same procedure as in Example 15 was performed except that the wool yarn was changed to Angora yarn, thereby producing an Angora spun yarn treated with hydrolyzed keratin.

(Comparative Examples 6 to 10)

The same woolen yarn used in Examples 16 to 20 was immersed in a solution added with 20 cc/L of 35% hydrogen peroxide at a liquid ratio of 1:20, and bleached at 60°C for 1 hour. After washing with water sufficiently, a spun yarn not treated with keratin was produced.

(result)

Table 9 shows the strength and elongation of yarns of each animal hair, Examples 16 to 20, and Comparative Examples 6 to 10. Bleaching tends to lower the strength and elongation of the yarn. It can be seen that treatment with keratin suppresses a decrease in yarn strength and elongation.

(Example 21)

Cashmere hair was pretreated by immersion in a commercially available 0.1% aqueous solution of hydrolyzed keratin (average molecular weight 1,000) at a temperature of 40°C for 60 minutes. Thereafter, the solution added with 20 cc/L of 35% hydrogen peroxide was immersed at a liquid ratio of 1:20, and bleached at 60°C for 1 hour. After bleaching, it was immersed in a 0.1% hydrolyzed keratin solution at a liquid ratio of 1:20 and a temperature of 40°C for 60 minutes, followed by post-treatment. After sufficiently washed with water, it was dried to prepare hairs treated with hydrolyzed keratin.

(Comparative Example 11)

The same procedure as in Example 21 was carried out except that the hydrolyzed keratin was changed to a commercially available hydrolyzed collagen (average molecular weight of 1,000) to prepare a mother treated with hydrolyzed collagen.

(Comparative Example 12)

The same procedure as in Example 21 was carried out except that the hydrolyzed keratin was changed to a commercially available hydrolyzed silk (average molecular weight of 1,000), to prepare hairs treated with hydrolyzed silk.

(result)

Table 21 shows the fiber damage test results (alkali solubility method) and light fastness of Example 21 and Comparative Examples 11 to 12. Compared to Comparative Examples 11 to 12 treated with hydrolyzed collagen and hydrolyzed silk, Example 21 treated with hydrolyzed keratin showed the lowest fiber damage and the highest light fastness.

Fig. 5 shows photographs of the fiber surface before and after dyeing methylene blue of Examples 21 and Comparative Examples 11 to 12. Since there is no damage to the fiber in light blue color, and the damage is in deep blue, it is possible to evaluate the fiber damage by the color concentration. In Fig. 5, Comparative Examples 11 to 12 are markedly darker than untreated. Example 21 is lighter colored than Comparative Examples 11 to 12. From this, it can be seen that, in the evaluation by the methylene blue dyeing method, Example 21 suppresses fiber damage due to bleaching as in the alkali solubility method. Therefore, it can be seen that among the hydrolyzed proteins, hydrolyzed keratin is effective in suppressing fiber damage.

Claims (11)

In the method of manufacturing processed fibers by bleaching and / or dyeing animal fibers,
And immersing the animal fiber in a hydrolysis keratin solution having a number average molecular weight of 150 to 3,000.
The immersion process is performed before and after the bleaching and/or dyeing process ,
The animal fibers are wool, cashmere, mohair, camel hair, llama, alpaca, vicuna, angora, mink ( mink) and one or more selected from the group consisting of silk
Method for manufacturing processed fibers.
According to claim 1,
In the immersion step, the hydrolyzed keratin solution is an aqueous hydrolyzed keratin solution having a concentration of 0.01 to 1% by mass.
Method for manufacturing processed fibers.
delete According to claim 1,
The hydrolyzed keratin is hydrolyzed keratin derived from feathers.
Method for manufacturing processed fibers.
According to claim 1,
The hydrolyzed keratin is a hydrolyzed keratin having a number average molecular weight of 300 to 2,000.
Method for manufacturing processed fibers.
delete The method of any one of claims 1, 2, 4 or 5 ,
The animal fibers processed in the immersion process are wool or yarn before becoming fabric.
Method for manufacturing processed fibers.
Number average molecular weight before and after bleaching and/or dyeing one or two or more animal fibers selected from the group consisting of wool, cashmere, mohair, camel hair, llama, alpaca, vicuna, angora, mink and silk Including the immersion process to immerse in the 150-3,000 hydrolysis keratin solution
Method for inhibiting damage to animal fibers.
Number average molecular weight before and after bleaching and/or dyeing one or two or more animal fibers selected from the group consisting of wool, cashmere, mohair, camel hair, llama, alpaca, vicuna, angora, mink and silk Including the immersion process to immerse in the 150-3,000 hydrolysis keratin solution
Animal fiber processing method.
Processed fiber produced by any one of claims 1, 2, 4 or 5 .
The method of any one of claims 1, 2, 4 or 5 ,
By the immersion process, damage to animal fibers caused by bleaching and/or dyeing treatment is suppressed.
Method for manufacturing processed fibers.

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