JP2000234268A - Method for solubilizing animal hair and method of using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a water-soluble animal hair keratin protein, and a method for imparting excellent hygroscopicity to fibers originally having poor hygroscopicity using the water-soluble protein. SOLUTION: Animal hair is added under normal pressure at room temperature to 50 ° C in an aqueous solution whose pH is adjusted to 7 to 9 by adding ammonia to 0.35 to 1.4% by weight of hydrogen peroxide. Pre-treatment step of dipping for 30 minutes, followed by 130-
A pressure heat treatment step of heating at 200 ° C. for 30 to 60 minutes, wherein the animal hair keratin protein is water-solubilized. A polyisocyanate compound in which at least three isocyanate groups in one molecule are blocked by sodium acid sulfite and the water-soluble wool keratin protein in an aqueous solution
A crosslinkable compound obtained by reacting at 0 to 50 ° C. and pH 8 to 11, and a fiber immersed in an aqueous solution of pH 8 in which the crosslinkable compound is dissolved, dehydrated and dried, and then dried at 150 to 160 ° C.
For imparting hygroscopicity to fibers to be heat-treated in step 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for solubilizing animal hair with water and a method for imparting hygroscopicity to fibers using the obtained water-soluble animal hair keratin fiber.

[0002]

2. Description of the Related Art Methods for solubilizing animal hair keratin protein are as follows: (1) Animal hair is sheared and pulverized, immersed in an 8M urea solution at 50 ° C. for 1 day, and sodium nitrite and tetrathionate are placed under a nitrogen atmosphere. Sodium, pH 9.5 for 24 hours, or (2) animal hair is sheared and pulverized and treated with an 8M urea solution at 50 ° C. for 30 minutes, and sodium dodecyl sulfate, 2-mercaptoethanol is added under a nitrogen atmosphere. (3) animal hair is sheared and pulverized, and then 25% with 8M urea solution.
At 30 ° C. for 30 minutes, stirred under a nitrogen atmosphere with 2-mercaptoethanol at pH 10.3 for 3 hours, and stirred with iodoacetic acid at pH 8.5-9.0 for 24 hours to dissolve. And (4) oxidizing animal hair in 70% glacial acetic acid and 30% hydrogen peroxide (v / v) at a bath ratio of 1:30 at 10 ° C. for 24 hours, and then using 0.05M sodium carbonate. A method of treating at a bath ratio of 1: 100, 10 ° C. for 24 hours, and (5)
Using 6N hydrochloric acid in a sealed tube under reduced pressure at 110 ° C., 20-
(6) a method of decomposing by heating for 70 hours, (6) a method of treating with 0.1% w / v trypsin for 10 hours using 0.01 M ammonia acetate / ammonia buffer (pH 7.8), 7) Treatment with 0.1% w / v pronase for 30 hours using 0.01M ammonia acetate / ammonia buffer (pH 7.8), (8) pH 6.7N
The enzyme treatment method of treating with 0.1% w / v papain and 0.2% w / v dithiothreitol for 10 hours using a 0.1 M phosphate buffer solution of animal hair keratin protein Although disclosed as solubilization techniques, these are academic techniques for isolating animal hair tissue and studying the amino acid sequence of animal hair keratin protein. These techniques require that the drug used for solubilization be separated and destroyed,
The processing time is long and cannot be said to be an industrial technique requiring solubilization at low cost. (9) JP-A-9-228249 discloses that treatment is performed by adjusting the pH to about 8 using 35% hydrogen peroxide (stock solution) and ammonia. It is necessary to use and separate and remove hydrogen peroxide after treatment, and it cannot be said to be an economical formulation.

[0003] Also, (10) Japanese Patent Application Laid-Open No. 4-126724 discloses that a water-soluble protein is reacted with a polyisocyanate compound in an aqueous system to make the protein-isocyanate compound insoluble in water. In a reaction system between a polyisocyanate compound in which an isocyanate group is protected by a water-soluble blocking agent and a water-soluble protein, the polyisocyanate compound is liberated by thermal action during the drying treatment. Immediately, the terminal reacts with water contained in the fiber to form an amino group, and self-crosslinking between the amino group and the isocyanate group of the polyisocyanate compound is performed, but the reaction speed is extremely fast. On the other hand, since the crosslinking reaction with the amino group and hydroxyl group in the water-soluble protein is slow, the crosslinking reaction of the protein-isocyanate compound is suppressed, and as a result, Riisoshiane - self-crosslinking by the door compound alone is a major reaction.

[0004] This can be represented by a chemical formula.

Embedded image And, by water and heat, the amino group is released, further heating proceeds, and when dry heat treatment is performed,

Embedded image The self-crosslinking instantaneously and selectively progresses to form a film, as shown in (1), but the reaction with the water-soluble protein (K-NH ₂ , K-OH) is suppressed, resulting in partial cross-linking. Is small, and unreacted proteins are dropped off by the water washing treatment. Solving this problem is one of the main objects of the present invention.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a method for preparing a water-soluble animal hair keratin protein, and a method for imparting excellent hygroscopicity to a fiber which originally has poor hygroscopicity by using the water-soluble protein. Things.

[0006]

According to the present invention, 0.35 to 1.
Add ammonia to 4% by weight concentration of hydrogen peroxide to adjust pH
Animal hair under normal pressure in an aqueous solution adjusted to 7 to 9, room temperature to
A method for water-solubilizing animal hair keratin protein comprising a pretreatment step of immersing at 50 ° C for 10 to 30 minutes and a subsequent pressure treatment step of heating at 130 to 200 ° C for 30 to 60 minutes in a closed state. About. The present invention also provides a water-soluble animal hair keratin protein obtained by the above method and a polyisocyanate compound in which at least three isocyanate groups in one molecule are protected by an acidic sodium sulfite blocking agent, in an aqueous solution at 20 to 50 ° C. It relates to a crosslinkable compound obtained by reacting at a pH of 8 to 11. Furthermore, the present invention
The fiber is immersed in an aqueous solution of pH 8 to 11 in which the above-mentioned crosslinkable compound is dissolved, dehydrated and dried, and then dried.
The present invention relates to a method for imparting hygroscopicity to fibers that are heat-treated at 0 ° C.

[0007] By subjecting animal hair to water-solubilizing treatment by the method of the present invention, a water-soluble animal hair keratin protein can be obtained at low cost. According to the method of the present invention, it is not necessary to remove the drug after treatment. There are features. By applying the water-soluble animal hair keratin protein thus obtained to the fiber surface by the method of the present invention, it is possible to impart high hygroscopicity to fibers that originally have poor hygroscopicity. Furthermore,
The high hygroscopicity imparted by the method of the present invention is excellent in water resistance and organic solvent resistance, and therefore has high durability such as washing resistance.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first subject of the present invention relates to a process for solubilizing animal hair with water. The features of the first subject of the present invention are:
A pretreatment in which animal hair is immersed in an aqueous solution in which 0.35 to 1.4% by weight of hydrogen peroxide is adjusted to pH 7 to 9 by adding ammonia at room temperature to 50 ° C for 10 to 30 minutes under normal pressure. Process followed by 3 hours at 130-200 ° C. in a closed state.
And a pressure heat treatment step of heating for 0 to 60 minutes. Animal hair keratin protein is decomposed in a short time by using a volatile drug, hydrogen peroxide, and ammonia as a pH adjuster, and is subjected to high-temperature and high-pressure treatment in a hermetically sealed condition under weak alkaline conditions. In this method, the drug used does not need to be exterminated and decomposed after the treatment. Therefore, according to the method for solubilizing animal hair of the present invention, animal hair keratin protein that is soluble in water can be obtained at lower cost than animal keratin.

The concentration of hydrogen peroxide used in the method for solubilizing animal hair of the present invention is 0.35 to 1.4% by weight, preferably 0.35 to 0.70% by weight. If the amount is less than 0.35% by weight, animal hair cannot be effectively treated, and satisfactory water solubility cannot be obtained. On the other hand, if hydrogen peroxide having a concentration higher than 1.4% by weight is used, it is necessary to remove excessively remaining hydrogen peroxide, so that the processing cost is increased and satisfactory results cannot be obtained. The pH of the treatment bath is 7-9, preferably 8. p
If H is lower than 7, the activity of hydrogen peroxide is reduced, while if it is higher than 9, animal hair keratin molecules are undesirably hydrolyzed to monomeric amino acids. The pH can be adjusted by an alkalizing agent other than ammonia, but volatile ammonia is preferred in terms of removing and separating the remaining alkalizing agent. The processing temperature and time at room temperature to 50 ° C. for 10 to 30 minutes are sufficient.
If the temperature is lower than room temperature, the treatment takes a long time, and there is no need for cooling. Decomposition of hydrogen peroxide when performed at a temperature higher than 50 ° C,
Ammonia volatilization occurs, and the treatment concentration decreases, and the effect of hydrolysis decreases, which is not preferable. Bath ratio is 1:10
1: 100 is preferable, and about 1:20 is particularly preferable.

In the pressure heat treatment step following the pretreatment step,
The system is kept closed, 130-200 ° C., preferably 130 ° C.
Heat at ~ 150 ° C for 30-60 minutes. If the temperature is lower than 130 ° C., animal hair cannot be sufficiently solubilized. If the temperature is higher than 200 ° C., animal hair keratin protein is hydrolyzed to amino acid monomers, which is not preferable. In order to recover the water-soluble animal hair keratin protein from the treated product thus obtained, for example, it can be separated from the treated solution as a precipitate by adjusting the pH to 4 with acetic acid. In order to use the water-soluble animal hair keratin protein recovered as a precipitate for use as an aqueous solution, the precipitate is adjusted to pH 1 with sodium carbonate.
It is sufficient to dissolve the precipitate in water that has been made 0, and the precipitate is dissolved to obtain an aqueous solution of animal hair keratin protein.

In the pressure heat treatment step, animal hair is sealed in a buffered aqueous solution having a pH of 6.5 to 7.5, for example, pH 7.0, and heated to 130 ° C. to 200 ° C., thereby obtaining animal animal disulfide. The bond breaks and exhibits a second degree of hypershrinkage, which melts. In order to accelerate this phenomenon and to treat the animal hair in a short time, the animal hair is first pretreated in the present invention. The animal hair that can be used is typically wool, other alpaca,
Mohair, angora, cashmere and the like can be exemplified, but not limited to these. The wool is not particularly limited, and various wools can be used. For example, wool as an industrial waste from the wool industry can be used, which, in addition to its volume,
It is preferable from the viewpoint of recycling. The water-soluble animal hair keratin protein obtained according to the present invention is generally a water-soluble suspension having a weight average molecular weight of 3,000 to 100,000. It is soluble in alkali.

A second subject of the present invention relates to a method for imparting hygroscopicity to synthetic fibers or natural fibers using the water-soluble animal hair keratin protein thus obtained. Prior to processing the water-soluble animal hair keratin protein into a fiber, the water-soluble animal hair keratin protein reacts with a polyisocyanate compound having at least three isocyanate groups in the molecule protected by a sodium acid sulfite blocking agent to form a crosslinkable compound. You. The crosslinking compound is prepared by adding a polyisocyanate compound to an aqueous solution in which water-soluble animal hair keratin protein is dissolved, and
It can be formed by stirring at 50 ° C. and reacting both. The pH of the reaction system is preferably adjusted in the range of 8 to 11, more preferably 10 to 11. A reaction of at least 60 minutes is sufficient.

In the above reaction step, the concentrations of the water-soluble animal hair keratin protein and the polyisocyanate compound used in the aqueous solution are 0.1 to 5% by weight and 5 to 2%, respectively.
0% by weight, preferably 0.5 to 2% by weight and 10 to 15% by weight, respectively.

Under the above-mentioned conditions, the polyisocyanate blocked with sodium acid sulfite hydrolyzes at the carbamoylsulfonate group to form an amino group at the terminal under the above-mentioned conditions. The polyisocyanate compound undergoes a cross-linking reaction and cures to form a film. The above reaction is represented by the following chemical reaction formula.

Embedded image In the above reaction, the carbamoylsulfonate group is an isocyanate group blocked with sodium acid sulfite, and the amino group is one generated by hydrolysis of the carbamoylsulfonate group and one derived from a water-soluble animal hair keratin protein.

In the reaction between the blocked polyisocyanate compound and the water-soluble animal hair keratin protein, the blocked polyisocyanate compound is rapidly hydrolyzed at room temperature or higher to release an amino group at a terminal group and self-crosslink. Since the reaction proceeds and the curing proceeds, the reaction with the soluble animal hair keratin protein is inhibited. Therefore, the preferable temperature condition is 20 to 50 ° C., particularly preferably around room temperature.

Here, the water-soluble animal hair keratin protein has a weight average molecular weight of 3,000 to 100,000 in order to impart sufficient water absorption to the fiber and to maintain the durability of its performance. Are preferred, 30,0
It is particularly preferred that the ratio be from 00 to 50,000.

The polyisocyanate compound is a polyisocyanate compound in which at least three isocyanate groups in one molecule are protected by an acidic sodium sulfite blocking agent and has a urethane bond in the molecule. A particularly preferred polyisocyanate compound is represented by the following general formula: It is represented. This compound is commercially available [trade name “PARADEN SSW” (solid content 30%, average molecular weight 3,000)
A mixture of 0 to 10,000; manufactured by Ohara Palladium Chemical Co., Ltd.)] The general formula is shown below.

Embedded image

In the second step of the process of imparting hygroscopicity to the fiber, the reaction is carried out in an aqueous solution in which the polyisocyanate compound partially crosslinked in the first step and the water-soluble animal hair keratin protein are present. In a state where the fiber is immersed in the fiber and these compounds are impregnated, the fiber is heat-treated. That is, by drying and curing at a temperature higher than the dissociation temperature of the blocking agent of the polyisocyanate compound, active isocyanate groups are released, and this is cross-linked with amino groups and / or hydroxyl groups of the water-soluble animal hair keratin protein. And imparts insoluble animal hair keratin protein on the fiber. The dissociation temperature of the sodium acid sulfite as the blocking agent is 50 ° C. or higher, and the curing temperature in the second step is preferably 120 to 180 ° C. A more preferred temperature is 150-160 ° C.

The bath ratio in the second stage is from 1:10 to 1: 5
0, preferably 1:20 to 1:30. The amount of liquid retained in the fiber at the stage of curing is such that the total amount of the water-soluble animal hair keratin protein and the polyisocyanate compound is 0.5 to 5% by weight, preferably 1 to 3% by weight of the fiber.
It is the amount to be% by weight.

The method of coating the fiber with the reaction product of the water-soluble animal hair keratin protein obtained in the first step and the polyisocyanate compound is not particularly limited. A solution in which a water-soluble animal hair keratin protein and the polyisocyanate compound are partially cross-linked with stirring is impregnated using a roller coating, a spray coating, or a padder. It may be a method.

The method of coating the reaction product of the water-soluble animal hair keratin protein with the polyisocyanate compound, that is, the crosslinkable compound, is not particularly limited. Physical attachment, and in some cases, chemical bonding by reaction to a functional group on the fiber, or a binder attachment method may be used. In any case, through the first and second heat treatment steps, the water-soluble animal hair keratin protein binds to the polyisocyanate, becomes insoluble in water while maintaining hydrophilicity, and strongly adheres to the fiber. Therefore, the washing durability of the performance is also excellent.

The fiber treatment method using the water-soluble animal hair keratin protein of the present invention and a polyisocyanate compound blocked by sodium acid sulfite comprises a nylon fiber,
It can be applied to synthetic fibers having poor hygroscopicity, such as polyester fibers and acrylic fibers, but in particular, has a lower relative humidity, for example, RH 20%, as compared with animal hair fibers (RH 20%, 4.25% water content). , Cotton (RH 20%, 3.74% water content) with poor hygroscopicity under RH 40%,
It can also be used for natural fibers of hemp, semisynthetic fibers such as acetate (RH 20%, 1.8% water content), and regenerated fibers such as rayon.

[0023]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. Of course, the present invention is not limited to these. Example 1 200 ml of water and 20 ml of hydrogen peroxide (35%) were placed in a 400 ml container using a MINI-COLOR dyeing machine (manufactured by Texam Giken Co., Ltd.), and adjusted to pH 8.0 with ammonia. Then, 10 g of waste wool from the spinning step was added to this aqueous solution and treated at 50 ° C. for 10 minutes. Next, close the lid of the container and raise the temperature to 130 ° C. at 1 ° C./min.
This temperature was maintained for 30 minutes and then cooled. Through this treatment, the waste wool completely loses its fiber form and has a pH of 6.8.
An aqueous solution of wool keratin protein consisting of a soluble portion and an insoluble portion was obtained. When sodium hydroxide was added to this solution and the pH was adjusted to 8, the insoluble portion was dissolved, and a solution of water-soluble wool keratin protein was obtained. The molecular weight of this solution was measured using high performance liquid chromatography (HPLC). As a result, at 220 nm, Rt (retention time) was 9.220 minutes, at 280 nm, Rt was 0.355 minutes,
Peaks were present at 2.908, 7.338 and 10.020 minutes. From the previously prepared calibration curve of the relationship between Rt and the molecular weight of the protein, it was estimated that the obtained water-soluble wool keratin protein was a mixture of those having molecular weights of about 50,000, about 30,000 and about several thousands.

As described above, the feature of the present invention is that the soluble fraction of the polymer is larger than that of the conventional commercial product, and it is most suitable for the crosslinking treatment with the polyisocyanate compound. The water-soluble wool keratin protein solution was diluted 1/10 and used for a cross-linking reaction with the polyisocyanate compound. FIG. 2 shows the molecular weight distribution (in terms of retention time Rt) of the obtained water-soluble wool keratin protein. Tables 3 and 4 show data on the retention time Rt and the estimated molecular weight.

The measurement of the molecular weight of the water-soluble wool keratin protein by the above HPLC was carried out as follows. 5 ml of a 10% by weight aqueous solution of a water-soluble wool keratin protein was collected,
Adjust the pH to 8 with 1N-NaOH aqueous solution, and
Centrifugation (10,000 rpm) for 10 minutes, filtration through a membrane filter (0.45 μm pore size), dilution by a factor of 10, 100 μL of the solution was passed through high performance liquid chromatography, and the optical density at 210 nm and 280 nm (OD. ) And retention time were measured. HPLC
The measurement conditions by HPLC are as follows: HPLC column: Tosoh TSK-GEL G200
0SW (hydrophilic silica gel) Column flow rate: 1.0 ml / min Temperature: 28 ° C. Elution buffer: 0.1 M sodium phosphate buffer (pH 8)

The above calibration curve of the relationship between Rt and molecular weight of the protein was prepared as follows: protein thyroglobulin of known molecular weight (molecular weight 670,000), bovine serum albumin (molecular weight 67,000) and ribonuclease When measured at 210 nm (molecular weight 13,680), peaks were shown at Rt of 6.028 minutes, 6.963 minutes, and 9.268 minutes, respectively. Further, when paraaminobenzoic acid (molecular weight: 137.13) was measured at 280 nm, one peak was shown at Rt of 11.869 minutes. The data is shown in FIG. 1, Table 1 and Table 2.

[0027]

[Table 1]

[0028]

[Table 2]

The molecular weight of the obtained water-soluble wool keratin protein is estimated to be about 50,000, 30,000 and several thousand based on the relationship between the retention time of the water-soluble wool keratin protein by HPLC and the above molecular weight to retention time. The data is shown in FIG. 2, Table 3 and Table 4.

[0030]

[Table 3]

[0031]

[Table 4]

Example 2 0.05% v / v of a penetrant and 10% v / v of a polyisocyanate compound described below were added to 500 mL of a 1/10 diluted aqueous solution of the water-soluble wool keratin protein obtained in Example 1, pH
Was adjusted to 8 with sodium bicarbonate. After the adjustment, the water-soluble wool keratin protein was reacted with the polyisocyanate compound at room temperature for 1 hour with stirring.
This liquid was padded with a polyester cloth (textile weight: 70 g / m ² ), adhered at a squeezing rate of 100%, dried, and cured at 160 ° C. After the curing treatment, it was washed with hot water, washed with water, and dried.

The polyisocyanate compound used here is a self-emulsifying type self-crosslinking compound having a polyether-based polyurethane bond as a main chain, having an active isocyanate group in a side chain group, and blocked with sodium acid sulfite. It is a water-based polyisocyanate compound "Parazin SSW" (average molecular weight of 4,000 which is a mixture having a solid content of 30% and a molecular weight of 3,000 to 10,000; manufactured by Ohara Palladium Chemical Co., Ltd.). The solid content was adjusted so that 3% was attached to the fiber. This polyisocyanate compound has a unique property, has an anionic dye property on the acidic side, penetrates into wool to the inside of cell tissue, and undergoes a cross-linking reaction with the active group of wool to reduce abrasion resistance. On the other hand, on the alkaline side, it is hydrolyzed to release an amino group at the terminal group,
It is a unique polymer that cures when heated (at 50 ° C. or higher) and cures at 160 ° C. when the blocking agent thermally dissociates to release active isocyanate groups and self-crosslink to cure.

[Fiber Adhesion Evaluation Test] In order to clarify the presence of water-soluble wool keratin protein adhering to fibers,
0 g of the ninhydrin reagent is dissolved in 1000 ml of acetone, this solution is sprayed on the fiber and heated to 100 ° C.,
The color reaction was performed and the evaluation was performed. Table 5 shows the results.

[Hygroscopicity test under RH of 20%] In order to enhance the comfort when wearing clothing, it is necessary to increase the hygroscopicity under low humidity. As a measure, 18 amino acids, especially amino acid, contained in wool keratin protein are used. Is to attach an amino acid having a carboxyl group or a carboxyl group to a fiber. This is the key to increasing hygroscopicity at low relative humidity. A saturated aqueous solution of potassium acetate (CH ₃ COOK) is placed in the bottom of the desiccator, placed in a constant temperature room at 20 ° C. for 24 hours, the relative humidity in the desiccator is set to 20%, and the fiber is placed on top of this.
After standing all day and night, the weight increase of the fiber was measured to determine the moisture absorption. Table 5 shows the results.

[Water repellency test] Based on JIS L 1092: 1998-6.3 rain test (shower test) method, 250 mL of water was added to 25-3.
Spraying was performed at 0 second to examine the wet state of the surface of the fiber cloth. Table 5 shows the results.

[Washing resistance test] Using a domestic electric washing machine, the washing weight was adjusted to 1 kg by combining the polyester attached cloth and the treated fiber cloth, and the washing weight was adjusted to 30 L of room temperature water.
g of household detergent top (manufactured by Lion Corporation)
After washing for 15 minutes, draining, washing with water for 30 minutes, and drying with hot air at 80 ° C. The state of shedding of wool keratin protein coated on the surface of the fiber cloth was evaluated by a ninhydrin color reaction. Table 5 shows the results.

Example 3 A nylon cloth (textile weight: 70 g / m ² ) was treated in the same manner as in Example 2, and the performance evaluation test described in Example 2 was performed. Table 5 shows the results.

Example 4 A cotton fabric (textile weight: 100 g / m ² ) was treated in the same manner as in Example 2, and the performance evaluation test described in Example 2 was performed.
Table 5 shows the results.

COMPARATIVE EXAMPLE 1 A performance evaluation test described in Example 2 was conducted using an untreated polyester cloth (a fabric weight of 70 g / m ² ). Table 5 shows the results.

COMPARATIVE EXAMPLE 2 The performance evaluation test described in Example 2 was performed using an untreated nylon cloth (woven fabric weight: 70 g / m ² ). Table 5 shows the results.

Comparative Example 3 The performance evaluation test described in Example 2 was performed using an untreated cotton cloth (woven fabric weight: 100 g / m ² ). Table 5 shows the results.

Comparative Example 4 In Example 2, a test was conducted on the treated fiber cloth to which only the polyisocyanate compound was adhered without using the water-soluble wool keratin protein to determine whether the protein was adhered on the fiber cloth. investigated. Table 5 shows the results.

Comparative Example 5 In Example 2, washing resistance was measured when only water-soluble wool keratin protein was adhered to the fiber without using a polyisocyanate compound, and the state was examined by a ninhydrite coloring reaction. Table 5 shows the results.

[0045]

[Table 5]

[0046]

It is very important to enhance the hygroscopicity under low relative humidity in order to enhance the comfort of clothing. Animal hair has an amino group, a carboxyl group, and a hydroxyl group as a water adsorption seat, and under low relative humidity, the amino group mainly participates, and the carboxyl group acts on it. Under high relative humidity, hydroxyl groups are involved. Therefore, by attaching the animal hair keratin protein to the target fiber, it is possible to impart a hygroscopic property to natural fibers such as synthetic fibers and cotton having poor hygroscopicity at low relative humidity. Further, the present invention is an ideal treatment method from the viewpoint of resource recycling because waste wool can be used as a raw material. By employing the treatment method of the present invention, a feeling peculiar to the protein treatment can be obtained without impairing the feeling of the treated fiber, and the heat-reactive self-crosslinkable polyisocyanate compound is used to crosslink the water-soluble animal hair keratin protein. It has excellent durability and washing resistance.

[Brief description of the drawings]

FIG. 1 is an HPLC chart showing the relationship between the molecular weight of a compound having a known molecular weight and the retention time. (A) Measurement at 210 nm, (b) Measurement at 280 nm.

FIG. 2 is an HPLC chart showing the molecular weight distribution of the water-soluble wool keratin protein obtained in Example 1. (A) Measurement at 210 nm, (b) Measurement at 280 nm.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takushi Kanda 25-1 Kuroda, Kisogawa-cho, Hagiri-gun, Aichi Prefecture Kurashiki Spinning Co., Ltd. Kisogawa Plant F-term (reference) 4L033 AA01 AA02 AA03 AA04 AB01 AC03 AC07 BA69 BA98 CA08 CA50

Claims (6)

[Claims] 1. Animal hair is added under normal pressure at room temperature to 50 ° C. in an aqueous solution adjusted to pH 7 to 9 by adding ammonia to 0.35 to 1.4% by weight of hydrogen peroxide. A pretreatment step of immersing for 30 minutes, followed by a 130-
A pressure heat treatment step of heating at 200 ° C. for 30 to 60 minutes, wherein the animal hair keratin protein is water-solubilized. 2. A polyisocyanate compound in which at least three isocyanate groups in one molecule are protected by an acidic sodium sulfite blocking agent, and a water-soluble animal hair keratin protein obtained by the method of claim 1, which are used in an aqueous solution.
A crosslinkable compound obtained by reacting at 0 to 50 ° C and pH 8 to 11. 3. The polyisocyanate compound represented by the general formula: The crosslinkable compound according to claim 2, represented by the formula: 4. A fiber immersed in an aqueous solution having a pH of 8 to 11 in which the crosslinkable compound according to claim 2 is dissolved,
A method of imparting hygroscopicity to fibers which is heat-treated at 120 to 180 ° C. after dehydration and drying. 5. The method according to claim 4, wherein the fibers are cotton fibers. 6. A synthetic or natural fiber imparted with hygroscopicity by the method of claim 4.