JP2000064173A - Treatment of regenerated collagen fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for treating a regenerated collagen fiber having low water absorptivity and excellent touch in a wet state and capable of allowing a carboxyl group to be also chemically modified by treating the regenerated collagen fiber with a halogenated aldehyde, and subjecting the treated fiber to an amidation reaction by using a specific diamine and a condensing agent. SOLUTION: A regenerated collagen fiber is subjected to an insolubilizing treatment with a halogenated aldehyde of the formula XnRCHO [X is a halogen; R is a <=3C hydrocarbon; (n) is an integer of 1-3], e.g. 2-chloroacetaldehyde, and the treated fiber is further subjected to an amidation treatment by using a diamine of the formula H2N(CH2)nSS(CH2)mNH2 [(n) and (m) are each an integer of 1-4] or H2NCH(COOR1)CH2SSCH2CH(COOR2)NH2 (R1 and R2 are each a 1-4C alkyl or benzyl) having a disulfide bond, e.g. cystamine dihydrochloride, and a condensing agent, e.g. 1-ethyl-3-(3'-dimethylaminopropyl) carbodiimide hydrochloride.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating regenerated collagen fibers for improving water absorption. For more details,
The present invention relates to a method for treating regenerated collagen fibers, which has a good feel when wet and is suitable for use as a substitute for human hair, animal hair, gut, etc., because the water absorption is reduced by treatment with a halogenated aldehyde.

[0002]

BACKGROUND OF THE INVENTION Regenerated collagen fibers are generally made from animal skins or bones, which are treated with an alkali or enzyme to decompose and remove the telopeptide portion of collagen to give water-soluble collagen. It is generally produced by a method of spinning and forming a fiber. Regenerated collagen fibers have been applied to various fields since they express high strength in the same manner as silk among protein fibers. In particular, since regenerated collagen fiber is a protein fiber that retains a characteristic molecular structure, its texture, gloss, and texture are similar to those of human hair, which is a natural protein fiber and has an extremely complicated fine structure. There is. Therefore, attempts have been made to use it for animal hair fibers such as hair and fur.

Generally, regenerated collagen fibers are produced by treating insoluble collagen with an alkali or an enzyme to make it soluble and then spinning it into an aqueous solution of an inorganic salt. Since the regenerated collagen fiber obtained is dissolved in water as it is, it is insolubilized. As a method of insolubilizing the regenerated collagen fiber, a method of treating with an aqueous aldehyde solution such as formaldehyde or glutaraldehyde or various chromium salts,
A method of treating with a metal salt such as an aluminum salt or a zirconium salt is known. These methods are generally known in the leather industry and are effective for leather containing insoluble collagen as a main component, but for regenerated collagen fibers made of solubilized collagen in a wet state. Has a high water absorption rate, which may lead to poor touch and mechanical strength due to swelling. In particular, the method of treating with the above-mentioned aqueous aldehyde solution was not satisfactory because the water absorption of the regenerated collagen fiber after treatment did not sufficiently decrease. Further, among the methods of treating with the metal salt, there is a method capable of reducing the water absorption rate, but since the metal salt blocks the carboxyl group which is a reactive group, it is chemically modified to the carboxyl group. It was not possible to add new functions such as permanent wave. (The permanent wave treatment described here is to give the hair an arbitrary shape having a holding property by a redox reaction by a drug at a beauty salon or at home.)

[0004]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for treating regenerated collagen fibers which has a low water absorption property, an excellent feel when wet, and a chemical modification to carboxyl groups.

[0005]

[Means for Solving the Problems] In view of the above situation, the present inventors have conducted extensive studies and as a result, when the amino groups of collagen molecules were treated with halogenated aldehydes, the water absorption rate of regenerated collagen fibers decreased. This has led to the completion of the present invention. Moreover, the regenerated collagen fiber obtained by the treatment of the present invention can be made into a fiber capable of permanent wave treatment and having improved water absorption by chemically modifying the carboxyl group to introduce a disulfide bond. That is, the present invention is a method for treating regenerated collagen fibers, which comprises treating with a halogenated aldehyde represented by the following general formula (I).

[0006]

[Chemical 4]

(In the formula, X is a halogen atom, R is a carbon atom of 3
The following hydrocarbon groups, n shows the integer of 1-3. ) Further, the halogenated aldehyde is preferably 2-chloroacetaldehyde. Further, the regenerated collagen fiber treated by the above method, a diamine having a disulfide bond, and a condensing agent may be used for an amidation reaction.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As a raw material for collagen used in the present invention, it is preferable to use a part of the floor skin. The floor skin is obtained from fresh rawhide obtained by slaughtering an animal such as cow or salted rawhide. Most of these floor skins and the like are made of insoluble collagen, but they are usually used after removing the flesh-like portion adhered in a reticulated form and removing the salt used for preventing spoilage and deterioration.

The insoluble collagen is glyceride,
Impurities such as lipids such as phospholipids and free fatty acids, glycoproteins, proteins other than collagen such as albumin are present. These impurities have a great influence on spinning stability, quality such as gloss and strength and elongation, odor, etc. in forming fibers, and therefore, for example, lime is used to hydrolyze the fat content in insoluble collagen to convert collagen into collagen. After unraveling, it is desirable to remove the impurities in advance by subjecting the leather treatment such as acid / alkali treatment, enzyme treatment, solvent treatment, etc. which has been generally performed conventionally.

The insoluble collagen treated as described above is subjected to a solubilization treatment in order to cleave the cross-linked peptide portion. As a method of such solubilization treatment, a generally adopted known alkali solubilization method, enzyme solubilization method, or the like can be applied. When the alkali solubilization method is applied, it is preferably neutralized with an acid such as hydrochloric acid. As an improved method of the conventionally known alkali solubilization method, Japanese Patent Publication No. 46-
The method described in 15033 may be adopted.

The enzyme solubilization method has the advantage that regenerated collagen having a uniform molecular weight can be obtained, and is a method that can be preferably used in the present invention.
As such an enzyme solubilization method, for example, Japanese Patent Publication No.
The method described in Japanese Patent Publication No. 829, Japanese Patent Publication No. 432753/43, or the like can be used. In addition, in the present invention, the alkali solubilization method and the enzyme solubilization method may be used in combination.

When the solubilized collagen is further subjected to operations such as pH adjustment, salting-out, washing with water and solvent treatment, regenerated collagen having excellent quality can be obtained. It is preferable to perform these treatments. The obtained solubilized collagen has, for example, 1 to 15
Wt%, especially 2 to 10% by weight to prepare a stock solution with a predetermined concentration of hydrochloric acid, acetic acid, acid such as lactic acid, pH 2 to
It is dissolved using an acidic solution adjusted to 4.5. In addition,
The obtained collagen aqueous solution may be subjected to defoaming under reduced pressure stirring as necessary, or may be filtered to remove fine dust which is a water-insoluble matter. The resulting solubilized collagen aqueous solution, if necessary, further stabilizers for the purpose of improving mechanical strength, improving water resistance and heat resistance, improving gloss, improving spinnability, preventing coloration, preserving, etc. An appropriate amount of additives such as a water-soluble polymer compound may be blended.

Regenerated collagen fibers are formed by discharging the solubilized collagen aqueous solution through, for example, a spinning nozzle or a slit and immersing it in the inorganic salt aqueous solution. As the inorganic salt aqueous solution, for example, an aqueous solution of a water-soluble inorganic salt such as sodium sulfate, sodium chloride or ammonium sulfate is used, and the concentration of these inorganic salts is usually 10 to 40% by weight.
Adjusted to. The pH of the inorganic aqueous solution is usually adjusted to pH 2 to 13, preferably pH 4 to 12 by adding a metal salt such as sodium borate or sodium acetate, hydrochloric acid, acetic acid, boric acid, sodium hydroxide or the like. Preferably. If the pH is less than 2 or more than 13, the peptide bond of collagen is likely to be hydrolyzed, and it tends to be difficult to obtain the target fiber. The temperature of the aqueous solution of the inorganic salt is not particularly limited, but is usually preferably 35 ° C or lower. When the temperature is higher than 35 ° C, the soluble collagen is denatured and the strength of the spun fiber is reduced, which makes it difficult to manufacture a stable yarn. The lower limit of the temperature is not particularly limited and may be appropriately adjusted usually according to the solubility of the inorganic salt.

The obtained regenerated collagen fiber may be stored in a high-concentration salt aqueous solution, an organic solvent such as water-soluble alcohols, aldehydes and ketones, or an aqueous solution thereof, if necessary. Alternatively, the stored fiber may be dried. Further, it may be further dried and then treated with another organic solvent or an aqueous solution of an organic solvent, or may be stored.

In the present invention, the regenerated collagen fiber described above is treated with a halogenated aldehyde represented by the following general formula (I) to react the amino group of the collagen molecule with the halogenated aldehyde.

[0016]

[Chemical 5]

(In the formula, X is a halogen atom, R is a carbon atom of 3
The following hydrocarbon groups, n shows the integer of 1-3. ) Specific examples of X in the general formula (I) include fluorine, chlorine, bromine and iodine. Specific examples of R in the general formula (I) include a methyl group, an ethyl group and a propyl group. Specific examples of the aldehyde represented by the general formula (I) include 2-chloroacetaldehyde, 2-bromoacetaldehyde, 3-fluoropropionaldehyde, 2-fluoropropionaldehyde, 3-chloropropionaldehyde, 2-chloropropionaldehyde, 3-bromopropionaldehyde, 2-bromopropionaldehyde, 3-iodopropionaldehyde, 2-iodopropionaldehyde, 4-fluorobutyraldehyde,
3-fluorobutyl aldehyde, 2-fluorobutyraldehyde, 4-chlorobutyraldehyde, 3-chlorobutyraldehyde, 2-chlorobutyraldehyde, 4-bromobutyraldehyde, 3-bromobutyraldehyde,
2-bromobutyraldehyde, 4-iodobutyraldehyde, 3-iodobutyraldehyde, 2-iodobutyraldehyde, 3-fluoro-2-methylpropionaldehyde, 3-chloro-2-methylpropionaldehyde, 3-bromo-2- Methyl propionaldehyde, 3
-Iodo-2-methylpropionaldehyde, 3-fluoroacrolein, 3-chloroacrolein, 3-bromoacrolein, 3-iodoacrolein, 4-fluorocrotonaldehyde, 4-chlorocrotonaldehyde, 4-bromocrotonaldehyde, 4-iodo Examples thereof include crotonaldehyde, and among them, 2-chloroacetaldehyde, which has high solubility in water and is inexpensive and easily available, is particularly preferable.

2-Chloroacetaldehyde is also called chloroacetaldehyde, monochloroacetaldehyde, 2-chloroethanal, and 2-chloro-1-ethanal, all of which refer to the same compound.
The treatment method of the present invention is performed, for example, by immersing the regenerated collagen fiber in a halogenated aldehyde aqueous solution, and the concentration of the halogenated aldehyde aqueous solution is determined by the solubility in water.

Taking 2-chloroacetaldehyde as an example, the concentration of the aqueous 2-chloroacetaldehyde solution is 0.05 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to It is adjusted to be 5% by weight. When the concentration of the aldehyde is less than 0.05% by weight, it becomes difficult to obtain the effect of decreasing the water absorption rate because the reaction is difficult to proceed, and when it exceeds 10% by weight, the effect of decreasing the water absorption rate is satisfactory. However, it is not preferable in terms of industrial handleability and environment.

The aqueous solution of halogenated aldehyde has a pH of 4-1.
3, preferably pH 6-9 is desirable. When the pH is 4 or less, the reaction with the amino group of collagen becomes slow or the reaction does not proceed. If the pH exceeds 13, the peptide bond of collagen is likely to be hydrolyzed, and the desired fiber tends to be difficult to obtain. Also,
Since the pH of the 2-chloroaldehyde aqueous solution decreases with time, the pH may be adjusted if necessary.

The treatment temperature of the regenerated collagen fiber with the halogenated aldehyde aqueous solution is 50 ° C. or lower, and the immersion time is 5 minutes or longer. If the treatment temperature exceeds 50 ° C., the regenerated collagen fibers will be denatured and the strength of the obtained fibers will decrease, making stable yarn production difficult. If necessary, the regenerated collagen fibers treated with halogenated aldehydes may contain, for example, monoaldehydes such as formaldehyde, acetaldehyde, methylglyoxal, acrolein; glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, dialdehyde starch, Dialdehydes; epoxy compounds such as glycidyl ethers of glycols and polyols, monocarboxylic acids, glycidyl esters of dicarboxylic acids and polycarboxylic acids; ureas, melanins, acrylamides, acrylic acid amides, and N-derived from polymers thereof. Methylol compound; Water-soluble polyurethane prepared by introducing isocyanate into polyol or polycarboxylic acid and adding sodium bisulfite; Monochlorotriazine or dichlorotriazine Derivatives of sulfuric acid ester or vinyl sulfone oxyethyl sulfone; derivatives of trichloromethyl pyridine; triazine derivatives such as derivatives of dichloroacetic Kino affectation phosphorus;
N-methylol derivative; isocyanate compound; phenol derivative; aromatic group having a hydroxyl group represented by tannin; treatment with a cross-linking agent such as a cation of a metal represented by aluminum, chromium, titanium, zirconium, etc. .

In the present invention, the regenerated collagen fibers are washed with water, oiled and dried, if necessary. Washing with water prevents precipitation of the oil agent due to salt,
Salt is precipitated from the regenerated collagen fiber during drying in the dryer, and the salt causes breakage in the regenerated collagen fiber, and the generated salt is scattered in the dryer and adheres to the heat exchanger in the dryer to increase the heat transfer coefficient. This is to prevent a decrease in When oiling is applied, the effect of preventing the fibers from sticking can be further enhanced during drying. In addition, the shape of the fiber can be made more stable by performing drying. Thus, the regenerated collagen fiber treated with a halogenated aldehyde has a reduced water absorption rate, has an excellent feel when wet, and can be suitably used as a substitute for human hair, animal hair, gut and the like.

Furthermore, since the regenerated collagen fiber treated with a halogenated aldehyde is not capped with a carboxyl group, it is possible to introduce a disulfide bond into the carboxyl group by chemical modification. The above method includes regenerated collagen fibers treated with a halogenated aldehyde and the following general formula (II)

[0024]

[Chemical 6]

(Where n and m are each an integer of 1 to 4) and / or the following general formula (III)

[0026]

[Chemical 7]

A diamine represented by the formula (R1 and R2 in the formula are an alkyl group having 1 to 4 carbon atoms or a benzyl group) is subjected to an amidation reaction using a condensing agent. Specific examples of general formula (II) include cystamine, cystamine dihydrochloride and cystamine sulfate, and specific examples of general formula (III) include D-cystine methyl ester, L-cystine methyl ester,
D, L-cystine methyl ester mixture, D-cystine ethyl ester, L-cystine ethyl ester, D, L
-Cysteine ethyl ester mixture, D-cystine propyl ester, L-cystine propyl ester, D, L-
Cystine propyl ester mixture, D-cystine butyl ester, L-cystine butyl ester, D, L-cystine butyl ester mixture, D-cystine benzyl ester, L-cystine benzyl ester, D, L-cystine benzyl ester mixture and their hydrochloric acid Examples include salt. This amidation reaction is carried out by immersing the regenerated collagen fiber treated with a halogenated aldehyde in a reaction solvent in which a diamine of the general formula (II) and / or (III) and a condensing agent are dissolved. General formula (II) at this time
Alternatively, the amount of the diamine (III) used is 0.05 mmol or more, preferably 0.6 mmol, per 1 g of collagen.
As described above, more preferably 1.2 mmol or more, and the amount of the condensing agent used is 0.1 mmol or more, preferably 1.2 mmol or more per 1 g of collagen. If the amount is less than this amount, the sulfur content required to exert the permanent wave treatment effect cannot be obtained. The treatment temperature is preferably 80 ° C. or lower, and the immersion time is preferably 5 minutes or longer. If the treatment temperature exceeds 80 ° C., the regenerated collagen fibers will be denatured or the strength of the fibers will decrease, making stable yarn production difficult.
-Ethyl-3- (3'-dimethylaminopropyl) carbodiimide and its hydrochloride salt, 1-benzyl-3- (3 '
-Dimethylaminopropyl) carbodiimide and its hydrochloride, 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide meso-p-toluenesulfonate, N, N'-diisopropylcarbodiimide, N,
Carbodiimides such as N′-dicyclohexylcarbodiimide; 1H-benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphonate, benzotriazol-1-yl-oxytris (dimethylamino) phosphonium hexafluorophosphonate, O- (benzo Triazol-1-yl) -N,
Benzotriazoles such as N, N ', N'-tetramethyluronium hexafluorophosphonate and O- (benzotriazol-1-yl) -N, N, N', N'-tetramethyluronium hexafluoroborate;
N, N'-carbonyldiimidazole, 2-ethoxy-
Examples thereof include 1-ethoxycarbonyl-1,2-dihydroquinone and diphenylphosphoryl azide. These condensing agents may be used alone or in combination. Further, in order to accelerate the reaction and suppress side reactions, a condensing agent and N-
Hydroxysuccinimide, 1-hydroxybenzotriazole, 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine and the like may be used in combination.

As the solvent for the amidation reaction, water; alcohols such as methyl alcohol, ethyl alcohol and isopropanol; ethers such as tetrahydrofuran and dioxane: halogenated organic solvents such as dichloromethane, chloroform and carbon tetrachloride: DMF, DMSO And the like, and a mixed solvent thereof may be used. When water is used as the reaction solvent, an aqueous solution of an inorganic salt such as sodium sulfate, sodium chloride or ammonium sulfate may be used if necessary, and if necessary, a metal salt such as sodium borate or sodium acetate, or The pH may be adjusted by adding hydrochloric acid, boric acid, acetic acid, sodium hydroxide or the like. In the case of this reaction, pH 3.0 to 7.0 is preferable.

When the regenerated collagen fiber thus treated with the halogenated aldehyde is chemically modified to introduce a disulfide bond, a fiber having an excellent feel when wet and capable of permanent wave treatment can be obtained.

[0030]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. (A) Preparation of Regenerated Collagen Fiber Using cattle floor skin as a raw material, solubilized with alkali, dissolved in an aqueous lactic acid solution, and adjusted to pH 3.5 and a collagen concentration of 6% by weight, a stock solution is stirred and defoamed under reduced pressure. Then, the solution was transferred to a piston type stock solution for spinning and further left standing under reduced pressure to defoam. After extruding the stock solution with a piston, the solution was quantitatively fed by a gear pump, filtered through a sintered filter having a pore size of 10 μm, passed through a spinning nozzle having a pore size of 0.35 mm, a pore length of 0.5 mm, and a pore number of 50, and boric acid and hydroxylated. PH with sodium
The mixture was discharged at a spinning speed of 4 m / min into a coagulation bath at 25 ° C. containing 20% by weight of sodium sulfate adjusted to 11. (B) Treatment with oil agent The obtained fiber is washed with water and immersed in a bath filled with an oil agent comprising an amino-modified silicone emulsion and a pluronic type polyether antistatic agent to adhere the oil agent. (Example 1) Regenerated collagen fibers were obtained by the method described in (A). This fiber was immersed in an aqueous solution containing 0.4 mol / L of 2-chloroacetaldehyde and 15% by weight of sodium sulfate (adjusted to pH 9 with boric acid and sodium hydroxide) at 25 ° C. for 24 hours. After washing the obtained fiber with water, (B)
After the treatment with the oil agent by the method described in 1), it was dried under tension using a soak air dryer at 75 ° C. (Comparative Example 1-8) Regenerated collagen fibers were obtained by the method described in (A). The compound shown in Table 1 was 0.4mo
Immersion in an aqueous solution containing 1 / L and 15% by weight of sodium sulfate (adjusted to pH 9 with boric acid and sodium hydroxide) at 25 ° C. for 24 hours. The obtained fiber was washed with water, treated with an oil agent by the method described in (B), and then dried under tension using a soak air dryer at 75 ° C.

Next, the physical properties of the obtained regenerated collagen fiber were examined by the following methods. (Fineness) Motorcycle Bro-type fineness measuring device DenierCo
mputer (registered trademark) DC-77A (Search Corporation)
(Manufactured by K.K.) and the fineness was measured in an atmosphere of a temperature of 20 ± 2 ° C. and a relative humidity of 65 ± 2%. (Water absorption) The weight (W) after the fibers were immersed in distilled water (temperature 27 ± 1 ° C) for 20 minutes and the water adhering to the surface was wiped off.
w) (unit: g), and then the weight (Wd) (unit: g) when it was dried with a soak air dryer at 105 ° C. to a constant weight, and calculated by the following formula. Water absorption rate (%) = {(Ww-Wd) / Wd} × 100 (S content) Fibers are completely burned using a sample combustion device QF-02 type (manufactured by Mitsubishi Kasei), and the combustion gas is 0.3%. Absorbed in hydrogen peroxide solution. Then, the sulfate ion concentration of the absorbed water was measured by ion chromatography IC-7000 SERIES.
The S content was determined by measuring with II (manufactured by Yokogawa). (Permanent Wave Treatment Test) The effect of the permanent wave treatment was tested as follows. 300
Approximately 350 fibers are bundled and cut into 20 cm pieces, which are wound on a No. 5 rod and wound on a No. 5 liquid for permanent wave 1st liquid (adjusting a 6.5% aqueous solution of monoethanolamine thioglycolate to a pH of 9.2 with monoethanolamine). (Adjusted to 9.6) at 40 ° C. for 15 minutes. Then, it was immersed in a second liquid for permanent wave (5% aqueous solution of sodium bromate) at 40 ° C. for 15 minutes. After the fibers were removed from the rod and washed with water in a free state, the water adhering to the surface of the fibers was removed, and then the length of the fibers in the suspended state was determined. The fiber length is 20c when the shape is retained by the permanent wave treatment.
It becomes shorter than m and becomes 20 cm when not applied. (Evaluation criteria) As an evaluation of permanent wave,
The following criteria were used.

[0032]

[Table 1]

The results of Example 1 and Comparative Examples 1-8 are shown in Table 2.

[0034]

[Table 2]

As is clear from the results shown in Table 2, the fibers treated with 2-chloroacetaldehyde have a significantly lower water absorption rate and excellent moist feel than the fibers treated with other similar compounds. (Example 2) In the same manner as in Example 1, after insolubilizing treatment with 2-chloroacetaldehyde, it was dried to obtain a fiber. The fiber was prepared in an aqueous solution containing 10% by weight of cystamine dihydrochloride and 3.5% by weight of 1-ethyl-3- (3′-dimethylaminopropyl) carbodiimide hydrochloride (adjusted to pH 4.5 with hydrochloric acid and sodium hydroxide). ) At 25 ° C. for 24 hours. Then, wash the fiber with water, and
It was dried under tension using a soak air dryer at 5 ° C. (Example 3) In the same manner as in Example 1, a fiber was obtained by insolubilizing with a 2-chloroacetaldehyde solution and then drying. 1.6% by weight of cystamine dihydrochloride
And N, N'-dicyclohexylcarbodiimide 2.
It was immersed in methanol containing 9% by weight at 25 ° C. for 24 hours. Then, after washing the fiber with methanol and water,
It was dried under tension using a soak air dryer at 75 ° C. (Comparative Example 9) In the same manner as in Comparative Example 1, a fiber was obtained by insolubilizing with a formaldehyde solution and then drying.
The fibers were mixed with 10% by weight of cystamine dihydrochloride and 1-
25 ° C. in an aqueous solution containing 3.5% by weight of ethyl-3- (3′-dimethylaminopropyl) carbodiimide hydrochloride (adjusted to pH 4.5 with hydrochloric acid and sodium hydroxide).
It was soaked for 24 hours. Then, the fibers were washed with water and dried under tension using a soak air dryer at 75 ° C.

[0036]

[Table 3]

From the results shown in Table 3, the regenerated collagen fibers were
When treatment with chloroacetaldehyde and chemical modification of the carboxyl group to introduce a disulfide bond,
It can be seen that a fiber having a low water absorption rate, an excellent feel when wet, and a permanent wave treatment can be obtained.

[0038]

EFFECTS OF THE INVENTION The regenerated collagen fiber obtained by the treatment method of the present invention has a reduced water absorbency and an excellent feel when wet, and can be suitably used as a substitute for human hair, animal hair, gut and the like. Further, according to the treatment method of the present invention, it is also possible to chemically modify the carboxyl group, and by introducing a disulfide bond, a fiber capable of permanent wave treatment and having significantly improved water absorption can be obtained. .

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Norio Hirokawa             7-3-20 Kasugadai, Nishi-ku, Kobe City, Hyogo Prefecture F term (reference) 4L033 AB01 AC15 BA09 BA46 CA08                       CA48 CA59 DA02                 4L035 AA06 BB03 BB60 CC20 EE05                       FF04

Claims (3)

[Claims] 1. A method for treating regenerated collagen fiber, which comprises treating with a halogenated aldehyde represented by the following general formula (I). [Chemical 1] (In the formula, X represents a halogen atom, R represents a hydrocarbon group having 3 or less carbon atoms, and n represents an integer of 1 to 3.) 2. The method for treating regenerated collagen fiber according to claim 1, wherein the halogenated aldehyde is 2-chloroacetaldehyde. 3. Regenerated collagen fiber treated by the method according to claim 1 and the following general formula (II): (N and m in the formula each represent an integer of 1 to 4) and /
Or the following general formula (III): (R1 and R2 in the formula each represent an alkyl group having 1 to 4 carbon atoms or a benzyl group.) A diamine having a disulfide bond and an amidation reaction using a condensing agent. Fiber treatment method.