JP2002249982A - Chemically modified regenerated collagen fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a regenerated collagen fiber having a light color, an excellent sense of touch in wetting, allowing readily forming a fixed shape, firmly setting and retaining the shape. SOLUTION: This regenerated collagen fiber has a structure in which >=50% of free amino group of regenerated collagen is modified with a 2-20C alkyl group of a main chain containing a hydroxy group or an alkoxy group at the B-position or γ-position and contains an aluminum compound in the fiber. In the regenerated collagen fiber, the alkyl group is preferably a compound represented by general formula (I) -CH2 -CH(OX)-R [R is a substituent group represented by R<1> -, R<2> -O-CH2 - or R<2> -COO-CH2 -; R<1> is a >=2C hydrocarbon group or CH2 Cl; R<2> is a >=4C hydrocarbon group; X is hydrogen or a hydrocarbon group].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a regenerated collagen fiber having improved setting properties. More specifically, a regenerated collagen fiber which is light-colored, has an excellent tactile sensation when wet, can easily impart a desired shape, can hold the shape firmly, and has a reduced odor generated during heat treatment, and a method for producing the same. About. Such a regenerated collagen fiber can be suitably used for a head decoration product such as a wig, a hairpiece or a doll hair, or a fiber product made of a woven or nonwoven fabric which requires a shape (set).

[0002]

2. Description of the Related Art In general, in order to produce regenerated collagen fibers, animal skin or bone is used as a raw material, and this is subjected to an alkali or enzyme treatment to decompose and remove the telopeptide portion of the collagen to remove water-soluble collagen. And a method of spinning this is adopted. Therefore, the obtained regenerated collagen fiber is still soluble in water, and further, when the regenerated collagen contains water, the regenerated collagen fiber starts to shrink at a temperature of about 30 to 40 ° C. and has extremely poor water resistance. Met.

Therefore, in order to make the regenerated collagen fiber light-colored and water-resistant, Japanese Patent Application Laid-Open Nos.
No. 173161 and JP-A-4-308221, a method of treating with a metal salt such as an aluminum salt and a zirconium salt, and a method of treating with an epoxy compound described in JP-A-4-352804. Proposed. As a method for imparting a shape to the regenerated collagen, there are known hot water or an aqueous solution containing a monovalent or divalent cation sulfate described in JP-A-4-333660 and JP-A-9-250081. There is known a method of performing a warming treatment by moistening with water. However,
When the shape is given to the regenerated collagen fiber which has been made water-resistant by treatment with a metal salt such as an aluminum salt or a zirconium salt by the above method, the shape can be given, but the force for retaining the shape (setting property) is extremely weak and the subsequent washing with water (Including shampoo washing) and drying repeatedly resulted in the loss of the provided shape, making it difficult to use it for hair materials such as wigs, hairpieces and doll hair.

[0004] Although light colored fibers can be obtained by using formaldehyde, they are not satisfactory from the viewpoint of shape formation. Further, Japanese Patent Application Laid-Open No. 4-35280
In the case of using a glycidyl ether of a polyhydric alcohol, which is particularly preferable among the epoxy compounds described in JP-A No. 4 (1999) -2014, the yarn is brittle and hard, and the strength is greatly reduced. The above problems tended to occur. Furthermore, this was not satisfactory from the point of shape provision.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a regenerated collagen fiber which is light-colored, has an excellent tactile sensation when wet, can easily impart a desired shape, and can firmly set and hold the shape. With the goal.

[0006]

SUMMARY OF THE INVENTION In view of the above-mentioned situation, collagen having a structure in which a free amino group of regenerated collagen is modified with a substituted alkyl group, and a regenerated collagen fiber containing an aluminum compound is used. The present inventors have found that it is possible to obtain a regenerated collagen fiber which retains the original light color tone, improves stiffness when wet with water, and has a good tactile sensation when wet, and has completed the present invention.

That is, the present invention relates to a regenerated collagen fiber having a structure in which at least 50% of the free amino groups of the regenerated collagen are modified with an alkyl group and containing an aluminum compound. Here, the alkyl group is an alkyl group having a hydroxyl group or an alkoxyl group at the β-position or the γ-position and having 2 to 20 carbon atoms in the main chain.

More preferably, the alkyl group is a compound represented by the following general formula (I). —CH ₂ —CH (OX) —R (I) wherein R is R ¹ —, R ² —O—CH ₂ — or R ² —CO
O-CH ₂ - represents a substituent represented by, R ¹ in the substituent is 2 or more hydrocarbon groups or CH ₂ Cl atoms,
R ² represents a hydrocarbon group having 4 or more carbon atoms, and X represents hydrogen or a hydrocarbon group. In addition, at least a part of the methionine residue in the regenerated collagen is preferably a sulfoxidized methionine residue or a sulfonated methionine residue, from the viewpoint of preventing odor.

Further, the aluminum content in the regenerated collagen fiber is preferably 1 to 10% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The regenerated collagen fibers of the present invention
At least 50% of the free amino groups of the regenerated collagen have a hydroxyl group or an alkoxy group at the β-position or the γ-position;
It is a regenerated collagen fiber having a structure modified with -20 alkyl groups and containing an aluminum compound in the fiber. Preferably, in addition to this, a regenerated collagen fiber in which at least a part of the methionine residue in the regenerated collagen is a sulfoxidized methionine residue or a sulfonated methionine residue.

The modification in the present invention means a structure in which part or all of the hydrogen on a free amino group is substituted by such an alkyl group.

The raw material of the regenerated collagen used in the present invention is:
It is preferred to use the part of the floor covering. The floor skin is obtained, for example, from fresh floor skin or salted rawhide obtained by slaughtering an animal such as a cow. These floor coverings are mostly composed of insoluble collagen fibers, but are usually used after removing the fleshy parts adhering in a net-like manner or removing the salt used for preventing rot and deterioration.

The insoluble collagen fibers contain impurities such as lipids such as glyceride, phospholipid and free fatty acid, and proteins other than collagen such as glycoprotein and albumin. These impurities are used for fiberization, such as spinning stability, gloss and high elongation.
Has a great effect on odors. Therefore, for example, after liming, the fat in the insoluble collagen fiber is hydrolyzed and the collagen fiber is disentangled, and then the conventional leather treatment such as acid / alkali treatment, enzyme treatment, and solvent treatment is performed. It is preferable to remove these impurities in advance.

The insoluble collagen treated as described above is subjected to a solubilization treatment in order to cut the cross-linked peptide portion. As the method of the solubilization treatment, a commonly used known alkali solubilization method, enzyme solubilization method, or the like can be applied.

When the alkali solubilization method is applied, it is preferable to neutralize with an acid such as hydrochloric acid, for example.
As an improved method of the conventionally known alkali solubilization method, a method described in JP-B-46-15033 may be used.

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 suitably employed in the present invention.
As such an enzyme solubilization method, for example, Japanese Patent Publication No. 43-2
Methods described in Japanese Patent No. 5829 and Japanese Patent Publication No. 43-27513 can be used. Further, the alkali solubilization method and the enzyme solubilization method may be used in combination.

When collagen solubilized in this way is further subjected to operations such as pH adjustment, salting out, washing with water and solvent treatment, it is possible to obtain regenerated collagen having excellent quality and the like. Preferably, these treatments are performed.

The obtained solubilized collagen is, for example, 1
PH with acid such as hydrochloric acid, acetic acid and lactic acid so as to obtain a stock solution having a predetermined concentration of about 15% by weight, especially about 2 to 10% by weight.
It is dissolved using an acidic solution adjusted to 2-4.5. In addition, the obtained collagen aqueous solution may be subjected to defoaming under stirring under reduced pressure as needed, or may be subjected to filtration in order to remove fine dust which is a water-insoluble component. The obtained solubilized collagen aqueous solution may further contain, if necessary, a stabilizer for the purpose of improving mechanical strength, improving water and heat resistance, improving gloss, improving spinnability, preventing coloring, preserving, etc.
An appropriate amount of an additive such as a water-soluble polymer compound may be blended.

The regenerated collagen fibers are formed by discharging the solubilized collagen aqueous solution into the inorganic salt aqueous solution through, for example, a spinning nozzle or a slit. Examples of the inorganic salt aqueous solution include sodium sulfate, sodium chloride,
An aqueous solution of a water-soluble inorganic salt such as ammonium sulfate is used, and the concentration of these inorganic salts is usually adjusted to 10 to 40% by weight. The pH of the aqueous inorganic salt solution is, for example, a metal salt such as sodium borate or sodium acetate, hydrochloric acid, boric acid,
It is preferable to adjust the pH to usually 2 to 13, preferably 4 to 12, by adding acetic acid, sodium hydroxide, or the like. When the pH is less than 2 or more than 13, the peptide bond of collagen is liable to be hydrolyzed, and the desired fiber tends to be hardly obtained. 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 or the strength of the spun fiber is reduced, making it difficult to produce a stable yarn. The lower limit of the temperature is not particularly limited,
Usually, it can be appropriately adjusted according to the solubility of the inorganic salt.

In the present invention, the free amino group of the regenerated collagen fiber is modified with an alkyl group having a main chain of 2 to 20 carbon atoms having a hydroxyl group or an alkoxy group at the β-position or γ-position. Such a carbon number main chain refers to a continuous carbon chain of an alkyl group bonded to an amino group, and does not take into account the number of carbon atoms present through other atoms. As the reaction for modifying a free amino group, a commonly known alkylation reaction of an amino group can be used. The alkyl group having 2 to 20 carbon atoms having a hydroxyl group or an alkoxy group at the β-position is preferably a compound represented by the following formula (I) from the viewpoint of reactivity, ease of treatment after the reaction, and the like.

—CH ₂ —CH (OX) —R (I) wherein R is R ¹ —, R ² —O—CH ₂ — or R ² —COO
-CH _2- represents a substituent represented by R ¹
Is 2 or more hydrocarbon groups or CH ₂ Cl atoms, R ²
Represents a hydrocarbon group having 4 or more carbon atoms, and X represents hydrogen or a hydrocarbon group. Preferred examples of the general formula (I) include a glycidyl group,
-Chloro-2-hydroxypropyl group and 1,2-dihydroxypropyl group. In addition, there is a structure in which a glycidyl group is added to a free amino group in collagen. Further, a structure in which the epoxy compound used is a ring-opening addition and / or ring-opening polymerization using the hydroxyl group contained in the alkyl group described in the above-mentioned preferred group as a starting point, and the addition and / or polymerization of the Examples of the terminal structure include those having the above-described alkyl group structure.

In the present invention, the amino acids constituting the free amino groups of the regenerated collagen fibers include lysine and hydroxylysine. Furthermore, although the amino acid that originally constitutes collagen is arginine, the amino group of ornithine generated by partial hydrolysis progresses during hydrolysis under alkaline conditions to obtain the regenerated collagen fiber. Are also alkylated. In addition, in the present invention, histidine 2
The reaction proceeds also with the secondary amine.

The modification rate of the free amino group can be measured by amino acid analysis. The amino acid analysis value of the regenerated collagen fiber before the alkylation reaction or the known composition of the free amino acid constituting the collagen used as the raw material can be obtained. It is calculated based on the standard. In the modification of the amino group in the present invention, the structure modified with an alkyl group having 2 or more carbon atoms having a hydroxyl group or an alkoxy group at the β-position or γ-position may be 50% or more of the free amino group. The other part may be a free amino group or a structure modified with another substituent.

In the present invention, the modification rate of the free amino acid of the regenerated collagen fiber must be 50% or more, more preferably 65% or more, and further preferably 80% or more. When the reaction rate is low, good properties cannot be obtained in setting property and heat resistance.

Here, in the modification of the free amino group,
Usually, one molecule of the alkylating agent reacts with one free amino group, but two or more molecules may react. further,
A cross-linking reaction within or between molecules may exist via a hydroxyl group or an alkoxy group or another functional group present at the β-position or γ-position of the alkyl group bonded to the free amino group.

Specific examples of the alkylation reaction include an addition reaction of an epoxy compound, an addition reaction of an aldehyde compound having a hydroxyl group or a derivative thereof at the α-position or the β-position, followed by a reduction reaction, a β-position or γ-position. Substitution reactions such as halides having 2 or more carbon atoms having a hydroxyl group or an alkoxy group at the position, alcohols, and amines, but are not limited thereto.

As the alkylating reagent, a modification reaction with an epoxy compound is preferred because of its excellent properties and reactivity and ease of processing conditions. Among the epoxy compounds, a monofunctional epoxy compound is preferred because a polyfunctional epoxy compound has a problem such as a decrease in the strength of a fiber obtained.

Specific examples of the monofunctional epoxy compound used here include, for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, octene oxide, styrene oxide, methylstyrene oxide, epichlorohydrin, epibromohydrin Olefin oxides such as glycidol, glycidyl methyl ether, butyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, undecyl glycidyl ether, tridecyl glycidyl ether, pentadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, Phenyl glycidyl ether, cresyl glycidyl ether, t-butylphenyl glycidyl ether, dibromophenyl glycidyl ether, benzyl Glycidyl ethers such as sidyl ether and polyethylene oxide glycidyl ether; glycidyl esters such as glycidyl formate, glycidyl acetate, glycidyl acrylate, glycidyl methacrylate and glycidyl benzoate; and glycidyl amides are examples of the present invention. It is not limited to only.

Among the monofunctional epoxy compounds, the water absorption of the regenerated collagen fiber is reduced.
The treatment is preferably performed using the monofunctional epoxy compound represented by I).

[0030]

Embedded image(Where R is R¹-, R^Two-O-CH_Two-Or R^Two-COO
-CH_Two-Represents a substituent represented by-¹
Is a hydrocarbon group having 2 or more carbon atoms or CH_TwoCl, R ^TwoIs carbon
It represents a hydrocarbon group of several or more. As specific examples of the compound represented by the general formula (II),
Butylene oxide, octene oxide, styrene oxide, methyl oxide
Styrene, epichlorohydrin, butyl glycidyl ester
-Tel, octyl glycidyl ether, nonyl glycidyl
Ether, undecyl glycidyl ether, trideci
Luglycidyl ether, pentadecyl glycidyl ether
, 2-ethylhexyl glycidyl ether, phenyl
Glycidyl ether, cresyl glycidyl ether, t
-Butylphenyl glycidyl ether, benzyl glycidyl
Zyl ether and glycidyl benzoate.

Further, in the above general formula, R ¹ has 2 to 2 carbon atoms.
Butylene oxide, octene oxide, styrene oxide, epichlorohydrin, etc., which is a hydrocarbon group of 6 or CH ₂ Cl, butyl glycidyl ether, phenyl glycidyl ether, and benzoic acid in which R ² is a hydrocarbon group having 4 to 6 carbon atoms Monofunctional epoxy compounds such as glycidyl acid are particularly preferably used because they have high reactivity and can be treated in a shorter time, and are relatively easily treated in water.

The amount of the monofunctional epoxy compound used is based on the amount of the amino group capable of reacting with the monofunctional epoxy compound in the regenerated collagen fiber measured by the amino acid analysis method.
0.1 to 500 equivalents, preferably 0.5 to 100 equivalents,
More preferably, it is 1 to 50 equivalents. When the amount of the monofunctional epoxy compound is less than 0.1 equivalent, the effect of insolubilizing the regenerated collagen fiber in water is not sufficient. On the contrary, when the amount of the monofunctional epoxy compound exceeds 500 equivalents, the insolubilizing effect can be satisfied. Tend to be unfavorable in terms of industrial handling and environment.

The monofunctional epoxy compound is used as it is or after being dissolved in various solvents. Examples of the solvent include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropanol; ethers such as tetrahydrofuran and dioxane; halogen-based organic solvents such as dichloromethane, chloroform, and carbon tetrachloride; dimethylformamide (DMF), dimethyl sulfoxide (DMSO). ) And the like, and a mixed solvent thereof may be used. When water is used as the solvent, an aqueous solution of an inorganic salt such as sodium sulfate, sodium chloride, or ammonium sulfate may be used as necessary. Usually, the concentration of these inorganic salts is adjusted to 10 to 40% by weight. Further, the pH of the aqueous solution may be adjusted by, for example, blending a metal salt such as sodium borate or sodium acetate, hydrochloric acid, boric acid, acetic acid, sodium hydroxide, or the like. In this case, the preferred pH is 6 or more, more preferably pH 8 or more. In particular, for the purpose of improving the reaction rate, a basic compound such as sodium hydroxide is added in an amount of 0.1 g / kg of the reaction solution.
It is effective to add 001 to 1 mol in the range. However, when controlling the pH using a strong basic compound,
Addition of 1 mol or more per 1 kg of the reaction solution is not preferable because the dissolution due to hydrolysis of the collagen fibers simultaneously proceeds during the crosslinking reaction. When the pH is less than 6, the reaction between the epoxy group of the monofunctional epoxy compound and the amino group of collagen becomes slow, and the insolubilization in water becomes insufficient. Further, since the pH tends to decrease with time, a buffer may be used if necessary.

The temperature for treating the regenerated collagen fibers with the monofunctional epoxy compound is preferably 70 ° C. or less. When the treatment temperature exceeds 70 ° C., the regenerated collagen fibers are denatured or the strength of the obtained fibers is reduced, and it is difficult to produce a stable yarn.

In order to achieve the desired modification ratio, the above reaction conditions may be adjusted and selected appropriately. For example, when the reaction is performed at a low temperature of about 25 ° C., the reaction needs to be performed for a relatively long time. Therefore, when the reaction time is desired to be reduced, an alkali is added or the reaction at a high temperature is effective. . In consideration of the influence on the denaturation of the regenerated collagen fiber, it is more preferable to perform the reaction at a low temperature of 30 ° C. or less in the initial stage of the reaction, and then to raise the temperature to 40 ° C. to 60 ° C. to accelerate the reaction.

In addition, various additives such as a catalyst and a reaction aid may be coexisted. For example, examples of the catalyst include amines and imidazoles. Specifically, amines include triethyldiamine, tetramethylguanidine, triethanolamine, N, N'-dimethylpiperazine, benzyldimethylamine, dimethylaminomethylphenol, 2,4,6-tris (dimethylaminomethyl) phenol Tertiary amines such as piperazine and morpholine; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt and benzyltriethylammonium salt. Examples of imidazoles include 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole,
-Cyanoethyl-2-isopropylimidazole, 2-
Ethyl-4-methylimidazole and the like. Furthermore, examples of the reaction assistant include salicylic acid or salicylic acid metal salt; thiocyanates such as thiocyanic acid and ammonium thiocyanate; tetramethylthiuram disulfide; and thiourea.

As the alkylating agent, an aldehyde compound having a hydroxyl group or a derivative thereof at the α-position or β-position can also be used. When an aldehyde compound is used, the desired structure can be obtained by treating with the aldehyde compound, washing as necessary after the reaction, and further performing a reduction reaction.

The aldehyde compound used is α-
A hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, and a substituent on silicon are substituted with an alkyl group having 1 to 20 carbon atoms at the β-position or the β-position; May be different, may have a siloxy group having a saturated or unsaturated hydrocarbon group, and an aldehyde compound having 1 to 30 carbon atoms in a skeleton excluding a substituent. It is not limited.

The treatment with the aldehyde compound having a hydroxyl group or a group derived from a hydroxyl group at the α-position or β-position of the regenerated collagen can be carried out according to JP-A-4-50370.

For example, it can be performed as follows.

A 10-20% by weight aqueous solution of sodium sulfate adjusted to pH 7.5-13 is added to the corresponding α-position or β-position.
An aldehyde compound having a hydroxyl group or a group derived from a hydroxyl group at the -position is added in the range of 0.01 to 10% by weight, and the regenerated collagen fiber is immersed in the range of 1 minute to 24 hours to adjust. It is possible.

After the aldehyde is allowed to act, an amino group having a desired structure can be obtained by reduction.
Although there is no particular limitation on the reduction reaction, a hydrogenation reaction can be given as a reaction that easily gives a desired structure.

The specific reaction of the hydrogenation reaction is as follows:
Examples include a reduction reaction with a compound having a hydrogen bond, a catalytic hydrogenation reaction in the presence of a hydrogenation catalyst, and a hydrogen transfer reaction from alcohol in the presence of a catalyst.

Since the reduction reaction is carried out after the treatment with the aldehyde compound, it is preferable to carry out the reduction reaction in the same medium as in the treatment with the aldehyde compound. In the treatment with an aldehyde compound, a medium having an active hydrogen group is usually used. For this reason, in the reduction reaction using a compound having a metal-hydrogen bond, sodium borohydride, which is stable among active hydrogen compounds, is mentioned as an effective component.

As the catalyst for performing the catalytic hydrogenation reaction and the hydrogen transfer reaction, those used in ordinary hydrogenation reactions and hydrogen transfer reactions can be used. Such compounds include transition metal complex compounds. Specific examples include metallocene-based complexes, Wilkinson complexes, cobalt acetate / triethylaluminum, nickel acetylacetate / triisobutylaluminum, palladium-carbon, ruthenium-carbon, nickel-diatomaceous earth and the like.

The reduction by the hydrogen transfer reaction is not particularly limited as long as it is a primary or secondary alcohol as a hydrogen source. However, alcohols having 2 to 10 carbon atoms are preferred because of their reactivity and ease of removal after completion of the reaction. Is effective, and isopropanol is particularly preferable.

The catalytic hydrogenation reaction and the hydrogen transfer reaction are carried out in a homogeneous or heterogeneous system depending on the type of the catalyst. Although the reduction reaction temperature is not particularly limited, it is preferable to carry out the reaction in the range of 0 ° C to 60 ° C in consideration of the purpose of suppressing denaturation of the regenerated collagen fiber by heat and the melting point of the reaction medium, and more preferably. Ranges from 10 ° C to 50 ° C. The catalytic hydrogenation reaction is usually performed under a hydrogen pressure of 1 to 200 atm. The hydrogenation conversion is desirably 90% or more, preferably 95% or more, and more preferably 99% or more.

Further, in the present invention, if necessary,
The regenerated collagen fibers are washed with water. Washing has the advantage of removing inorganic salts contained during spinning, organic compounds used in the reaction, or decomposed products thereof.

Next, in the present invention, since it is necessary that the regenerated collagen fiber contains an aluminum compound, the regenerated collagen fiber is immersed in an aqueous solution of aluminum salt to carry out the treatment. By this treatment, stiffness is added to the regenerated collagen fibers when wet, the wet feel is improved, and the shape imparting such as curl setting becomes good. In addition, as a conventionally known method of improving the aluminum salt treatment, a method described in JP-A-6-173161 may be employed.

In the present invention, the treatment is preferably carried out so that the aluminum content of the fiber after the treatment is 1 to 10% by weight, more preferably 3 to 10% by weight.
9% by weight. If the amount is less than 1% by weight, the wet feel becomes poor and the shape imparting such as curl set becomes weak. Also 10
If the amount is more than 10% by weight, the fibers after the treatment become hard and the texture is impaired.

The aluminum salt used here is not particularly limited, and examples thereof include aluminum sulfate, aluminum chloride, basic aluminum chloride and basic aluminum sulfate. Here, basic aluminum chloride and basic aluminum sulfate are represented by the following formulas (III) and (IV).

Al (OH) _N Cl _3-N (III) Al ₂ (OH) ₂ N (SO ₄ ) _3-N (IV) wherein N is 0.5 to 2.5 Aluminum salts can be used alone or in combination of two or more. The aluminum salt concentration of the aqueous solution of aluminum salt may be aluminum oxide (Al
It is preferred in terms of ₂ O ₃₎ is 0.3 to 5 wt%. When the content is less than 0.3% by weight, the content of aluminum in the regenerated collagen fiber is small, the wet feel is poor, and the shape imparting such as curl setting is weak. If it exceeds 5% by weight, the fibers after the treatment become hard and impair the texture.

The pH of the aqueous aluminum salt solution is usually 2.5 to 6.5, preferably 2.5 to 6.5 using hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, sodium carbonate or the like.
Adjust to 5.5. If the pH is less than 2.5, the structure of the regenerated collagen tends to be destroyed and denatured, and if it exceeds 6.5, precipitation of the aluminum salt occurs, making it difficult for the fibers to penetrate the fiber. This pH is
For example, it can be adjusted by adding sodium hydroxide, sodium carbonate, or the like. At first, it is adjusted to 2.2 to 5.0 to allow the aqueous solution of aluminum salt to penetrate into the regenerated collagen fiber, and then to 3.5 to 6 It is preferable to adjust the value to 0.5 to complete the treatment. When a highly basic aluminum salt is used, only the initial pH adjustment of 2.5 to 6.5 may be used. The temperature of the aqueous aluminum salt solution is not particularly limited, but is preferably 50 ° C. or lower.
When the solution temperature exceeds 50 ° C., the regenerated collagen fibers tend to be denatured.

The time for penetrating the regenerated collagen fibers into the aqueous aluminum salt solution is 10 minutes or more, preferably 1-2 minutes.
5 hours. If the immersion time is less than 10 minutes, the reaction of the aluminum salt does not easily proceed, and the improvement of the wet feel of the regenerated collagen fibers becomes insufficient. The upper limit of the immersion time is not particularly limited, but the reaction of the aluminum salt sufficiently proceeds within 25 hours, and the wet feel is improved.

In order to prevent the aluminum salt from being rapidly absorbed into the regenerated collagen fiber and causing concentration unevenness, an inorganic salt such as sodium chloride, sodium sulfate, potassium chloride or the like is appropriately added to the aqueous solution of the aluminum salt.
It may be added so as to have a concentration of 20% by weight. Further, in order to improve the stability of the aluminum salt in water, an organic salt such as sodium formate or sodium citrate is appropriately added to the aqueous solution of the aluminum salt in an amount of 0.1 to 5% by weight, preferably 0.5 to 2% by weight. % May be added.

The regenerated collagen fibers thus treated with the aluminum salt are then washed with water, oiled and dried. Washing can be performed by, for example, washing with running water for 10 minutes to 4 hours. As the oil agent used for oiling, for example, an emulsion such as amino-modified silicone, epoxy-modified silicone, and polyether-modified silicone, and an oil agent composed of a Pluronic-type polyether-based antistatic agent can be used. The drying temperature is preferably 100 ° C. or less, more preferably 75 ° C.
Hereinafter, the load at the time of drying is 9.8 × 1 for 1 dtex.
0 ^{-5 to} 2.45 × 10 ⁻³ N, preferably 1.96 × 10
It is preferable to apply a load of ^{-4 to} 1.47 × 10 ^-3 N.

Here, the washing with water is performed to prevent the precipitation of the oil agent due to the salt, to cause the salt to precipitate from the regenerated collagen fiber during drying in the dryer, and to cause the regenerated collagen fiber to be cut by the salt, or to be formed. The salt is prevented from scattering in the dryer and adhering to the heat exchanger in the dryer to reduce the heat transfer coefficient. Further, when oiling is applied, it is effective in preventing fiber sticking during drying and improving surface properties.

By the way, the fiber treated with the monofunctional epoxy compound generates an odor when heat is applied in a drying step or the like, and this odor is generated particularly when the fiber is exposed to a higher temperature using a hair dryer or a hair iron as a hair material. The problem of becoming intense occurs. The cause of this odor is that the monofunctional epoxy compound reacts with the sulfur atom in the methionine residue, and the unstable methionine residue is thermally decomposed during the drying step and other heat treatments. Compound. The generation of this odor is achieved by using a regenerated collagen fiber obtained by oxidizing a methionine residue in the regenerated collagen and changing it to a sulfoxided methionine residue or a sulfonated methionine residue, for reaction with a monofunctional epoxy compound. Can be suppressed.

In particular, when a monofunctional epoxy compound and a metal salt such as an aluminum salt are used in combination as in the present invention, these metal salts may act as a catalyst for thermal decomposition and generate odor in some cases. In such a case, it is particularly effective to use a regenerated collagen fiber obtained by oxidizing a methionine residue and changing it to, for example, a sulfoxidized methionine residue or a sulfonated methionine residue, with a monofunctional epoxy compound. .

As a method of oxidizing methionine residues in regenerated collagen, there is a method of treating collagen with an oxidizing agent. The treatment with the oxidizing agent may be performed at any stage before the treatment with the monofunctional epoxy compound.
In the case of treating solids such as floor coverings and regenerated collagen fibers after spinning, these can be treated by immersing them in an oxidizing agent or a solution thereof. When the solubilized collagen aqueous solution is treated, the treatment can be performed by adding an oxidizing agent or a solution thereof to the collagen aqueous solution and thoroughly mixing the oxidizing agent or the solution.

As the oxidizing agent, peracetic acid, perbenzoic acid, benzoyl peroxide, perphthalic acid, m-chloroperbenzoic acid,
t-butyl hydroperoxide, periodic acid, sodium periodate, peroxides such as hydrogen peroxide, nitrogen dioxide, nitric acid, nitrous oxide, nitrogen oxides such as pyridine-N-oxide, potassium permanganate, Chromic anhydride,
Metal oxides such as sodium dichromate and manganese dioxide; halogens such as chlorine, bromine and iodine; halogenating agents such as N-bromosuccinimide, N-chlorosuccinimide and sodium hypochlorite. . Among them,
Hydrogen peroxide is preferably used because by-products do not remain in the regenerated collagen fiber and handling is easy.

The oxidizing agent is used as it is or after being dissolved in various solvents. Examples of the solvent include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropanol; ethers such as tetrahydrofuran and dioxane; halogen-based organic solvents such as dichloromethane, chloroform, and carbon tetrachloride; neutral organic solvents such as DMF and DMSO; However, these mixed solvents may be used. When water is used as the solvent, an aqueous solution of an inorganic salt such as sodium sulfate, sodium chloride, or ammonium sulfate may be used as necessary. The concentration of the inorganic salt is usually adjusted to 10 to 40% by weight.

As the amount of the oxidizing agent used, it is most industrially desirable that all the used oxidizing agent contributes to the reaction. In this case, the amount of the oxidizing agent used is determined by the amount of methionine residue in the regenerated collagen fiber (as a result of amino acid analysis, for example, the amount of methionine residue in the regenerated collagen fiber derived from cow skin is
6 equivalents per 1000 amino acids constituting collagen). However, since some oxidizing agents do not actually contribute to the reaction, it is necessary to use 1.0 equivalent or more.

When a solid material such as a floor skin or a regenerated collagen fiber after spinning is immersed in an oxidizing agent solution for treatment, an amount of the oxidizing agent solution in which the floor skin or the regenerated collagen fiber is completely immersed is required. . The amount of the oxidizing agent used at this time is at least 1.0 equivalent, preferably at least 5.0 equivalent, more preferably at least 10.0 equivalent to the methionine residue.
The concentration of the oxidizing agent in the oxidizing agent solution is 0.01% by weight or more,
Preferably at least 0.1% by weight, more preferably 0.5% by weight.
% By weight, most preferably 0.8% by weight or more.
When the concentration of the oxidizing agent is less than 0.01% by weight, the number of reaction points is reduced, so that the reaction with the methionine residue of the regenerated collagen hardly proceeds. The effect of suppressing the odor of collagen fibers is not sufficient. The processing temperature is usually desirably 35 ° C. or lower. The processing time is usually 5 minutes or more. When the regenerated collagen fiber is processed, the effect of suppressing odor is exhibited in about 10 minutes. On the other hand, in the case of floor covering in which the oxidizing agent does not easily penetrate into the inside, the reaction is sufficiently advanced by keeping the immersion in the oxidizing agent solution for about one night.

When treating a solubilized collagen aqueous solution,
The amount of the oxidizing agent to be added is 1.0 equivalent or more, preferably,
It is 5.0 equivalents or more, more preferably 10.0 equivalents or more. The concentration of the oxidizing agent in the aqueous collagen solution is 0.0
It is at least 1% by weight, preferably at least 0.05% by weight, more preferably at least 0.1% by weight, most preferably at least 0.2% by weight. When the concentration of the oxidizing agent is less than 0.01% by weight, the number of reaction points is reduced, so that the reaction with the methionine residue of the collagen hardly proceeds. When the concentration is less than 1.0 equivalent, the odor of the regenerated collagen fiber is suppressed. The effect is not enough. The above treatment is also desirably performed at 35 ° C. or lower. After the addition of the oxidizing agent, it is preferable that the solubilized collagen aqueous solution is sufficiently mixed using a kneader or the like for at least 30 minutes to bring the oxidizing agent into contact with the collagen.

The regenerated collagen fiber of the present invention can be imparted with a desired curl and firmly set and maintained in other shapes by, for example, a wet heat treatment at 40 to 160 ° C. and a subsequent drying treatment. Although the details of the mechanism of the shape imparting are unknown, the hydrogen bond inside the regenerated collagen fiber is cut by the wet heat treatment, and then the hydrogen bond is recombined to the desired shape by the subsequent drying. We believe that it can give shape. Further, the treatment temperature condition is extremely important for providing a strong shape.

The wet heat treatment is a heat treatment performed in the presence of moisture, which is left in a steam atmosphere adjusted to a predetermined temperature, immersed in water adjusted to a predetermined temperature, or immersed in water once. Then, the fibers sufficiently filled with water may be put in a plastic bag or the like, sealed, and then put in an air thermostat adjusted to a predetermined temperature.

Specifically, the regenerated collagen fiber is fixed in a desired shape (spiral shape or the like) in advance, and the temperature of the regenerated collagen fiber is set to 40 to 160 in the presence of water.
It is preferable to use a treatment capable of adjusting the temperature to ℃ and keeping the temperature.

It is extremely difficult to determine the amount of water to be present on the surface of the regenerated collagen fiber when the regenerated collagen fiber is treated in the presence of water. In order to
It is preferable to make adjustment so that water is present on the surface almost uniformly.

In the treatment in the presence of moisture, it is difficult to give a desired shape to the regenerated collagen fiber when the temperature of the regenerated collagen fiber is too low. In this case, the regenerated collagen fibers may be deteriorated. Usually 40 ° C to 160 ° C,
Preferably 50 to 100 ° C, more preferably 70 to 1
The treatment is preferably performed at a temperature of 00 ° C, most preferably in the range of 80 to 95 ° C.

It is necessary to appropriately adjust the treatment time of the hot water treatment depending on the atmosphere for treating the regenerated collagen fibers, the treatment temperature, and the like. Usually more than 5 minutes, preferably 15
It is better to process for more than a minute.

The subsequent drying means putting the fiber bundle in a hot air convection dryer or drying with a dryer or the like, and any known method can be used without any limitation. Specifically, after the wet heat treatment, 1
Drying is preferably performed under an atmosphere temperature condition of 50 ° C. or less.

If the drying temperature exceeds 150 ° C., the regenerated collagen fibers may be altered or colored. Usually 1
The treatment is performed at a temperature of 50 ° C. or less, preferably 110 ° C. or less, and more preferably 90 ° C. or less.

By performing the above treatment, the regenerated collagen fibers can be set and the shape can be firmly maintained.

Examples of a method of fixing the regenerated collagen fiber in a desired shape in advance include, for example, a method of winding the regenerated collagen fiber around a pipe or a rod.
A method of tensioning the regenerated collagen fiber between two or more fulcrums, a method of sandwiching the regenerated collagen fiber between plate-like objects, and the like can be mentioned. Other methods may be used as long as they can be sufficiently imparted and dried.

The regenerated collagen fiber of the present invention is preferably used as a fiber for hair, blanket, surgical thread, gut, non-woven fabric, paper, etc., because of its light color and excellent water resistance. Can be used.

Further, the regenerated collagen fiber of the present invention comprises:
Not only is it light-colored and has a good wet feel, it can also easily give the desired shape, and it can be set and held firmly.For example, curls on head decoration products such as wigs, hairpieces or doll hair It can be suitably used for giving a set or giving (setting) the shape of a woven or nonwoven fabric.

[0078]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 1200 g of skin pieces (collagen content 180
g), 30 g of an aqueous solution of hydrogen peroxide diluted to 30% by weight was added thereto, and then dissolved in an aqueous solution of lactic acid to have a pH of 3.5 and a solid content of 7.
A stock solution adjusted to 5% by weight was prepared. The stock solution was subjected to a stirring and defoaming process under reduced pressure by a stirring and defoaming machine (8DMV type, manufactured by Dalton Co., Ltd.), transferred to a piston-type spinning stock solution tank, and left to stand under reduced pressure to perform defoaming. After extruding the undiluted solution with a piston, a fixed amount of a gear pump is fed, and the pore size is 10 μm.
After filtration through a sintering filter having a pore size of 0.275 mm, a hole length of 0.5 mm, and a number of holes of 300, a coagulation bath containing 20% by weight of sodium sulfate (boric acid and hydroxide) containing 20% by weight of sodium sulfate was passed. (Adjusted to pH 11 with sodium) at a spinning speed of 5 m / min.

Next, the obtained regenerated collagen fibers (30
0, 20 m) were converted to epichlorohydrin 1.7% by weight,
25 ° C. was added to 1.32 kg of an aqueous solution containing 0.0246% by weight of sodium hydroxide and 17% by weight of sodium sulfate.
For 4 hours, the temperature of the reaction solution was further increased to 43 ° C., and the mixture was impregnated for 2 hours.

After the completion of the reaction, the reaction solution was removed, and the mixture was washed three times with 1.32 kg of water at 25 ° C. using a fluidized apparatus. Thereafter, 5% by weight of aluminum sulfate, 0.9% by weight of trisodium citrate and 1.
1.32 kg of an aqueous solution containing 2% by weight was impregnated at 30 ° C., and 2 hours, 3 hours, and 4 hours after the start of the reaction, 13.2 g of a 5% by weight aqueous sodium hydroxide solution was added to the reaction solution, and the total was added. The reaction was performed for 6 hours. After the completion of the reaction, the reaction solution was removed, and the mixture was washed three times with 1.32 kg of water at 25 ° C. in a fluidized apparatus three times.

Next, a part of the prepared fiber was immersed in a bath filled with an oil agent comprising an emulsion of amino-modified silicone and a Pluronic type polyether antistatic agent, to thereby adhere the oil agent. One end of the fiber bundle is fixed inside the hot air convection dryer set to 50 ° C., and the fiber 1 is fixed to the other end.
A 2.8 g weight was suspended from the book and dried under tension for 2 hours, after which measurements were taken.

(Example 2) The solid content of the stock solution was adjusted to 7.0%.
The experiment was performed in the same manner as in Example 1, except that

(Example 3) The solid concentration of the stock solution was 8.0%.
The experiment was performed in the same manner as in Example 1, except that

Example 4 An experiment was conducted in the same manner as in Example 1 except that the reaction time at 43 ° C. in the reaction with epichlorohydrin was changed to 1 hour.

Example 5 An experiment was performed in the same manner as in Example 1 except that the reaction time at 43 ° C. in the reaction with epichlorohydrin was changed to 4 hours.

Example 6 An experiment was performed in the same manner as in Example 1 except that the reaction time at 43 ° C. in the reaction with epichlorohydrin was changed to 18 hours.

Example 7 An experiment was performed in the same manner as in Example 1 except that the reaction time during the treatment with aluminum sulfate was changed to 15 minutes.

(Example 8) The treatment with an aluminum salt was performed using 5.9% by weight of basic aluminum chloride (Velcotan AC-P, manufactured by Nippon Seika Co., Ltd.) and 4.9% of sodium chloride.
After immersing in 1.32 kg of an aqueous solution containing 0.98% by weight and 0.98% of sodium formate at 2 ° C. for 15 hours, the obtained fiber was washed with running water for 2 hours, and the same procedure as in Example 1 was carried out. An experiment was performed.

Reference Example 1 1200 g of skin pieces (collagen content 180
g), 30 g of an aqueous solution of hydrogen peroxide diluted to 30% by weight was added thereto, and then dissolved in an aqueous solution of lactic acid to have a pH of 3.5 and a solid content of 7.
A stock solution adjusted to 5% by weight was prepared. The stock solution was subjected to a stirring and defoaming process under reduced pressure by a stirring and defoaming machine (8DMV type, manufactured by Dalton Co., Ltd.), transferred to a piston-type spinning stock solution tank, and left to stand under reduced pressure to perform defoaming. After extruding the undiluted solution with a piston, a fixed amount of a gear pump is fed, and the pore size is 10 μm.
After filtration through a sintering filter having a pore size of 0.275 mm, a hole length of 0.5 mm, and a number of holes of 300, a coagulation bath containing 20% by weight of sodium sulfate (boric acid and hydroxide) containing 20% by weight of sodium sulfate was passed. (Adjusted to pH 11 with sodium) at a spinning speed of 5 m / min.

Next, the obtained regenerated collagen fibers (30
0, 1.5 m) were converted to deuterated epichlorohydrin 1.
After immersing in 100 g of an aqueous solution containing 7% by weight, 0.0246% by weight of sodium hydroxide, and 17% by weight of sodium sulfate at 25 ° C for 4 hours, the temperature of the reaction solution was further increased to 43 ° C.
And soaked for 2 hours. After the reaction was completed, the reaction solution was removed, and then washed with running water for 30 minutes.

Reference Example 2 An experiment was performed in the same manner as in Reference Example 1, except that the reaction time at 43 ° C. in the reaction with epichlorohydrin was changed to 4 hours.

Reference Example 3 An experiment was performed in the same manner as in Reference Example 1, except that the reaction time at 43 ° C. in the reaction of epichlorohydrin was changed to 18 hours.

Comparative Example 1 The reaction with epichlorohydrin was carried out at 25 ° C. for 2 hours in 1.32 kg of an aqueous solution containing 1.7% by weight of epichlorohydrin and 17% by weight of sodium sulfate. An experiment was performed in the same manner as in Example 1.

Comparative Example 2 An experiment was conducted in the same manner as in Example 1 except that epichlorohydrin treatment and the accompanying water washing were not performed.

Comparative Example 3 An experiment was performed in the same manner as in Example 1 except that the treatment with the aluminum salt was not performed.

(Example 9) 1200 g of skin pieces (collagen content: 180
g) was dissolved in an aqueous lactic acid solution to prepare a stock solution adjusted to pH 3.5 and a collagen concentration of 7.5% by weight. The stock solution was subjected to a stirring and defoaming process under reduced pressure by a stirring and defoaming machine (8DMV type, manufactured by Dalton Co., Ltd.), transferred to a piston-type spinning stock solution tank, and left to stand under reduced pressure to perform defoaming. After extruding the undiluted solution with a piston, a fixed amount of gear pump is supplied and filtered with a sintered filter having a pore diameter of 10 μm, and then a pore diameter of 0.30 m is obtained.
m, through a spinning nozzle with a hole length of 0.5 mm and 300 holes,
It was discharged at a spinning speed of 5 m / min into a coagulation bath containing 25% by weight of sodium sulfate (adjusted to pH 11 with boric acid and sodium hydroxide) at 25 ° C.

Next, the obtained regenerated collagen fiber was mixed with 1.7% by weight of epichlorohydrin, 0.9% by weight of 2,4,6-tris (dimethylaminomethyl) phenol, 0.09% by weight of salicylic acid, And 16.5 kg of an aqueous solution containing 13% by weight of sodium sulfate at 25 ° C. for 24 hours.

After washing with running water for 1 hour, an aqueous solution containing 10% by weight of basic aluminum chloride (Velcotan AC-P, manufactured by Nippon Seika Co., Ltd.) and 5% by weight of sodium chloride.
It was immersed in 6 kg at 25 ° C. for 12 hours. Thereafter, the obtained fibers were washed with running water for 2 hours.

The subsequent processing was performed in the same manner as in Example 1.

(Evaluation method) The fineness of the regenerated collagen fiber obtained above, the aluminum content, the measurement of the heat resistance of the hair iron, the curl shape and the curl characteristic value measurement for the regenerated collagen fiber, the presence or absence of odor generation, the wetness Tactile sensation, analysis of gas components contained in the gas phase, quantification of alkylation reaction rate, and confirmation of structure were examined by the following methods.

(Fineness) Motorcycle blow type fineness measuring instrument De
Using Nier Computer DC-77A (manufactured by Search Co., Ltd.), the temperature was 20 ± 2 ° C. and the relative humidity was 65 ± 2.
The fineness was measured in a% atmosphere.

(Aluminum content) After the regenerated collagen fiber was dried with a desiccator, 0.1 g of the fiber was put into a mixed solution of 5 ml of nitric acid and 15 ml of hydrochloric acid and heated and dissolved. After cooling, this solution was diluted 50-fold with water, and the aluminum content in the diluted aqueous solution was measured using an atomic absorption spectrometer (model Z-5300, manufactured by Hitachi, Ltd.).

(Hair Iron Heat Resistance) (1) Fiber bundles (3.5 g / 50 Cm) which were well opened and adjusted to 70,000 dtex were arranged on newsprint so that the fibers did not overlap. (2) The fiber bundle was wound around an aluminum pipe having an outer diameter of 30 mm together with the newspaper in a direction in which the fiber became parallel to the pipe, and both ends were firmly fixed with rubber bands so that the newspaper did not shift. (3) The wound rod is put into a steam setter auto vacuum sterilizer (HA-300P, manufactured by Hirayama Seisakusho),
The fiber was wet at 85 ° C. for 30 minutes. (4) Next, remove the rod from the auto vacuum sterilizer,
The mixture was placed in a hot-air convection dryer (PV-221 manufactured by Tabai Espec Corp.) adjusted at 115 ° C. for 30 minutes to be dried. (5) Then, the rod was taken out from the hot air convection dryer and cooled at room temperature for about 30 minutes, and then the fiber bundle was removed from the rod. (6) After the fibers are well opened in an atmosphere of a temperature of 20 ± 2 ° C. and a relative humidity of 65 ± 2%, the entire length of the fiber bundle is folded in two, bundled with a thread, and a test length of 20 cm from the cut. By the way, the fiber bundle was cut off to make the fiber length uniform. (7) Curling iron (GOL) adjusted to various temperatures
DEN SUPREMEINC. Was lightly nipped and slid quickly (about 3 seconds) to evaporate the water on the fiber surface, and then the fiber bundle was nipped again and slid from the root of the bundle to the tip for 5 seconds. After this operation, the contraction rate of the fiber bundle and the crimped state of the fiber tip were examined. The shrinkage ratio is L for the length of the fiber bundle before ironing, and Lo for the length of the fiber bundle after ironing. (If the fiber bundle swells during ironing, measure the length when the fiber bundle is stretched. Do)
It was determined from the following equation.

Shrinkage = [(L−Lo) / L] × 100 The heat resistance of the hair iron is such that the maximum shrinkage of the hair iron during the ironing process is 5% or less, and the maximum temperature of the iron that does not cause fiber shrinkage is determined. It was described as the iron heat resistance temperature.
Also, the hair iron temperature is set in increments of 10 ° C,
Each time the temperature was measured, the fiber bundle was changed to a new fiber bundle without a hair iron, and the measurement was performed.

(Curl Shape Giving and Curling Characteristic Value Measuring Method)
The curl shape was imparted and the curl characteristics were measured as follows. (1) The entire length of the fiber bundle is shifted to 66.0 cm by inserting a fiber bundle (2.5 g / 58.4 Cm) adjusted to 42800 dtex by opening the fiber well, and the center of the fiber bundle is shifted by 2 at the center. I folded it and tied it with a thread. (2) The fiber bundle was wound around an aluminum pipe having an outer diameter of 9 mm while being twisted once per pitch, and both ends were firmly fixed with rubber bands so that the fiber bundle did not shift. (3) The wound rod is put into a steam setter auto vacuum sterilizer (HA-300P, manufactured by Hirayama Seisakusho),
The fiber was wet at 90 ° C. for 2 hours. (4) Next, remove the rod from the auto vacuum sterilizer,
It was placed in a hot air convection dryer (PV-221, manufactured by Tabai Espec Co., Ltd.) adjusted at 30 ° C. for 1 hour to be dried. (5) Then, the rod was taken out from the hot air convection dryer and cooled at room temperature for about 30 minutes, and then the fiber bundle was removed from the rod. (6) After shampooing the fiber bundle while performing the combing operation 20 times in warm water at 40 ° C., the fiber bundle was dried using a drier while the fiber bundle was unraveled by hand. (7) For the shampoo resistance of curl (curl formation rate by the number of repetitive shampooing), the above-mentioned operation (6) was repeated three times, and it was observed whether the curl shape was maintained. 、, those with a slight curl shape were rated as Δ, and those with little curl shape were rated as x.

(Confirmation of Odor Generation) Assuming a heat treatment of the regenerated collagen fibers with a drier or the like, the fibers were put into a hot air convection dryer at 100 ° C. and heat-treated for 10 minutes.
By smelling this odor, it was determined whether or not any odor peculiar to the sulfur-containing compound was generated.

(Tactile sensation when wet) 25 g of regenerated collagen fiber
The tactile sensation after being immersed in water at 5 ° C. for 5 minutes was observed. A sample having a firm and good tactile sensation was rated as ○, and a sample having a stiffness and swelling due to water absorption was rated as x.

(Analysis of Gas Components Contained in Gas Phase) 100
0.2 g of the fiber sample that had been heat-treated at 20 ° C. was placed in a 20 ml vial, heated again at 60 ° C. for 10 minutes, and the gas phase was separated by Shimadzu gas chromatograph mass spectrometer QP-5050.
The amount of ions detected was measured while increasing the column temperature from 40 ° C. to 200 ° C. at a rate of 10 ° C./min and from 200 ° C. to 280 ° C. at a rate of 20 ° C./min.

(Quantification of Reaction Rate and Confirmation of Structure) A fiber sample (3 mg) obtained by drying fibers obtained in Examples and Comparative Examples was weighed, and 0.200 ml of 6N hydrochloric acid was added thereto.
The reaction was performed at 10 ° C. for 22 hours. After drying under reduced pressure, the obtained solid was dissolved in 12.0 ml of pure water. Solution 0.05
Using 0 ml as a sample, the amount of amino acids was quantified using an amino acid analyzer 835 manufactured by Hitachi. The amino acid consumption rate was calculated by comparing the amount of change in amino acid before and after the reaction with reference to alanine which is not affected by the crosslinking reaction in amino acid analysis of the regenerated collagen fiber before the crosslinking reaction.

Similarly, a fiber sample (80 mg) obtained by drying the fiber obtained in the reference example was weighed, 5 ml of 6N hydrochloric acid was added thereto, and the reaction was carried out at 110 ° C. for 22 hours. After cooling to room temperature, 1.1 g of the obtained solution was weighed, and 10 mg of deuterated chloroform was added thereto to obtain a sample. The sample was subjected to measurement of deuterium nuclei (resonance frequency: 76.5 MHz) using a superconducting nuclear magnetic resonance apparatus manufactured by JASCO Corporation, and structural analysis of epichlorohydrin-derived components contained in the fibers based on the signal of deuterated chloroform was performed. Quantification was performed.

(Fiber color tone) The fiber color tone was 4
By combing the fiber bundle adjusted to 2800 dtex, 1
The width was adjusted to a cm width, and the observation was made visually under sunlight in fine weather.

[0113]

[Table 1]

[0114]

[Table 2] From the results shown in Tables 1 and 2, when the free amino group of the regenerated collagen fiber is treated with an alkylating agent represented by a monofunctional epoxy compound, and further treated with a metal aluminum salt, the regenerated collagen fiber has a pale color and excellent wet feel. After maintaining the temperature of the regenerated collagen fiber at 20 to 100 ° C. in a saturated or high humidity steam atmosphere or in the presence of moisture, 2
It can be seen that by drying at a temperature of 0 ° C. to 220 ° C., a fiber capable of giving an arbitrary shape firmly is obtained.

Here, when the alkylation reaction is insufficient,
The desired properties could not be sufficiently exhibited, and the property was achieved that both the curl retention during shampooing and the heat resistance were achieved by performing a sufficient reaction by adding an alkali and heating. In addition, as a result of examining the influence of the amount of aluminum introduced, when aluminum was not introduced at all, both the curl retention during shampooing and the heat resistance of the iron were not satisfactory. As a result of the examination, it was confirmed that the curl retention was exhibited by the introduction of an aluminum compound, and that the iron heat resistance increased as the amount of aluminum increased. Therefore, as a regenerated collagen fiber showing satisfactory properties, the modification rate of free amino groups is 50% or more,
It became clear that it was necessary to contain an aluminum compound.

Furthermore, the sample obtained by acid hydrolysis of the regenerated collagen fibers obtained in Reference Examples 1 to 3 was observed by deuterium nuclear magnetic resonance. As a result, a structure in which epichlorohydrin was added to the amino group was confirmed; Hydrogen nuclear NMR
(76.5MHz, 6N hydrochloric acid) 3.80ppm _{(broad, 1D, N-CD 2 -CD} (OH)), 3.65ppm
(Br, 2D, N-CD 2 -CD (OH) -CD 2),
3.20ppm (br, 2D, N- CD 2). In addition, as a result of amino acid analysis of the sample, it was observed that lysine, hydroxylysine and histidine were consumed by the alkylation reaction. Therefore, it is apparent that the reactive (free) amino groups lysine, hydroxylysine and histidine are protected by an alkyl group having a hydroxyl group.

Further, by treating collagen with an oxidizing agent, it was possible to obtain a fiber which does not generate an odor peculiar to a sulfur-containing compound even when heated.

In the analysis of the gas generated from the fiber obtained in Example 9 where odor was observed, four peaks were detected. The results of analyzing these four peaks by mass spectrometry are as follows. Compound name (retention time, M +)
In the order: methyl mercaptan (2.74 minutes, 4
7), dimethyl sulfide (3.03 min, 62), dimethyl disulfide (5.19 min, 94), 3- (methylthio) -propionaldehyde (8.12 min, 104).

No odor was observed in the other regenerated collagen fibers to which the aqueous hydrogen peroxide solution was added, and the same analysis was carried out, but no peak was detected.

From the above results, the regenerated collagen fiber obtained by the method of treating collagen with an oxidizing agent and then reacting the monofunctional epoxy compound with collagen is preferable because it can suppress the generation of odor peculiar to sulfur-containing compounds. I understand.

[0121]

The regenerated collagen fiber of the present invention has a light color and a good wet feel. Furthermore, by treating a methionine residue in collagen with an oxidizing agent and then reacting it with a monofunctional epoxy compound, it is possible to suppress the generation of an odor peculiar to a sulfur-containing compound generated during heat treatment. Moreover, a desired shape can be easily imparted, and furthermore, the shape can be firmly set and held, and a curl setting can be applied to head decoration products such as a wig, a hairpiece or a doll hair, or a shape application of a textile product made of woven or nonwoven fabric ( It is an excellent material that can be suitably used for (set) and the like.

Continued on the front page F term (reference) 4L031 AA03 AA11 AB01 AB04 BA13 BA33 DA08 4L033 AA03 AA10 AB01 AC01 AC15 BA08 4L035 AA01 BB03 BB07 BB16

Claims (4)

[Claims] 1. 50% of free amino groups of regenerated collagen
The above is a structure in which the main chain having a hydroxyl group or an alkoxyl group at the β-position or γ-position is modified with an alkyl group having 2 to 20 carbon atoms, and the regenerated collagen containing an aluminum compound in the fiber. fiber. 2. The regenerated collagen fiber according to claim 1, wherein the alkyl group is a compound represented by the following general formula (I). —CH ₂ —CH (OX) —R (I) wherein R is R ¹ —, R ² —O—CH ₂ — or R ² —CO
O-CH ₂ - represents a substituent represented by, R ¹ in the substituent is 2 or more hydrocarbon groups or CH ₂ Cl atoms,
R ² represents a hydrocarbon group having 4 or more carbon atoms, and X represents hydrogen or a hydrocarbon group. ] 3. The regenerated collagen fiber according to claim 1, wherein at least a part of the methionine residue in the regenerated collagen is a sulfoxidized methionine residue or a sulfonated methionine residue. 4. The regenerated collagen fiber according to claim 1, wherein the content of aluminum in the regenerated collagen fiber is 1 to 10% by weight.