JP3109755B2 - Artificial hair comprising fibers of poly-α-amino acid derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to artificial hair comprising a fibrous poly-.alpha.-amino acid derivative having an amino group and a mercapto group or a disulfide group on the side chain of a polymer.

[0002]

2. Description of the Related Art Poly-α-amino acids, although being synthetic polymers, are close to proteins in chemical structure, and have been studied for a long time as biopolymer models. In addition to substituting general-purpose natural proteins such as natural leather and silk, research on application to artificial skin, enzyme-immobilized carriers, piezoelectric elements, cosmetics, etc. is also being conducted ("Polyamino acids-applications and prospects", Kodansha). (1974)).

[0003] Also, studies have been conducted to convert the ester of the side chain of the polyacidic amino acid ω-ester into various functions by transesterification or amidation reaction (J
ournal of Polymer Science: Part C: Polymer Letter
s, 27 , 399 (1989)). And as an application example,
Artificial hair having a perm like human hair using a poly-α-amino acid having a mercapto group or a disulfide group on its side chain has been proposed (JP-A-63-191829).

[0004] However, poly-α-amino acids generally have poor dyeing properties, and this artificial hair is also very complicated and cumbersome in the process of being deposited by combining pigments in order to correspond to various human hair colors. At present, such a coloring step is required, which is disadvantageous in cost.

Therefore, poly-α-amino acids having amino and mercapto groups or disulfide groups and having a plurality of functions are desired as materials for artificial hair.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an artificial artificial fiber comprising a fiber of a poly-α-amino acid derivative which has a shape-retaining property after molding, is capable of being acid-dyeable, and is insoluble in water or alcohol. To provide hair.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a fibrous poly-α-amino acid in which an amino group and a mercapto group or a disulfide group are appropriately supported on a polymer side chain. The inventors have found that the above problems can be solved by using a derivative as a material for artificial hair, and based on such findings, completed the present invention.

That is, the present invention provides a compound represented by the following general formula (1):
The present invention relates to artificial hair composed of fibers of a poly-α-amino acid derivative which is insoluble in water or alcohol and represented by (4).

[0009]

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Wherein Z is an alkyl group having 1 to 6 carbon atoms, a tertiary aminoalkyl group having 3 to 6 carbon atoms or H
And n is an integer of 50 to 4000.

[0011]

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Here, Z represents an alkyl group having 1 to 6 carbon atoms or H, and n is an integer of 50 to 4000.

[0013]

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Wherein Z represents an alkyl group having 1 to 6 carbon atoms, and n + m is an integer of 50 to 4000.

[0015]

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Here, Z represents an alkyl group having 1 to 6 carbon atoms, and n + m is an integer of 50 to 4000.

[0017] Here, R (1) to (4) wherein the following general formula (5) are each represented by R ^a, R ^b or R ^c (6) or (7), and , R ^a and R ^b are each contained in R in an amount of 1 mol% or more, and the sum of R ^a and R ^b is 55 mol% or less in R.

Here,

[0019]

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(Where k is 1 or 2 and l is 1 to
Represents an integer of 4. R ¹ , R ² and R ³ represent H or an alkyl group having 1 to 4 carbon atoms. ),

[0021]

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[Where k is 1 or 2 and 1 is 1 to
Represents an integer of 4. R ¹ is H or an alkyl group having 1 to 4 carbon atoms, and R ² is H or S (CH ₂ ) _j NR ³ R
⁴ (j represents an integer of 1 to 4; R ³ and R ⁴ represent H or an alkyl group having 1 to 4 carbon atoms). Also, R
^{In b} , R ^b may be cross-linked to each other by a disulfide bond within a molecule and / or between molecules. ],

[0023]

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(Where k is 1 or 2. R 'represents an alkyl group having 1 to 4 carbon atoms or a benzyl group).

The poly-α-amino acid, which is a raw material of the poly-α-amino acid derivative used as the material of the artificial hair of the present invention, is a homopolymer or copolymer of glutamic acid or an ω-ester of aspartic acid, or glutamic acid and / or It may be a copolymer of an aspartic acid ω-ester and a neutral α-amino acid such as glycine, alanine, valine, norvaline, leucine, phenylalanine, methionine and the like. Further, a copolymer of an ω-ester of glutamic acid and / or aspartic acid and two or more neutral α-amino acids may be used. Hereinafter, these are collectively referred to as raw material poly-α-amino acids.

In order for the fibrous poly-α-amino acid derivative used as the material of the artificial hair of the present invention to have sufficient strength and durability, the degree of polymerization must be at least 50 to 4000, and is preferably Is 100-2000. For that purpose, the polymerization degree of the raw material poly-α-amino acid is desirably 50 to 10,000.

As a method for producing such a raw material poly-α-amino acid having a molecular weight, a polycondensation method of amino acid N-carbonic anhydride has been partially completed and industrialized. Examples of the initiator in the polycondensation reaction include butylamine, ethylamine, and ammonia as monoamine-type initiators, butanol, ethanol, water, and the like as monol-type initiators, and hexamethylenediamine, ethylenediamine, and the like as diamine-type initiators. However, examples of the diol type initiator include hexamethylene glycol, ethylene glycol and the like.

The raw material poly-α- produced in this way
A poly-α-amino acid derivative can be prepared from an amino acid by directly amidating the raw material poly-α-amino acid with an organic diamine and an organic amine having a mercapto group or a disulfide group. By the way,
The poly-α-amino acid derivative thus obtained is a novel substance.

The organic diamine is represented by the general formula HR ¹ N (CH ₂ ) _n NR ² R ³ (10) (where n is an integer of 1 to 4, and R ¹ , R ² and R
³ represents H or an alkyl group having 1 to 4 carbon atoms. ), Ethylenediamine, N
-Methyl-1,3-diaminopropane, N, N-dimethyl-1,3-diaminopropane and the like. The organic amine having a mercapto group or a disulfide group includes a compound represented by the general formula HR ¹ N (CH ₂ ) _m SR ² (11) [where m is an integer of 1 to 4, R ¹ is H or 1 carbon atom. And R ² is H or S (C
H ₂ ) _n NR ³ R ⁴ (n represents an integer of 1 to 4; R ³ and R ⁴ represent H or an alkyl group having 1 to 4 carbon atoms)]. And cysteamine, cystamine and the like.

The above-mentioned direct amidation reaction is carried out using the starting poly-α
-Directly amidating the amino acid and the amine (organic diamine and organic amine) in a homogeneous system,
That is, the amine is added to a solution of the raw material poly-α-amino acid as in a normal organic reaction, and then added at room temperature to 100 ° C. for 1 hour.
The reaction is carried out at a temperature of 40 to 60 ° C for several hours, preferably for 2 hours to 2 days. At this time, the solvent is preferably a solvent that is a good solvent for the raw material poly-α-amino acid and does not react with the amine, and specific examples include chloroform, methylene chloride, tetrachloroethylene, and trichloroethylene.
Thereafter, by forming into a fibrous form, a fibrous poly-α-amino acid derivative serving as a material for the artificial hair of the present invention can be obtained.

Further, such a fibrous poly-α-amino acid derivative can be obtained as follows. That is, the raw material poly-α-amino acid is first formed into a fibrous form, and then immersed in a solution in which the amine is dissolved at room temperature to 100 ° C. for 1 hour to 1 week, preferably at 50 to 80 ° C. for 5 to 72 hours. To an amidation reaction. At this time, as the solvent, a solvent which is a poor solvent for the raw material poly-α-amino acid after forming into a fibrous form and which does not react with an amine is desirable. Specifically, water, methanol, ethanol, isopropanol, acetonitrile , Dioxane and the like, and the amine concentration in the solution is 0.1 to 70 wt%, preferably 1 to 50 wt%.

In the above-mentioned amidation reaction, the organic diamine and the organic amine having a mercapto group or a disulfide group may be combined to carry out the amidation reaction at one time, or may be divided into two and separately. An amidation reaction may be performed. By performing such an amidation reaction, a desired poly-α-amino acid derivative having an amino group and a mercapto group or a disulfide group on the side chain can be obtained. 2
When the reaction is carried out step by step, the order of the reaction of the organic diamine and the organic amine to be reacted with the poly-α-amino acid does not particularly matter.

The fibrous poly-α- obtained in this manner
In order for an amino acid derivative to exhibit excellent acid stainability, it is necessary that an amino group required for expression of stainability is appropriately carried. For this purpose, the above general formulas (1) to (1)
Among the side chains R of the fibrous poly-α-amino acid derivative represented by (4), ^Ra represented by the above general formula (5) is 1
A fibrous poly-α-amino acid derivative containing at least mol% is preferred. Less than 1 mol% of the fibrous poly-α-amino acid derivative has few amino groups and does not show practical dyeability.

In order for the fibrous poly-α-amino acid derivative according to the present invention to exhibit excellent shape retention, it is necessary that a mercapto group or a disulfide group necessary for the expression of shape retention be appropriately carried. is there. For this purpose,
Fibrous poly- represented by the above general formulas (1) to (4)
Among the side chains R of the α-amino acid derivative, the above general formula (6)
A fibrous poly-α containing 1 mol% or more of R ^b represented by
-Amino acid derivatives are preferred. Less than 1 mol% of fibrous poly-
The α-amino acid derivative has a small number of crosslinks between molecules and does not exhibit practical shape retention.

In the side chain R of the fibrous poly-α-amino acid derivative represented by the general formulas (1) to (4), the sum of ^Ra and ^Rb is 55 mol% or less. It is desirable. A fibrous poly-α-amino acid derivative containing a total of ^Ra and ^Rb of more than 55 mol% becomes soluble in water and alcohols because it carries too many amino groups and mercapto groups, It is not a suitable material for artificial hair in terms of durability in daily life.

The artificial hair comprising the fibrous poly-α-amino acid derivative of the present invention is insoluble in water or alcohol. The alcohol referred to here is methanol, ethanol, propanol and isopropanol.

The artificial hair of the present invention can be dyed in the same manner as human hair, and can easily cope with subtle shades of human hair of 10 colors and 10 colors. Also, once the cross-linking between disulfide bond molecules is once cleaved with perm liquid 1 (reducing agent), the wave is set to a desired wave, and the cross-linking between disulfide bond molecules is reapplied with perm liquid 2 (oxidizing agent). The favorite wave is retained, and it has an excellent performance with so-called perm.

[0038]

The fibrous poly-α-amino acid derivative according to the present invention has an amino group in the side chain of the polymer, and can be arbitrarily dyed with an acidic dye, and has a mercapto group or a disulfide group. By exchanging the cross-linking between the molecules, it is possible to give the shape retention, so that excellent artificial hair can be obtained.

[0039]

EXAMPLES Hereinafter, the present invention will be described with reference to Examples to further clarify the features of the present invention, but the present invention is not limited to these Examples.

Example 1 (Synthesis of Derivative (Part 1)) 2.65M N, N-dimethyl-formate was added to 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride and 162 g of chloroform.
50 μl of a 1,3-diaminopropane solution in dioxane was added, and the mixture was stirred at room temperature for 12 hours. N, N-Dimethyl-1,3-diaminopropane (4.09 g) and cysteamine (3.08 g) were added to 191 g of a chloroform solution of the obtained poly-γ-methyl-L-glutamate (PMG) (degree of polymerization: 1200).
The mixture was stirred at 3 ° C. for 3 hours to obtain a solution of the poly-α-amino acid derivative (resin concentration: 15% by weight).

As a result of ¹ H-NMR measurement, the total amidation ratio was 35%.

Example 2 (Synthesis of Derivative (Part 2)) 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride
45.9 g of L-leucine N-carbonic anhydride and chloroform 4
147 μl of 2.65 M N, N-dimethyl-1,3-diaminopropane in dioxane was added to 50 g, and the mixture was stirred at room temperature for 12 hours to carry out polymerization. To 511 g of a chloroform solution of the obtained γ-methyl-L-glutamate / L-leucine copolymer (degree of polymerization: 1300), 5.1 g of N, N-dimethyl-1,3-diaminopropane and 3.7 g of cysteamine were added.
The mixture was stirred at 6 ° C. for 6 hours to obtain a solution of a poly-α-amino acid derivative (resin concentration: 13% by weight).

As a result of ¹ H-NMR measurement, the total amidation ratio was 45%.

Example 3 (Synthesis of Derivative (Part 3)) 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride and 162 g of chloroform were cooled to 10 ° C., and 40 μl of 2.65 M butanol in dioxane and 0.1 g of triethylamine were cooled.
Was added, and the mixture was heated to room temperature and stirred for 12 hours. P obtained
N, N is added to 191 g of a chloroform solution of MG (polymerization degree: 1000).
-Dimethyl-1,3-diaminopropane (4.09 g) and cysteamine (3.08 g) were added, and the mixture was stirred at 60 ° C. for 3 hours to give poly-.
A solution of the α-amino acid derivative (resin concentration 15% by weight) was obtained.

As a result of ¹ H-NMR measurement, the total amidation ratio was 32%.

Example 4 (Synthesis of Derivative (Part 4)) To 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride and 162 g of chloroform were added 30 μl of a 2.65 M ethylenediamine dioxane solution, and the mixture was stirred at room temperature for 12 hours. . 191 g of a chloroform solution of the obtained PMG (degree of polymerization: 1100)
N, N-dimethyl-1,3-diaminopropane 4.09g
And 3.08 g of cysteamine, and stirred at 60 ° C. for 3 hours to obtain a solution of the poly-α-amino acid derivative (resin concentration: 15% by weight).
I got

As a result of ¹ H-NMR measurement, the total amidation ratio was 33%.

Example 5 (Synthesis of Derivative (No. 5)) 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride and 162 g of chloroform were cooled to 10 ° C., and 30 μl of 2.65 M ethylene glycol in dioxane and 0.1% of triethylamine were cooled. After adding g, the mixture was heated to room temperature and stirred for 12 hours. 191 g of a chloroform solution of the obtained PMG (degree of polymerization: 950)
N, N-dimethyl-1,3-diaminopropane 4.09g
And 3.08 g of cysteamine were added, and the mixture was stirred at 60 ° C. for 3 hours to obtain a solution of a poly-α-amino acid derivative (resin concentration: 15% by weight).

As a result of ¹ H-NMR measurement, the total amidation ratio was 30%.

Example 6 (Artificial Hair (Part 1)) 2.65M in 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride and 162 g of 1,2-dichloroethane (EDC)
50 μl of a dioxane solution of N, N-dimethyl-1,3-diaminopropane was added, and the mixture was stirred at room temperature for 12 hours. The obtained EDC solution of PMG (degree of polymerization: 1200) was used for the nozzle diameter.
0.4mmφ, dope discharge speed 0.86ml / min (6.79m / min),
Coagulating solvent: Tetrachloroethylene: kerosene = 3: 1, spinning under the conditions of a coagulating bath length of 3 m, to obtain a fiber having a circular cross section of 163 denier in thickness. 5 g of this PMG fiber drawn 1.8 times was fixed in a frame, and 50 ml of methanol, N, N-
Amidation was carried out by immersing in 7.5 g of dimethyl-1,3-diaminopropane and 7.5 g of cysteamine at 60 ° C. for 24 hours.

Washing was repeated twice with 30 ml of methanol and then dried to obtain a fibrous poly-α-amino acid derivative.

The obtained fibrous poly-α-amino acid derivative was confirmed to exhibit excellent dyeability by the following acidic dyeing test, and was confirmed to be subjected to permanent wave by the following permanent wave effect test. For comparison, the poly-γ-methyl-L-glutamate fiber obtained in JP-B-43-28787 and the human hair of barban hair (hair of a 10-year-old girl) were similarly dyed and subjected to permanent wave treatment.

The results are shown in Table I. From the results in Table I, it was found that this fibrous poly-α-amino acid derivative had excellent performance when used as artificial hair.

[0054]

[Table 1]

[Acid Dyeing Test] A test as to whether or not it shows a dyeing property with respect to an acid dye was carried out as follows.

The fiber or film was immersed in a dyeless solution at 90 ° C. for 1 hour in a state of no tension. Thereafter, the fibers were washed with water and air-dried.

The dyeability was evaluated as follows. That is, ●: dark color, ○: medium color, Δ: light color to contamination, and ×: unstained.

The composition of the dyeing solution was 2% by weight of dye: Irgaran Black BGL (manufactured by Seiwa Co., Ltd.) and 5% by weight of anhydrous sodium sulfate.

[Permanent Wave Effect Test] A test as to whether or not a permanent wave is applied was performed as follows.

The fiber is wound on a rod with a tension of 70 g, and a first liquid for permanent wave (a 6.5% aqueous solution of ammonium thioglycolate is prepared, and p is added with aqueous ammonia).
H adjusted to 9.2 to 9.6) for 15 minutes.
Then, it was immersed in the second liquid for permanent wave (5% aqueous solution of sodium bromate) for 15 minutes. The fiber was removed from the rod, washed with water in a free state, and air-dried.

The permanent wave effect was obtained by the following equation.

[0062]

(Equation 1)

Example 7 (Artificial Hair (Part 2)) 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride
To 45.9 g of L-leucine N-carbonic anhydride and 450 g of EDC
147 μl of 2.65 M N, N-dimethyl-1,3-diaminopropane in dioxane was added, and the mixture was stirred at room temperature for 12 hours to carry out polymerization.

The obtained γ-methyl-L-glutamate /
The EDC solution of the L-leucine copolymer (degree of polymerization: 1300) was spun, amidated, and washed under the same conditions as in Example 6 to obtain a fibrous poly-α-amino acid derivative.

The resulting fibrous poly-α-amino acid derivative exhibited a deep color dyeing property, a permanent wave effect of 3.9, and was found to have excellent performance when used as artificial hair.

Example 8 (Artificial Hair (Part 3)) 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride and 162 g of EDC were cooled to 10 ° C., and 40 μl of 2.65 M butanol in dioxane and 0.1 g of triethylamine were added. After the addition, the mixture was heated to room temperature and stirred for 12 hours. PMG obtained
The EDC solution (polymerization degree: 1000) was spun, amidated and washed under the same conditions as in Example 6 to obtain a fibrous poly-α-amino acid derivative.

The resulting fibrous poly-α-amino acid derivative shows a dark color, and a permanent wave effect is obtained.
3.2, which indicates that the hair had excellent performance when used as artificial hair.

Example 9 (Artificial Hair (Part 4)) To 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride and 162 g of EDC were added 30 μl of a 2.65 M ethylenediamine dioxane solution, and the mixture was stirred at room temperature for 12 hours. The obtained EDC solution of PMG (degree of polymerization: 1100) was spun, amidated and washed under the same conditions as in Example 6 to obtain a fibrous poly-α-amino acid derivative.

The resulting fibrous poly-α-amino acid derivative shows a deep-colored dyeing property, and has a permanent wave effect.
3.5, which indicates that the hair had excellent performance when used as artificial hair.

Example 10 (Artificial Hair (Part 5)) 37.4 g of γ-methyl-L-glutamic acid N-carbonic anhydride and 162 g of EDC were cooled to 10 ° C., and 30 μl of 2.65 M ethylene glycol in dioxane and 0.1% of triethylamine were added.
After adding g, the mixture was heated to room temperature and stirred for 12 hours. The obtained EDC solution of PMG (degree of polymerization 950) was spun, amidated and washed under the same conditions as in Example 6 to obtain a fibrous poly-α-amino acid derivative.

The obtained fibrous poly-α-amino acid derivative shows a deep coloration, and the permanent wave effect is
3.2, which indicates that the hair had excellent performance when used as artificial hair.

Example 11 (Artificial Hair (Part 6)) A solution of the poly-α-amino acid derivative obtained in Example 1 was spun under the same conditions as in Example 6 to obtain a fiber having a circular cross section of 160 denier in thickness. Obtained. The fiber was washed three times with 300 ml of water, dried, dried and stretched 1.7 times to obtain a fibrous poly-α-amino acid derivative.

Under the same conditions, the poly-
A fibrous poly-α-amino acid derivative was obtained from the solution of the α-amino acid derivative. The obtained fibrous poly-α-amino acid derivative was found to have excellent performance when used as artificial hair by an acid dyeing test and a permanent wave effect test.

The results are shown in Table II.

[0075]

[Table 2]

[0076]

The poly-α-amino acid derivative according to the present invention is a synthetic polymer, but is close to a protein in chemical structure even though it is a synthetic polymer. Therefore, this fibrous molded product is more natural in terms of texture, heat resistance, and strain. Shows physical properties. In addition, since the poly-α-amino acid derivative has an amino group, it can be acid-stained similarly to a natural protein, and since it has a mercapto group or a disulfide group, it has an intermolecular structure by an oxidation-reduction reaction. The shape can be maintained by changing the cross-linking. Therefore, it gives excellent artificial hair.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-191829 (JP, A) JP-A-62-206007 (JP, A) JP-B-46-1355 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) A61L 27/00-27/60 C08G 69/00-69/50

Claims (1)

(57) [Claims] 1. Artificial hair comprising fibers of a polyamino acid represented by any of formulas (1) to (4). Embedded image [Z ¹ is H, an alkyl group having 1 to 6 carbon atoms or a tertiary aminoalkyl group having 3 to 6 carbon atoms, Z ² is H or an alkyl group having 1 to 6 carbon atoms, Z ³ Is an alkyl group having 1 to 6 carbon atoms, n is an integer of 50 to 4000, m and p are each an integer of 1 or more, the sum of m and p is 50 to 4000, and R is R ^a , R ^b or R ^c , R ^a and R ^b are each at least 1 mol% of the sum of R ^a , R ^b and R ^c , and the sum of R ^a and R ^b is R ^a , R ^b and 55 of the sum of R ^c
Or less mol%, the _{^{R a - (CH 2) k}} CONR 1 (CH 2) l NR
Is ^{2 (R 3),} the _{^{R b - (CH 2) k}} CONR 1 (CH 2) a l SR ^{4, R c} may _{^{-R 5, - (CH 2)}} k COOR 6 or -CH
₂ CH ₂ SMe (k is 1 or 2, l is an integer of 1 to 4, R ¹ is H or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each independently is H or an alkyl group having a carbon number of 1 to 4, ^{R 4} is H or ^{_{-S (CH 2) l NR 2}} (R 3), or the SH of ^{R b,} other ^{R b} within the same molecule S
H or a group formed by forming a disulfide bond with SH of R ^b in another molecule, R ⁵ is H or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is a group having 1 to 4 carbon atoms. Is an alkyl group or a benzyl group. ). ]