JP2530455B2 - Amino acid derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an amino acid derivative useful as a compounding ingredient for cosmetics. More specifically, the present invention relates to an amino acid derivative having excellent adsorption and softening effects on hair, excellent moisturizing properties, water solubility, and low irritation and high safety.

[Conventional technology]

BACKGROUND ART Amino acids have hitherto been used as a compounding agent for cosmetics because they are hypoallergenic, rapidly metabolized, excellent in safety, and have a moisturizing action.

However, the wetting action of amino acids is small,
If anything, the image effect that it is safe and useful for hair and skin because it is a constituent material of protein is stronger, and the actual effect is not so large.

Therefore, various amino acid derivatives have been developed for the purpose of imparting surface activity, oiliness, water solubility and the like to amino acids to enhance the cosmetic effect. For example, N-lauroyl-L-
N-acyl amino acid salts such as sodium glutamate and sodium N-coconut oil fatty acid methylalanine are typical ones, and although they are excellent in the effect as a surfactant for cosmetics, they are not adsorbable to the hair and have a moisturizing property. There is a problem that it is not sufficient and the water solubility is low depending on the type of amino acid, and the applicable cosmetics are limited.

In addition, although ester derivatives of amino acids have been proposed (for example, JP-A-58-110512), these also have insufficient adsorptivity to hair and moisturizing properties like N-acyl amino acid salts, and Depending on the type of amino acid, there is a problem that its water solubility is low and its application range is limited.

[Problems to be solved by the invention]

INDUSTRIAL APPLICABILITY The present invention has a property that amino acids are hypoallergenic and highly safe, but has little cosmetic effect, and the amino acid derivatives that have been proposed so far to improve it are also adsorbable to hair. It also has the problem of insufficient moisture retention and lack of water solubility depending on the type of amino acid and limited application range, and has excellent adsorption and softening effects on hair and moisture retention. Another object of the present invention is to provide an amino acid derivative that is highly water-soluble, has low irritation, and is highly safe.

[Means for solving problems]

The present inventors have synthesized various derivatives using amino acids, and have repeatedly studied their properties. As a result, the following general formula (I) (In the formula, R _{1 to} R ₃ are alkyl groups having 1 to ₃ carbon atoms, X is a hydrogen atom or a hydroxyl group, R ₄ is a side chain of α-amino acid, and Y is O.
Yes H, Cl, Br, cationic amino acid derivatives having a quaternary ammonium represented by NO ₃ or SO _4/2) is the excellent adsorption effect and flexibility effect on the specific hair cationic substance In addition, they have found that they have excellent moisturizing properties and water-solubility, are easy to adapt to hair and skin, have low irritation and are excellent in safety, and have completed the present invention.

That is, the amino acid derivative represented by the above general formula (I) has an adsorbing action to the hair and a softening action by the introduction of quaternary ammonium, and also has significantly improved moisturizing properties and water solubility as compared with amino acids. Moreover, it retains the properties of amino acids that are hypoallergenic and safe for the skin and hair without impairing them, and exerts an excellent effect as a compounding agent for cosmetics for hair and skin.

In the above general formula (I), α whose side chain is represented by R ₄
-As the amino acid, alanine, glycine, valine, leucine, isoleucine, proline, phenylalanine,
Examples include tyrosine, cystine, cysteine, serine, threonine, methionine, arginine, histidine, lysine, aspartic acid, glutamic acid, asparagine, glutamine and tryptophan.

Since the quaternary ammonium is introduced into the amino acid derivative represented by the general formula (I) as described above, it is more cationic than the original amino acid, and has high adsorptivity to hair, and It is also highly hydrophilic. For example, some amino acids such as methionine, tyrosine, and tryptophan are known to have adsorptivity to hair, but the amino acid derivative of the present invention is cationic because of the introduction of quaternary ammonium. Not only the above specific amino acids, but the adsorptivity to hair is improved, the hair is well adsorbed, the hair is prevented from being damaged, and the cationic compound exhibits a peculiar softening effect to the hair to condition the hair. To facilitate. Of course, methionine, tyrosine, tryptophan, and other amino acids that originally have adsorptivity to hair have further improved adsorptivity to hair, preventing hair damage and exerting a softening effect, making hair conditioning easy. To do. Also, for example, cystine, tyrosine,
Even an amino acid having a high hydrophobicity such as leucine and hardly soluble in water can be easily dissolved in water by using the derivative of the present invention. Moreover, since it has strong hydrophilicity, it also has improved moisturizing properties and hygroscopic properties, and can be used as an emollient (humectant) for skin cosmetics. Further, the derivative of cysteine can be used as the main agent of the permanent wave first agent in place of thioglycolic acid or a salt thereof, or a total amount of a salt such as cysteine or a hydrochloride thereof, or a part thereof. In that case, compared to the permanent wave first agent containing thioglycolic acid or a salt thereof or cysteine or a salt thereof as a main agent, the feel and feel given to the hair are better, and there is an effect of reducing the damage to the hair and finishing it softly. . In addition, with the first permanent wave agent containing cysteine or a salt thereof, the cystine produced by the oxidation of cysteine is extremely difficult to dissolve in water, so the permanent wave treatment causes cystine to remain in the hair and gives an unpleasant feeling. There was an inconvenience such as giving, or a crystal which remains on the surface of the practitioner's hand and is difficult to wash and causes rough hands, but the cysteine derivative of the present invention is used in place of cysteine or a salt thereof, or Such a point can be improved by substituting a part of cysteine or a salt thereof with the cysteine derivative of the present invention.

Such an amino acid derivative has the general formula (I) as described above. (In the formula, R _{1 to} R ₃ are alkyl groups having 1 to ₃ carbon atoms, X is a hydrogen atom or a hydroxyl group, R ₄ is a side chain of α-amino acid, and Y is O.
H, Cl, Br, is shown in NO ₃ or SO _4/2), an amino acid derivative represented by the general formula (I), and α- amino acids such as 3-halogen -
2-hydroxypropyltrialkylammonium salt,
It is obtained by reacting with 3-halgenpropyltrialkylammonium salt or glycidyltrialkylammonium salt.

The reaction between an α-amino acid and a 3-halogen-2-hydroxypropyltrialkylammonium salt, a 3-halgenpropyltrialkylammonium salt or a glycidyltrialkylammonium salt is usually carried out in an aqueous solution of an α-amino acid with a 3-halogen- It is carried out by dropping a solution of 2-hydroxypropyltrialkylammonium salt, 3-halogenpropyltrialkylammonium salt or glycidyltrialkylammonium salt and bringing them into contact with each other in water. The pH of the reaction system during the reaction is set to 8
It is preferable to keep it at -12, especially 9-11, for which purpose an alkaline solution of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like is added dropwise into the reaction solution if necessary. During the reaction, the pH in the reaction system is maintained within the above range because the amino group of the α-amino acid is 3-halogen-2.
-Hydroxypropyltrialkylammonium salt, 3
-In order to react with a halogen propyltrialkylammonium salt or a glycidyltrialkylammonium salt, it is desirable that the alkali side has a pH of 8 or more, and if the pH exceeds 12, 3-halogen-2-hydroxypropyltrialkylammonium salt , 3-halgenpropyltrialkylammonium salt or glycidyltrialkylammonium salt causes hydrolysis.
The reaction proceeds even at room temperature, but the higher the temperature, the faster the reaction. However, if the temperature and pH are high, the hydrolysis of 3-halogen-2-hydroxypropyltrialkylammonium salt, 3-halgenpropyltrialkylammonium salt or glycidyltrialkylammonium salt is also accelerated, so that the temperature is 100 ° C or less at the highest. When using an alkali- or heat-labile α-amino acid such as cystine, cysteine, glutamine, asparagine, and arginine, the reaction temperature must be 70 ° C. or lower. Especially in the case of cysteine, it is very unstable against alkali and heat,
A method in which cysteine is used as a derivative of cysteine by a known method of reacting with cystine and then obtaining cysteine from cystine is preferable. The 3-halogen-2-hydroxypropyltrialkylammonium salt, 3-halogenpropyltrialkylammonium salt or glycidyltrialkylammonium salt may be used in the form of crystals, but a solution of water or alcohol may be added dropwise. preferable. The dropping of the 3-halogen-2-hydroxypropyltrialkylammonium salt, 3-halogenpropyltrialkylammonium salt or glycidyltrialkylammonium salt to the α-amino acid solution is preferably completed in 15 minutes to 6 hours. The reaction time depends on the temperature, p
In addition to H, concentration, etc., in the case of low solubility α-amino acids such as cystine and tyrosine, α-amino acid
Since the reaction proceeds with the dissolution of the amino acid, it may depend on the solubility of the α-amino acid used in the reaction.

The reaction formulas are slightly different depending on whether the 3-halogen-2-hydroxypropyltrialkylammonium salt or the 3-halogenpropyltrialkylammonium salt is used or the glycidyltrialkylammonium salt is used. .

When using a 3-halogen-2-hydroxypropyltrialkylammonium salt (wherein X = OH) or a 3-halogenpropyltrialkylammonium salt (wherein X = H): In the formula, Z represents halogen of any one of Cl, Br, and I, but normally, when the same Y and Z are used, counter ions do not coexist. Of course, it does not matter if Y and Z are different.

When using glycidyl trialkyl ammonium salt: When a 3-halogen-2-hydroxypropyltrialkylammonium salt or a 3-halogenpropyltrialkylammonium salt is used, hydrogen halide is generated by the reaction and the pH of the reaction solution decreases, so alkali is used to start the reaction. At the same time, it is necessary to add dropwise and stir to maintain the pH in the liquid suitable for the reaction. Also,
Even when using a glycidyltrialkylammonium salt, in order to ensure reactivity and allow a certain reaction to proceed,
It is preferable to maintain the pH of the liquid during the reaction at 8 to 12.

In addition, α- having two or more amino groups or imino groups in one amino acid such as lysine, cystine, and histidine
In the case of amino acids, 3-halogen-2-used in the reaction
Hydroxypropyltrialkylammonium salt, 3-
Both the respective amino or imino groups can be derivatized by increasing the amount of halogenpropyltrialkylammonium salt or glycidyltrialkylammonium salt.

The progress and termination of the reaction are determined by the Van Slyke method for the reaction to the amino group, and α- in the reaction solution is used.
This can be confirmed by measuring the amino nitrogen of the amino acid. In the case of reacting with imino groups such as proline and hydroxyproline, the reaction is performed by quantifying unreacted proline and imino nitrogen such as hydroxyproline by measuring the absorbance at a wavelength of 440 nm of ninhydrin color development. You can check. After the reaction is completed, the reaction solution can be used as a solid or a concentrated solution by appropriately concentrating or purifying by ion exchange resin, gel filtration, electrodialysis, etc., and then concentrating appropriately.

The amino acid derivative thus obtained is generally used as a compounding agent for cosmetics by being mixed in cosmetics in an amount of about 0.01 to 10% (% by weight, the same applies hereinafter). For example, in the case of shampoo, 0.1 to 5%, Hair rinse
It is preferable to add 0.2 to 7%, 0.2 to 10% to the first and second permanent wave agents, and 0.01 to 3% to various creamy products. The cysteine derivative may be used in place of thioglycolic acid or a salt thereof, or cysteine or a salt thereof, which is used as a main component of a conventional first agent for permanent wave, or a part thereof. In that case, in addition to improving the feel of the hair subjected to permanent wave treatment, when it is used as a permanent wave first agent containing cysteine or a salt thereof as a main agent, cystine crystals formed by natural oxidation of the first agent It also has the effect of suppressing generation.

Cosmetics that can use the amino acid derivative of the present invention include:
In addition to the above shampoo, hair rinse, permanent wave first and second agents, hair cream, etc.,
For example, aerosol type foam, hair conditioner, set lotion, hair color, hair bleach, hair treatment lotion, hair pack,
Hair cosmetics such as hair tonic, lotion, after shave lotion, cleansing cream, emollient cream, cold cream, moisturizing cream and other creams, emulsion, body shampoo, soaps, makeup products, sunscreen products, etc. be able to.

And, as the components that can be blended into the cosmetics at the same time, for example, various surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, cationic polymers, anionic polymers, Polymers such as nonionic polymers and amphoteric polymers, naturally extracted oils, higher fatty acids, hydrocarbons, fatty acid esters, glycerides, waxes, alkyl alcohols,
Oils such as alkylamides, silicone oils (eg, dimethylpolysiloxane, methylphenylpolysiloxane, and various modified silicone oils), protein hydrolysates such as collagen polypeptides, keratin polypeptides, silk polypeptides, or their derivatives, moisturizers , Alcohols, thickeners, plant extracts, animal extracts, ultraviolet absorbers, pH adjusters, chelating agents, preservatives, pigments, fragrances and other various cosmetic compounding agents.

〔Example〕

Next, the present invention will be described in more detail with reference to examples and application examples.

Example 1 (N- (3-trimethylammonio-2-hydroxypropyl) -L-serine hydrochloride) In a 300 ml beaker, 10 g of L-serine and 60 g of ion-exchanged water were placed and stirred at a liquid temperature of 45 ° C. After heating and melting,
A pH electrode was inserted into the solution, and while measuring the pH, a 20% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 10. To this solution, 35.8 g of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (corresponding to 1.0 equivalent of L-serine) was added dropwise at a dropping rate of about 1 g / min, and at the same time measuring 20% water with pH. Sodium oxide aqueous solution is added dropwise to adjust the pH to 10
Was maintained.

After the dropwise addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, the reaction was terminated by heating to 60 ° C. and further maintaining pH 10 for 2 hours while continuing heating and stirring.

The reaction solution was desalted and purified with an ion exchange resin, and then vacuum dried to obtain a dry powder product of N- (3-trimethylammonio-2-hydroxypropyl) -L-serine hydrochloride.
Obtained 23 g. Amino nitrogen is 1330 mg before the reaction and 8 after the reaction.
It was 0 mg, and the reaction yield was 94%.

Example 2 (N- (3-trimethylammonio-2-hydroxypropyl) glycine hydrochloride) Instead of 10 g of L-serine in Example 1, 10 g of glycine was used.
Was used in the same manner as in Example 1 except that 55.1 g of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (corresponding to 1.1 equivalents of glycine) was used. 33 g of a dry powder product of 2-hydroxypropyl) glycine hydrochloride were obtained. The amount of amino nitrogen was 1860 mg before the reaction and 30 mg after the reaction, and the reaction yield was 98%.

Example 3 (N, N'-bis (3-trimethylammonio-2-hydroxypropyl) -L-cystine dihydrochloride) Instead of 10 g of L-serine in Example 1, 10 g of L-cystine and 500 g of ion-exchanged water. Of 3-chloro-2-hydroxypropyltrimethylammonium chloride
N, N'-bis (3-trimethylammonio-2) was prepared in the same manner as in Example 1 except that 34.5 g of a 50% aqueous solution (corresponding to 2.2 equivalents of L-cystine) was added dropwise at a dropping rate of 0.2 mg / min. 21 g of a dry powder product of -hydroxypropyl) -L-cystine dihydrochloride were obtained. Amino nitrogen is 1170 mg before the reaction,
It was 60 mg after the reaction, and the reaction yield was 95%.

Example 4 (N, N′-bis (3-trimethylammonio-2-hydroxypropyl) -L-lysine dihydrochloride) Instead of 10 g of L-serine in Example 1, 10 g of L-lysine monohydrochloride was used. , 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride 4
N, N'-Bis (3-trimethylammonio-2-hydroxypropyl) -L-lysine was prepared in the same manner as in Example 1 except that 3.3 g (corresponding to 2.2 equivalents of L-lysine monohydrochloride) was used. 29 g of a dry powder product of the dihydrochloride were obtained. The amount of amino nitrogen was 1500 mg before the reaction and 60 mg after the reaction, and the reaction yield was
It was 94%.

Example 5 (N- (3-trimethylammonio-2-hydroxypropyl) -L-cysteine hydrochloride) Since the thiol group of cysteine is easily oxidized or hydrolyzed in an alkaline solution and unstable, N- (3- Trimethylammonio-2-hydroxypropyl) -L-
The cysteine salt was synthesized by the following method. 10 g of the dry powder product of N, N'-bis (3-trimethylammonio-2-hydroxypropyl) -L-cystine dihydrochloride obtained in Example 3 was dissolved in 100 ml of 0.1N hydrochloric acid aqueous solution to carry out electrolytic reduction. To reduce the SS bond of cystine to a thiol group,
Synthesis of-(3-trimethylammonio-2-hydroxypropyl) -L-cysteine salt was performed. After reduction, the reaction solution was freeze-dried to obtain 10 g of a dry powder product of N- (3-trimethylammonio-2-hydroxypropyl) -L-cysteine hydrochloride. The thiol (SH) group of the product was quantified and found to be 2.8 mmol per 3.1 g. From this result, it was confirmed that the obtained product was almost pure N- (3-trimethylammonio-2-hydroxypropyl) -L-cysteine hydrochloride.

Example 6 (N- (3-trimethylammonio-2-hydroxypropyl) -L-proline hydrochloride) In place of 10 g of L-serine in Example 1, 12 g of proline was used.
Was used in the same manner as in Example 1 except that 28.8 g of a 50% aqueous solution of glycidyltrimethylammonium chloride (corresponding to 1.0 equivalent of proline) was used instead of 3-chloro-2-hydroxypropyltrimethylammonium chloride. Dry powder product of (3-trimethylammonio-2-hydroxypropyl) -L-proline hydrochloride 21
got g. Imino nitrogen is 1200 mg before the reaction and 120 after the reaction.
and the reaction yield was 90%.

Next, examples of application of the amino acid derivative of the present invention to cosmetics will be shown. In addition, when displaying the blended components of the application example, all the blended components are converted into pure components, and the blended amount is shown in parts by weight.

Application Example 1 (Shampoo) N- (3-trimethylammonio-2 obtained in Example 1
A shampoo containing -hydroxypropyl) -L-serine hydrochloride was prepared. The compounding composition is as shown in Table 1.

For comparison, a shampoo having the same composition as in Application Example 1 was prepared except that the N- (3-trimethylammonio-2-hydroxypropyl) -L-serine hydrochloride was not added, and the results were compared. It is referred to as Example 1. The composition of the shampoo of Comparative Example 1 is shown in Table 1.

20 kinds of shampoos are used by 20 women, and which one is better for moisturizing hair (moisturizing), fluffy hair (volume feeling), ease of combing hair, and quickness of gathering hair. I decided to feel it. The result is displayed on the second display.

As shown in Table 2, the number of people who answered that the shampoo of Application Example 1 containing N- (3-trimethylammonio-2-hydroxypropyl) -L-serine hydrochloride, which is an amino acid derivative of the present invention, is good is There were overwhelmingly many. This is because N- (3-trimethylammonio-2-hydroxypropyl) -L-serine hydrochloride compounded in the shampoo exerts a good adsorption action and flexibility on hair, and is good for hair. It is considered that this is due to the result of imparting wettability.

Application Example 2 (Shampoo) A shampoo containing N, N′-bis (3-trimethylammonio-2-hydroxypropyl) -L-cystine dihydrochloride obtained in Example 3 was prepared. The composition is as follows.

Sodium lauryl ether sulfate 11.0 Collagen polypeptide coconut fatty acid condensate potassium salt (Promois ECP, trade name, manufactured by Seiwa Kasei Co., Ltd.) 1.0 Collagen polypeptide (average molecular weight 1000) 0.2 Lauric acid diethanolamide 4.0 N, N'-bis (3-Trimethylammonio-2-hydroxypropyl) -L-cystine dihydrochloride 1.5 Stearyltrimethylammonium chloride 0.08 Polyoxyethylene nonylphenyl ether 2.1 Cationized cellulose (Rheogard G, trade name, manufactured by Lion Corporation) 0.1 Ethylene Glycol distearate 1.5 Preservative (seicept, trade name, manufactured by Seiwa Kasei Co., Ltd.) 0.5
EDTA 0.1 Malic acid 0.1 Fragrance A suitable amount of sterilized ion-exchanged water 100 The shampoo of the above-mentioned Application Example 2 is N, N′-bis (3-trimethylammonio-2) which is an amino acid derivative of the present invention.
-Hydroxypropyl) -L-cystine dihydrochloride was not added, and compared to the shampoo having the same composition as in Application Example 2, the hair had a moisturizing and voluminous feel, and combing or brushing was easy.

Application Example 3 (Hair rinse) A hair rinse containing N, N'-bis (3-trimethylammonio-2-hydroxypropyl) -L-lysine dihydrochloride obtained in Example 4 was prepared. The compounding composition is as follows.

Stearyl alcohol 2.0 Palmityl trimethyl ammonium chloride 1.2 Distearyl dimethyl ammonium chloride 1.0 Collagen polypeptide isostearic acid condensate 2-
Amino-2-methyl-1,3-propanediol salt (Promois E-118D, trade name, manufactured by Seiwa Kasei Co., Ltd.) 0.65 N, N'-bis (3-trimethylammonio-2-hydroxypropyl)- L-Lysine dihydrochloride (Example 4) 2.5
Hexadecyl stearate 2.0 Preservative (Seicept, supra) 0.3 Propylene glycol 3.0 Keratin polypeptide (average molecular weight 1000) 0.5 Citric acid (pH 5.5) Appropriate amount Fragrance Appropriate amount Sterilized ion-exchanged water 100 Hair rinse of N, N'-bis (3-trimethylammonio-), which is an amino acid derivative of the present invention.
Compared with the hair rinse having the same composition as in Application Example 3 except that 2-hydroxypropyl) -L-lysine dihydrochloride was not added, the hair was able to be imparted with softness, fluffiness and volume.

Application Example 4 (Hair Treatment) A hair treatment containing the N, N′-bis (3-trimethylammonio-2-hydroxypropyl) -L-cystine dihydrochloride obtained in Example 3 was prepared. The compounding composition is as follows.

25 Collagen Polypeptide Isostearic Acid Condensate
% Hexadecyl isostearate solution (Promois E-
118 (HI), trade name, manufactured by Seiwa Kasei Co., Ltd. 2.5 Collagen polypeptide quaternary ammonium derivative (Promois W-42Q, trade name, manufactured by Seiwa Kasei Co., Ltd.) 0.1
Hexadecyl isostearate 7.0 Stearic acid 13.0 Cetyl alcohol 2.0 Ethylene glycol monostearate 4.0 Methyl paraben 0.2 Silicone oil (polydimethylsiloxane) 0.2 N, N'-bis (3-trimethylammonio-2-hydroxypropyl) -L-cystine Dihydrochloride (Example 3) 0.
3 Triethanolamine 1.6 1,3-butylene glycol 8.0 EDTA 0.1 Fragrance Appropriate amount of sterilized ion-exchanged water The total amount of the hair treatment of Application Example 4 is 100, and the amino acid derivative of the present invention is N, N′-bis (3-trimethyl). Compared to the air treatment of the same composition as in Application Example 4 except that ammonio-2-hydroxypropyl) -L-cystine dihydrochloride was not added, the effect of giving hair a easier and more voluminous finish Was recognized.

Application Example 5 (Permanent Wave First Agent) N- (3-trimethylammonio-2 obtained in Example 5
-Hydroxypropyl) -L-cysteine hydrochloride was mixed to prepare a permanent wave first agent. The composition is as follows.

L-Cysteine hydrochloride monohydrate 10.0 N- (3-Trimethylammonio-2-hydroxypropyl) -L-cysteine hydrochloride (Example 5) 2.0 Monoethanolamine 2.5 Ammonia water (28%) pH 9.2 Edetate 0.1 perfume suitable amount polyoxyethylene nonyl phenyl ether suitable amount sterilized ion-exchanged water 100 total of the above-mentioned application example 5 of the permanent wave and the amino acid derivative of the present invention N- (3-trimethylammonio) 2-Hydroxypropyl) -L-cysteine hydrochloride was not added, but the amount of L-cysteine hydrochloride monohydrate was increased accordingly, except that the permanent wave first agent having the same composition as in Application Example 5 (Comparative Example 2) was used. ) In each first agent, 1g of hair bundle is wound on a rod and immersed at a liquid temperature of 35 ° C for 15 minutes, and after washing with water, the hair bundle is wound on the rod at 8%. Permanent wave treatment was carried out by immersing the permanent wave second agent consisting of an aqueous solution of sodium bromate in a liquid temperature of 35 ° C. for 15 minutes.

Each expert will determine which permanent wave first agent is better for each moisturized hair (moisturizing), fluffy hair (volume feeling), luster of hair, and texture of hair. The results obtained are shown in Table 3.

As shown in Table 3, the number of the respondents who preferred the permanent wave first agent of Application Example 5 was overwhelmingly large for any of the moist feeling, fluffy feeling, gloss and touch of the hair, and the amino acid derivative of the present invention The effect of adding N- (3-trimethylammonio-2-hydroxypropyl) -L-cysteine hydrochloride, which is

Then, a small amount of the permanent wave first agent of Application Example 5 and the permanent wave first agent of Comparative Example 2 were applied to the palm, dried, and then the portions were observed.
White powdery crystals of L-cystine were formed in the permanent wave first agent of Comparative Example 2, but no such white powdery crystals were observed in the permanent wave first agent of Application Example 5.

Application Example 6 (Permanent Wave First Agent) N- (3-trimethylammonio-2 obtained in Example 5
-Hydroxypropyl) -L-cysteine hydrochloride was mixed to prepare a permanent wave first agent. The composition is as follows.

Keratin Polypeptide Quaternary Ammonium Derivative (Promois WK-HQ, trade name, manufactured by Seiwa Kasei Co., Ltd.) 0.3 Silk Polypeptide (SILK-1000, trade name, manufactured by Seiwa Kasei Co., Ltd.) 0.2 Ammonium thioglycolate 8.0 N- (3-Trimethylammonio-2-hydroxypropyl) -L-cysteine hydrochloride (Example 5) 2.0 Monoethanolamine 0.75 Ammonia water (28%) 0.6 Ammonium bicarbonate 3.5 Polyoxyethylene (20 mol) cetyl Ether 0.2 EDTA 0.1 Fragrance A suitable amount of sterilized ion-exchanged water 100 The permanent wave first agent of the above-mentioned Application Example 6 is N- (3-trimethylammonio-2-hydroxypropyl) -L- which is the amino acid derivative of the present invention. The same composition as in Application Example 6 except that the amount of ammonium thioglycolate was increased without adding cysteine hydrochloride. Compared to whereof waving agent, moisture in the hair, a sense of volume, gloss,
It was possible to impart a good touch and the like.

Application Example 7 (second permanent wave agent) N- (3-trimethylammonio-2 obtained in Example 2)
-Hydroxypropyl) glycine hydrochloride was compounded to prepare a permanent wave second agent. The composition is as follows.

Collagen polypeptide (average molecular weight 500) 0.5 N- (3-trimethylammonio-2-hydroxypropyl) glycine hydrochloride (Example 2) 2.0 Sodium bromate 6.0 Citric acid 0.01 Sodium citrate 0.3 Sterile ion-exchanged water Total 100 The permanent wave second agent of the above-mentioned Application Example 7 has the same composition as that of Application Example 7 except that N- (3-trimethylammonio-2-hydroxypropyl) glycine hydrochloride, which is the amino acid derivative of the present invention, was not compounded. Compared with the permanent waving agent of No. 1, it was possible to make the hair supple and to give a natural wave having a long lasting effect.

Application Example 8 (shaving cream [aerosol type]) N- (3-trimethylammonio-2 obtained in Example 6
A shaving cream [aerosol type] containing -hydroxypropyl) -L-proline hydrochloride was prepared. The composition is as follows.

Myristic acid 10.0 Sodium dioctyl sulfosuccinate 0.5 Collagen poly (polypeptide) undecylenic acid condensate potassium salt (Promois ECP, trade name, manufactured by SEIWA KASEI CO., LTD.) 5.0
N- (3-trimethylammonio-2-hydroxypropyl) -L-proline hydrochloride (Example 6) 1.5 Triethanolamine (98% or more) 5.0 Concentrated glycerin 7.5 Perfume proper amount Menthol proper amount Purified water Total of 100 above bases 8.0 Freon gas (Freon 12 / Freon 114 50/50) 92.0 The shaving cream of the above Application Example 8 is N- (3-trimethylammonio-) which is the amino acid derivative of the present invention.
Compared with the shaving cream having the same composition as in Application Example 8 except that 2-hydroxypropyl) -L-proline hydrochloride was not blended, it had the effects of softening the beard and facilitating shaving.

Application Example 9 (After-shaving lotion) N- (3-trimethylammonio-2 obtained in Example 1
-Hydroxypropyl) -L-serine hydrochloride was added to prepare an aftershaving lotion. The composition is as follows.

Collagen polypeptide isostearic acid condensate 2-
Amino-2-methyl-1,3-propanediol salt (Promois E-118D, trade name, manufactured by Seiwa Kasei Co., Ltd.) 2.0 Emulsifier (Ayacol A-100, trade name, manufactured by Seiwa Kasei Co., Ltd.) 2.0 N- (3-Trimethylammonio-2-hydroxypropyl) -L-serine hydrochloride (Example 1) 0.3 Menthol 0.1 Fragrance Suitable amount Ethyl alcohol 63.0 Purified water 100 bases above 8.0 Freon gas (Freon 12 / Freon 114 50 / 50) 92.0 The after shaving lotion of Application Example 9 above is
Compared to the after-shaving lotion having the same composition as in Application Example 9 except that the amino acid derivative of the present invention, N- (3-trimethylammonio-2-hydroxypropyl) -L-serine hydrochloride was not blended, after drying. It was moist and had the effect of retaining the moisture of the skin.

Application Example 10 (Heartonic) A heartonic containing N, N'-bis (3-trimethylammonio-2-hydroxypropyl) -L-cystine dihydrochloride obtained in Example 3 was prepared. The composition is as follows.

Ethyl Alcohol (99%) 65.0 Collagen Polypeptide Ethyl Ester 25% Ethyl Alcohol Solution (Promois A, trade name, manufactured by Seiwa Kasei Co., Ltd.) 0.5 Diisobutyl adipate 0.5 Togarashi tincture 0.4 L-menthol 0.4 Calcium pantothenate 0.4 Vitamin B ₆ 0.2 N, N'-bis (3-trimethylammonio-2-hydroxypropyl) -L-cystine dihydrochloride (Example 3).
2 Hinokitiol 0.1 EDTA 0.01 Piosol 0.1 Perfume 0.5 Sterile ion-exchanged water Total 100 The above-mentioned application example 10 is the articulated N, N′-bis (3-trimethylammonio-2-hydroxypropyl) which is an amino acid derivative of the present invention. ) -L-cystine dihydrochloride was not used, and hair styling was easier than that of Hairnic with the same composition as in Application Example 10, and it had an effect of keeping the hair moist and gloss after drying.

〔The invention's effect〕

As described above, the amino acid derivative of the present invention has excellent adsorbing action and softening action on hair, moisturizing property,
Good water solubility, hypoallergenic and safe, shampoo, hair rinse, hair treatment, permanent wave first agent, permanent wave second agent, hair cream, shaving cream, after shaving lotion, hairnic, hair blow As a compounding agent for hair cosmetics and skin cosmetics, it was possible to exhibit excellent effects depending on the respective cosmetics.

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Claims (1)

(57) [Claims] 1. A general formula (I) (In the formula, R _{1 to} R ₃ are alkyl groups having 1 to ₃ carbon atoms, X is a hydrogen atom or a hydroxyl group, R ₄ is a side chain of α-amino acid, and Y is O.
H, an amino acid derivative represented by Cl, Br, an NO ₃ or SO _4/2).