JP2890834B2 - Moisturizers and cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides at least one of an alkali metal salt and / or a monoethanolamine salt and / or a diethanolamine salt and / or a triethanolamine salt of a polyamino acid as an active ingredient. And a cosmetic containing the same.

[Prior art and its problems] In general, cosmetics, ointments, confectionery, and the like, which lose quality when moisture is lost, and lotions for skin, creams,
For the purpose of imparting moist and moisturizing properties such as shoe creams, those having high hygroscopicity are used as moisturizing agents. The types of humectants that can actually be used are limited due to their effects on safety and product stability, and humectants are required simultaneously with hygroscopicity. A commonly used humectant satisfies these properties and is often used in combination. However, of these, sodium lactate,
Since sodium pyrrolidone carboxylate and the like are electrolytes, they have unfavorable points such as an emulsification inhibitory effect, and their use amount and use are restricted. On the other hand, polyol-based humectants such as glycerin, sorbitol, and propylene glycol have a strong sticky feeling and have a problem in use feeling. In addition, since hyaluronic acid is a rare natural product and extremely expensive, its use is limited by itself. Also,
The water-soluble polyglutamate is disclosed as a humectant in JP-A-59-209635 and as a cosmetic in JP-A-1-224309.Although the humectant is excellent, the sticky feeling is still a little felt, and the feeling of use is slightly increased. There is a problem that there is a difficulty and the setting force when used as a hair styling agent is slightly inferior due to insufficient film forming ability.

[Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned problems, and has excellent moisture absorbing and moisturizing properties, has no sticky feeling, has a good feeling in use, and has excellent film-forming ability. Getting cosmetics.

[Means for Solving the Problems] The present inventors have conducted intensive studies in order to solve such problems, and as a result, have found that an alkali metal salt and / or a monoamino acid of a polyamino acid which is a copolymer of an acidic amino acid and a neutral amino acid. A humectant consisting of an ethanolamine salt and / or a diethanolamine salt and / or a triethanolamine salt and a cosmetic containing the same have a hygroscopicity and a moisture retention equivalent to that of a water-soluble polyglutamate and are used without stickiness. The present inventors have found that they have good feeling and excellent film-forming ability, and have completed the present invention. That is, the present invention provides (1) a copolymer of an acidic amino acid and a neutral amino acid,
In a polyamino acid having an acidic amino acid content of 40 to 90 mol%, an alkali metal salt of a carboxylic acid and / or a monoethanolamine salt and / or a diethanolamine salt and / or a triethanolamine salt are added to a polymer side chain in an amount of 40 mol based on the polymer side chain. Moisturizer consisting of a polyamino acid containing at least 10%.

(2) A cosmetic containing the humectant according to (1).

Consists of

 Hereinafter, the present invention will be described in detail.

The polyamino acids used in the present invention are copolymers of one or more of acidic amino acids such as glutamic acid and aspartic acid and neutral amino acids such as valine, norvaline, leucine, isoleucine, norleucine, phenylalanine and methionine. The acidic amino acid is in the α form, and the amino acid can be any of an optically active form and a racemic form. As a method for synthesizing a polyamino acid, the general formula (However, R ₁ is an alkyl group having 1 to 4 carbon atoms, m is an ω-alkyl acidic amino acid N-carbonic anhydride represented by 1 or 2) (However, R ₂ is an alkyl group having 3 to 8 carbon atoms, CH ₃ SCH ₂ —CH ₂ — group) represented by the following formula:
Then, the side chain ester of the acidic amino acid is obtained as an alkali metal salt using sodium hydroxide, potassium hydroxide, lithium hydroxide or the like. The monoethanolamine salt, diethanolamine salt and triethanolamine salt can be obtained by subjecting the alkali metal salt obtained by the above method to a salt exchange by reacting with a large excess of ethanolamine, diethanolamine and triethanolamine. The content of the acidic amino acid is 40 to 90 mol%, preferably 60 to 80 mol%. When the content of the acidic amino acid is less than 40 mol%, the compound does not become water-soluble after the above-mentioned saponification, which is not preferable in use. Further, as the alkali metal salt of the carboxylic acid of the polymer side chain, sodium salt, potassium salt, lithium salt, and the like,
The total of the alkali metal salt, monoethanolamine salt, diethanolamine salt and triethanolamine salt is 40 to 90 mol%, preferably 60 to 80 mol%, based on the side chain of the polymer. If the total amount of the salts is less than 40 mol%, the composition will not be water-soluble and is not preferable in use, and if it is more than 90 mol%, a sticky feeling is produced and the film forming ability is slightly inferior. . The degree of polymerization of the polyamino acid is 10 or more, preferably 20 to 200. When the degree of polymerization is less than 10, the stickiness is strong. Those having a degree of polymerization of 2,000 or more are difficult to synthesize. The polyamino acid salt of the present invention can be used as it is as an aqueous solution or as a solid and then redissolved in water as needed. The aqueous solution has a pH of 3 to 10, preferably 5 to 9. You can choose according to your purpose.

The polyamino acid salt of the present invention exhibits excellent moisture absorption and retention properties, and can impart a moist feeling without being sticky to an object to be coated by an excellent film-forming force by the effect of a neutral amino acid. Therefore, the polyamino acid salt of the present invention can maintain and improve the quality by being added to those having a tendency to lose moisture in the air, for example, shoe cream, paint, papers, etc. Addition or immersion processing to materials that dislike chargeability, etc., impart appropriate hygroscopicity, and increase the moist feeling for fibers,
The texture can be improved.

As described above, the polyamino acid salt of the present invention is effective for all products, but can be added to cosmetics and the like because it is a highly safe substance.

Examples of cosmetics to which the polyamino acid salt of the present invention can be added include hair sprays, hair styling agents, creaming creams, lotions, shampoos, rinses, hair treatments, emulsions, lotions, shaving creams, cold creams, hand creams, and permanents. Examples thereof include liquids, solid detergents, liquid detergents, and sweat-absorbing agents, and can be used regardless of the form of the product. When the polyamino acid salt of the present invention is added to various products, the moisturizing property can be imparted according to the amount added, but the initial purpose is achieved by using 0.01 to 10% by weight, preferably 0.05 to 5% by weight. You can do it.

Furthermore, the effect of the polyamino acid salt of the present invention is not impaired even when other humectants such as glycerin, propylene glycol, sorbitol, sodium pyrrolidonecarboxylate, sodium lactate, polyglutamate, and amino acids are used in combination. Various surfactants as needed,
A solubilizing agent, an oil agent and the like can be used in combination.

Hereinafter, the present invention will be described in more detail with reference to examples. The dialysis membrane used was a Seamless Cellulose Tubing Size 30/32 (available from Sanko Junyaku Co., Ltd.).

Example 1 Synthesis Example 1 γ-methyl-L-glutamate N-carbonic anhydride (hereinafter referred to as γ-methyl-L-glutamate N-carbonic anhydride)
374 g, L-leucine N-carbonic anhydride (hereinafter L)
471 g of NCA was placed in a 101 three-necked flask, and 2,250 g of 1,2-dichloroethane (hereinafter abbreviated as EDC) and 3375 g of trichloroethylene were added thereto, followed by stirring at room temperature. Then as an initiator
1.28 g of N, N-dimethyl-1,3-propanediamine (hereinafter abbreviated as p-amine) was added, and the mixture was polymerized at room temperature for 3 hours and at 50 ° C. for 1 hour. The intrinsic viscosity of this polymer (referred to as polymer A) was 1.21 (25 ° C., dichloroacetic acid). Weigh 250 g of polymer A formed into a film using release paper in a 21-separable flask, 35.4 g of sodium hydroxide, 1 kg of water
Was added thereto, and the mixture was reacted with stirring at 60 ° C. for 8 hours to dissolve, dialyzed for 2 days, and concentrated to dryness. Yield 250.8 g Synthesis Example 2 748 g of MGNCA and 157 g of LNCA were placed in a 101 three-necked flask, and EDC49 was added.
32 g and 1233 g of trichloroethylene were added and stirred at room temperature. Then, 1.28 g of p-amine was added as an initiator, and polymerization was carried out at room temperature for 3 hours and at 50 ° C. for 1 hour. The intrinsic viscosity of this polymer (referred to as polymer B) was 1.32 (25 ° C., dichloroacetic acid). Weigh out 274 g of polymer B formed into a film using release paper in a 21-separable flask, add 70.8 g of sodium hydroxide and 1.1 kg of water and stir at 60 ° C.
For 8 hours to dissolve, dialyzed for 2 days, and concentrated to dryness. Yield 271.3 g Synthesis Example 3 274 g of the polymer B film obtained in Synthesis Example 2 was weighed into a 21-separable flask, and potassium hydroxide 99.3 g and water
1.1 kg was added, and the mixture was reacted at 60 ° C. for 8 hours with stirring to dissolve, dialyzed for 2 days, and concentrated to dryness. Yield 295.6 g Synthesis Example 4 274 g of the polymer B film obtained in Synthesis Example 2 was weighed into a 21 separable flask, and 42.3 g of lithium hydroxide and water were added.
1.1 kg was added, and the mixture was reacted at 60 ° C. for 8 hours with stirring to dissolve, dialyzed for 2 days, and concentrated to dryness. Yield: 247.0 g Synthesis Example 5 20 g of the polymer obtained in Synthesis Example 1 was placed in a 500 ml three-necked flask, and 242 g of water was added to dissolve it.
g was added and reacted at 80 ° C. for 5 hours with stirring. The reaction was dialyzed for 2 days and concentrated to dryness. Yield: 17.9 g Synthesis Example 6 20 g of the polymer obtained in Synthesis Example 1 was placed in a 500 ml three-necked flask, dissolved by adding 215 g of water, and 65.6 g of diethanolamine.
Was added thereto and reacted at 80 ° C. for 5 hours while stirring. The reaction was dialyzed for 2 days and concentrated to dryness. Yield: 20.1 g Synthesis Example 7 20 g of the polymer obtained in Synthesis Example 1 was placed in a 500 ml three-necked flask, and 187 g of water was added to dissolve it.
g was added and reacted at 80 ° C. for 5 hours with stirring. The reaction was dialyzed for 2 days and concentrated to dryness. Yield: 22.3 g Synthesis Example 8 20 g of the polymer obtained in Synthesis Example 2 was placed in a 500 ml three-necked flask, and 212 g of water was added to dissolve the same.
g was added and reacted at 80 ° C. for 5 hours with stirring. The reaction was dialyzed for 2 days and concentrated to dryness. Yield: 19.5 g Synthesis Example 9 20 g of the polymer obtained in Synthesis Example 2 was placed in a 500 ml three-necked flask, 163 g of water was added and dissolved, and 117.2 g of diethanolamine was obtained.
Was added thereto and reacted at 80 ° C. for 5 hours while stirring. The reaction was dialyzed for 2 days and concentrated to dryness. Yield 23.4 g Synthesis Example 10 20 g of the polymer obtained in Synthesis Example 2 was placed in a 500 ml three-necked flask, and 114 g of water was added to dissolve the same.
3 g was added and reacted at 80 ° C. for 5 hours with stirring. The reaction was dialyzed for 2 days and concentrated to dryness. Yield: 27.4 g Synthesis Example 11 25.6 g of the polymer obtained in Synthesis Example 1 was placed in a 500 ml three-necked flask, and dissolved by adding 230 g of water to obtain monoethanolamine 1.
2 g, diethanolamine 2.1 g, triethanolamine 3.
0 g was added and reacted at 80 ° C. for 5 hours with stirring. The reaction was dialyzed for 2 days and concentrated to dryness. Yield 21.5 g Synthesis Example 12 28.7 g of the polymer obtained in Synthesis Example 2 was placed in a 500 ml three-necked flask, and 258 g of water was added to dissolve the same.
7 g, diethanolamine 6.3 g, triethanolamine 8.
9 g was added and reacted at 80 ° C. for 5 hours with stirring. The reaction was dialyzed for 2 days and concentrated to dryness. Yield: 25.0 g The intrinsic viscosity of the polyamino acids obtained in Synthesis Examples 1 to 12 was measured by the following method. Table 1 shows the results.

[Measurement method] Approximately 140 mg of a vacuum-dried sample is accurately weighed into a 20-ml volumetric flask, and dissolved by adding a 0.2 N NaCl aqueous solution.
ml. Put 10 ml of this solution in an Ubbelohde viscometer,
The drop speed was measured at 25.5 ° C. Below, 0.2N NaCl
The intrinsic viscosity was determined by diluting the solution to 15 ml and 20 ml by adding an aqueous solution and extrapolating to a concentration of 0.

Example 2 Polymers obtained in Synthesis Examples 1 to 12 and glycerin, sodium pyrrolidonecarboxylate (PCANa) as comparative examples,
Sodium poly-α-glutamate (SPG, degree of polymerization 300)
Prepare 10% aqueous solution of polyamino acid salt and SPG at pH
After adjusting the pH to 5.0, the aqueous
Measured as the amount of antifreeze water per humectant dry weight at -20 ° C by MR method (Fregnance Journal 10 (5),
59 (1982)). Table 1 shows the results.

From Table 1, the polyamino acids of the present invention are glycerin, PCAN
a, It was shown to have the same moisture absorption and retention as SPG.

Example 3 Polymers obtained in Synthesis Examples 1 to 12 and PCAN as a comparative example
a, 3 g of a 1% aqueous solution of SPG was introduced at a constant temperature of 25 ° C. into which air with a humidity of 25% was introduced at 101 / min, and the weight loss due to drying of water was examined. Table 2 shows the results.

Table 2 shows that the polyamino acid of the present invention has the same moisture retention as PCANa and SPG.

Example 4 Milk Lotion A milk lotion having the following formulation was prepared by the following method (unit: g). As a comparative example, SPG (polymerization degree: 300) was prepared in the same manner as in the present invention instead of the polyamino acid salt of the present invention.

[Formulation] Water layer Polyamino acid (Synthesis examples 1 to 10) 1.0 PCANa 1.0 Water 50.0 Preservatives 0.1 Oil layer Liquid paraffin 31.6 Solid paraffin 4.5 Cetanol 4.5 Sorbitan monostearate 1.8 Polyoxyethylene (20) Sorbitan monooleate 2.8 Water layer, The oil layers were each heated to 80 ° C., the aqueous layer was gradually added while stirring the oil layer, and cooled to 40 ° C. while stirring to obtain a milk lotion.

Table 3 shows the results of evaluation of the above blended products. Table 3 shows that the polyamino acid of the present invention has a better feeling in use than SPG.

[Sensory Evaluation Method] Moist and sticky feelings were evaluated as evaluation items by 50 adult women according to the following criteria, and the average value of 50 persons was used as a score.

0 No 1 Slight 2 Slight 3 Slight 4 Very Very Example 5 Hair Shampoo A hair shampoo having the following formulation was prepared (unit: g).
In addition, instead of the polyamino acid salt of the present invention as a comparative example,
It was prepared similarly using SPG (degree of polymerization 300).

[Prescription] Coconut fatty acid acylglutamic acid triethanolamine salt (30%) 30.0 Sodium lauryl ether sulfate (25%) 20.0 Coconut fatty acid diethanolamide 3.0 Disodium citrate 1.5 hydrate 2.0 Polyethylene glycol monostearate 1.0 Propylene glycol 3.0 Poly Oxyethylene Lanolin Alcohol 2.0 Polyamino Acid Salt (Synthesis Examples 1 to 10) 1.0 Water 38.0 Table 4 shows the results of the evaluation of the two shampoos in the same manner as in Example 4. Table 4 shows that the polyamino acid salt of the present invention is SPG
It was shown that the feeling of use was excellent as compared with.

Example 6 Hair Liquid The following hair liquid was prepared (unit: g). As a comparative example, SPG (polymerization degree: 300) was prepared in the same manner as in the present invention instead of the polyamino acid salt of the present invention.

[Prescription] (A) diisobutyl adipate 0.3 polyoxypropylene butyl ether 21.0 ethyl alcohol 50.0 (B) collagen hydrolyzate 2.0 polyamino acid salt (Synthesis Examples 1 to 10) 0.1 malic acid 0.02 propylene glycol 3.0 flavor appropriate amount purified water remaining amount component B was mixed and dissolved, and component A mixed with stirring was added thereto, followed by thorough mixing to obtain a hair liquid.

The setting power of the above-mentioned compound as a hair liquid was examined by sensory evaluation at the time of setting and after 12 hours. Table 5 shows the results. From Table 5, it was shown that the hair liquid using the polyamino acid salt of the present invention had excellent setting power.

[Sensory Evaluation Method] The hair setting power was evaluated by 50 adult males according to the following criteria, and the average value of the 50 males was used as the score.

0 Not at all 1 Very weak 2 Somewhat weak 3 Somewhat strong 4 Very strong [Effect of the Invention] The polyamino acid salt of the present invention has excellent hygroscopicity and moisturizing properties, has no sticky feeling, is excellent in film-forming ability, and can be used as a moisturizing agent and cosmetics having a good feeling in use.

Claims (2)

(57) [Claims] 1. A polyamino acid, which is a copolymer of an acidic amino acid and a neutral amino acid, wherein the content of the acidic amino acid is 40 to 90 mol%, wherein an alkali metal salt and / or a monoethanolamine salt of a carboxylic acid is added to a polymer side chain. And / or a humectant comprising a polyamino acid containing at least 40 mol% of a diethanolamine salt and / or a triethanolamine salt with respect to a polymer side chain. 2. A cosmetic comprising the humectant according to claim 1.