JPH08337515A - Cosmetics - Google Patents

Abstract

PURPOSE: To obtain a cosmetic having excellent hair restoration-stimulating effect, moisture retaining activity, subcutaneous blood flow-stimulating activity, etc., and suitable for hair restoration and skin care by using an acylamino acid having an acyl group of a specific number of carbon atoms or its salt. CONSTITUTION: N-acylamino acid having an acyl group of an odd number of carbon atoms or its salt is used for this cosmetic. The acylamino acid can be produced from an amino acid such as an α-amino acid or an aromatic amino acid. A compound of formula I (R is a straight chain aliphatic hydrocarbon having an even number of carbon atoms, which may has a substituted group; R<1> and R<2> are each H, an alkyl, a hydroxyalkyl, a hydroxyaryl, etc.; x=0-4), especially a compound of formula II [R<3> is (CH2 )y COOH (y=0-4); n=9-17] is especially suitable as the acylamino acid having an acyl group of an odd number of carbon atoms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cosmetics such as hair-growth agents and hair-growth agents, and more particularly, to excellent hair-growth promoting effect, moisturizing effect,
The present invention relates to a cosmetic suitable for hair growth, skin, etc. having a subcutaneous blood flow increasing effect and the like.

[0002]

2. Description of the Related Art Conventionally, cosmetics containing various medicinal agents have been known. For example, in hair restorers, such medicinal agents include vitamins such as vitamin E, amino acids such as serine and methionine, vasodilators such as acetylcholine derivatives, anti-inflammatory agents such as purple root extract, and female hormones such as elastdiol. Agents, skin function enhancers such as cefarantin, melanin synthesis catalysts such as copper pantothenate, keratolytic agents such as salicylic acid, etc.
It is used for the prevention and treatment of alopecia. As an example of blending a fatty acid or a derivative thereof into a cosmetic such as a hair restorer,
It is known that natural vegetable oils such as olive oil and castor oil or stearic acid are blended for the purpose of improving the physical properties of the product. Constituent fatty acids of various naturally occurring lipids such as vegetable oils and animal oils, whether they are saturated fatty acids such as stearic acid and palmitic acid, or unsaturated fatty acids such as oleic acid and linoleic acid, almost all have even carbon numbers. It is known to be a fatty acid having a chain. On the other hand, as an example in which a fatty acid having an odd number of carbon atoms or a derivative thereof is mixed in a hair cosmetic composition, there is a compound described in JP-B-63-41363, for example.

[0003]

However, although the above-mentioned conventional cosmetics such as hair-growth agents are effective in preventing and improving dandruff, itchiness, hair loss, etc., and are said to promote hair growth and hair-growth, they are still known. The reality is that no one has achieved satisfactory results. The present invention has been made under such circumstances, and an object of the present invention is to provide a cosmetic suitable for hair growth, skin, etc., which has an excellent hair growth promoting effect, moisturizing effect, subcutaneous blood flow increasing effect and the like. .

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that an acylamino acid having an acyl group having a specific carbon number or a salt thereof is effective in cosmetics. It has been found that when used as a component, it has excellent hair growth promoting effect, moisturizing effect, subcutaneous blood flow increasing effect and the like. The present invention has been completed based on such findings. That is, the present invention provides a cosmetic containing an N-acyl amino acid having an odd number carbon atom acyl group or a salt thereof as an active ingredient.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The present invention relates to a cosmetic comprising an N-acyl amino acid having an odd number carbon atom acyl group or a salt thereof as an active ingredient, and the N-acyl amino acid having an odd number carbon atom acyl group to be blended herein is At least one of the amino groups in the amino acid is acylated with an acyl group having an odd number of carbon atoms.

As the amino acid used for producing the N-acyl amino acid having an odd-numbered carbon atom acyl group or a salt thereof, any of naturally occurring amino acids, non-proteinogenic amino acids or amino acids produced by chemical synthesis can be used. , For example, α-amino acid, β-amino acid, γ-amino acid, δ-amino acid, aliphatic amino acid, aromatic amino acid, heterocyclic amino acid, neutral amino acid, basic amino acid,
Acid amino acids, alanine, valine, leucine, isoleucine, methionine, tryptophan, phenylalanine, glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, lysine, arginine, aspartic acid, glutamic acid, β-alanine, hydroxylysine, ornithine, citrulline , 5-aminolevulinic acid, γ-aminobutyric acid and the like are used. In the present invention, a compound represented by the following general formula (I) is preferably used as the acylamino acid having an acyl group having an odd number of carbon atoms.

[0007]

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In the formula, R represents a linear aliphatic hydrocarbon group having an even number of carbon atoms which may have a substituent, and R ¹ and R ²
Are hydrogen, alkyl group, hydroxyalkyl group,
Aryl groups, hydroxyaryl groups, - (CH _{2) y} CO
OH or - (CH ₂₎ represents the _z NH _2, these groups each carboxyl group (-COOH) or an amino group (-
It may be substituted with NH ₂ ). Also, x, y and z
Each represents an integer of 0 to 4. In the general formula (I), the even-numbered linear aliphatic hydrocarbon group represented by R may be saturated or unsaturated, but is preferably CH ₃ (CH ₂ ) _n- (here And n is an odd integer of 9 to 17). In the present invention, a compound represented by the following general formula (II) can be preferably used as the N-acyl amino acid represented by the general formula (I).

[0009]

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In the formula, R ³ is — (CH ₂ ) _y COOH (where y is the same as in the general formula (I) above), and n is the same as above. In the present invention, the above y is preferably 1 or 2. Further, the N-acyl amino acid having an odd-numbered carbon acyl group of the present invention has an odd-numbered carbon-number acyl group having 11 to 11 carbon atoms.
19, more preferably an odd number within the range of 13 to 17 can be preferably used. If the carbon number deviates from the above range, the effect of the present invention may not be sufficiently obtained. Furthermore,
The N-acyl amino acid is preferably an acidic amino acid, and particularly N-acyl aspartic acid or N-acyl glutamic acid is preferably used in the present invention.

The salt of the N-acyl amino acid having an odd number carbon atom acyl group used in the present invention is sodium,
Examples thereof include alkali metal salts such as potassium, alkaline earth metal salts such as calcium, ethanolamine salts such as monoethanolamine, diethanolamine and triethanolamine. Among these, monosalts are preferable, and monosodium salts and mono-triethanolamine salts are particularly preferably used. N having the above-mentioned odd carbon number acyl group
The amount of the acylamino acid or salt thereof to be incorporated in the cosmetic of the present invention can be appropriately determined depending on the purpose of use, the form of formulation, etc., but usually 0.01 to 1 with respect to the entire composition.
It can be used in the range of 0% by weight. Compounding amount is 0.0
If it is less than 1% by weight, the effect of the present invention may not be obtained, and if it exceeds 10% by weight, the effect is not so different, but it is not preferable from the economical point of view.

The N-acyl amino acid having an acyl group having an odd number of carbon atoms can be synthesized, for example, by a condensation reaction between a higher fatty acid chloride having an odd number of carbon atoms and an amino acid. Specifically, the so-called Schotten-Baumann (Scho
tten ・ Baumann) reaction, or “Biochemistry”, No. 35
Vol., No. 2, pp. 67-74 (1963), "Study of lipoamino acids (I)". The higher fatty acid having an odd number of carbon atoms can be produced by a conventionally known method. That is, for example, it is possible to synthesize it from an α-olefin having an even number of carbon atoms by the so-called oxo method, and see JP-A-6-
It can also be produced by the method using a microorganism described in Japanese Patent No. 253866.

The cosmetic of the present invention can be prepared by applying a solvent to the above-mentioned N-acyl amino acid having an odd number carbon atom acyl group or a salt thereof. As such a solvent, any solvent can be used as long as it can dissolve the above compound. Therefore, although water can be used, when an organic solvent is used, both hydrophilic and lipophilic ones can be used, and alcohols are particularly preferably used from the viewpoint of affinity with the skin. Specific examples of the solvent that can be used include methanol, ethanol, propyl alcohol,
Examples include isopropyl alcohol, glycerin, propylene glycol, polyethylene glycol, n-paraffin and the like.

In the cosmetic of the present invention, in addition to the above-mentioned N-acyl amino acid having an acyl group having an odd number of carbon atoms or a salt thereof, if necessary, other components may be added within a range that does not impair the object of the present invention. Can be compounded. Such components are appropriately selected according to their use, type, dosage form, etc., but for example, distilled water, alcohols, polyhydric alcohols, surfactants, oils and fats, polysaccharides and other base materials and colorings. Fee,
Perfumes, vitamins, amino acids, hormones, vasodilators, anti-inflammatory agents, keratolytic agents, bactericides, preservatives and the like are appropriately mixed. In addition, the form of cosmetics is liquid depending on the application,
It can be prepared in various forms such as powder and paste, and is commercialized as a hair restorer, hair restorer, etc.

[0015]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Production Example 1 Synthesis of N-tridecanoyl-L-aspartic acid (1) Synthesis of tridecanoyl chloride In a 1-liter two-necked flask, 158.7 g of tridecanoic acid was added.
(0.74 mol) and cyclohexane (200 ml) were added, and thionyl chloride (83.3 g, 0.7 mol) was added.
A 0 ml dropping funnel and a reflux tube were set. While stirring and heating the flask at 80 ° C. in an oil bath,
Tridecanoic acid was completely dissolved. Then, thionyl chloride was added dropwise over 2 hours. Furthermore, the oil bath temperature was kept at 80 ° C. for 1 hour. Cyclohexane and thionyl chloride were removed from this reaction solution under reduced pressure by an aspirator,
The resulting reaction mixture was distilled under reduced pressure to obtain 166.0 g (0.71 mol) of tridecanoyl chloride. The yield based on the charged tridecanoic acid was 95.9%.

(2) Synthesis of N-tridecanoyl-L-aspartic acid In a 1-liter three-necked flask, 15.8 L-aspartic acid was added.
g (0.12 mol) and sodium hydroxide 9.6g (0.24 mol)
(Mol) was added and stirred with an aqueous solution of 150 ml of water. Acetone 12 after dissolution of aspartic acid
0 ml was added. The reaction solution was cooled to 0 ° C., and 23.3 g (0.1 mol) of tridecanoyl chloride and an aqueous solution of 4 g of sodium hydroxide dissolved in 30 ml of water were simultaneously added dropwise over 30 minutes. Meanwhile, the reaction temperature is 0 to 5
The temperature and pH were kept at 11-12. Then, the mixture was stirred for 2 hours while slowly raising the temperature to room temperature (25 ° C.), and N-
A disodium tridecanoyl-L-aspartate solution was obtained. To the solution, 65 ml of 5N hydrochloric acid was added to adjust the pH of the solution to 1, the precipitated crystals were separated by vacuum filtration, washed with water, and dried under reduced pressure. The obtained crystals were washed with 500 ml of hexane, dried and then recrystallized from a solvent of ethanol: water = 3: 7 to obtain 14.4 g (0.044 mol) of N-tridecanoyl-L-aspartic acid. The yield based on the charged tridecanoyl chloride is 36.8.
%Met. The physical properties of the obtained N-tridecanoyl-L-aspartic acid were as follows.

¹ H-NMR (CD ₃ OD); δ (ppm) 0.89 (t, 3H) 1.29 (s, 22H) 1.55-1.65 (m, 2H) 2.23 (t , 2H) 2.72-2.92 (m, 1H) 4.74 (dd, 1H) IR (cm ^-1 ); 3353, 3310, 2926, 17
25,1296,1196,928 Elemental analysis (C ₁₇ H ₃₁ NO ₅ ); Measured values: carbon 62.15%, hydrogen 9.54%, nitrogen 4.22
% Theoretical value: Carbon 61.98%, hydrogen 9.48%, nitrogen 4.25
% Melting point: 117.5-119.7 ° C

Production Example 2 Synthesis of N-tridecanoyl-L-aspartic acid monosodium salt 10.0 g (0.03 mol) of N-tridecanoyl-L-aspartic acid obtained by the above method was added to 500 ml 2
Place in a necked flask, add 300 ml of water and stir, then add an aqueous solution of 1.2 g (0.03 mol) of sodium hydroxide in 50 ml of water, heat to 50 ° C. in a water bath, and add N 2. An aqueous solution of tridecanoyl-L-aspartate monosodium was obtained. This was cooled to room temperature, the precipitated crystals were filtered, dried under reduced pressure, and
8.53 g (0.024 mol) of tridecanoyl-L-aspartic acid monosodium salt was obtained. The yield based on the charged N-tridecanoyl-L-aspartic acid was 80.0%.
Met.

Production Example 3 Synthesis of N-tridecanoyl-L-aspartic acid disodium salt 2.1 g (6.0 mmol) of 30 g of N-tridecanoyl-L-aspartic acid monosodium salt obtained by the above method
Place in a 0 ml flask, add 100 ml of water, stir, and add sodium hydroxide 0.24.
An aqueous solution prepared by dissolving g (6.0 mmol) in 20 ml of water was added to obtain an aqueous disodium N-tridecanoyl-L-aspartate solution. This is freeze-dried and N
-Tridecanoyl-L-aspartic acid disodium salt
2.12 g (5.7 mmol) were obtained. The yield based on the charged monosodium N-tridecanoyl-L-aspartic acid salt was 95.0%.

Production Example 4 Synthesis of N-pentadecanoyl-L-aspartic acid (1) Synthesis of pentadecanoyl chloride 160.0 g of pentadecanoic acid in a 1-liter two-necked flask.
(0.66 mol) and cyclohexane (200 ml) were added, and thionyl chloride (83.3 g, 0.7 mol) was added.
A 0 ml dropping funnel and a reflux tube were set. While stirring and heating the flask at 80 ° C. in an oil bath,
After completely dissolving pentadecanoic acid, thionyl chloride was added dropwise over 2 hours. In addition, set the oil bath temperature to 80
Hold at ℃ for 1 hour. Cyclohexane and thionyl chloride were removed from this reaction mixture under reduced pressure of an aspirator, and the resulting crude reaction product was distilled under reduced pressure to obtain 110.0 g (0.42 mol) of pentadecanoyl chloride. The yield based on the charged pentadecanoic acid was 63.9%.

(2) Synthesis of N-pentadecanoyl-L-aspartic acid L-aspartic acid 31.9 was added to a 1-liter three-necked flask.
g (0.24 mol) and sodium hydroxide 19.2 g (0.4
8 mol) and an aqueous solution of 150 ml of water were added and stirred. Acetone 1 after aspartic acid is dissolved
20 ml was added. The reaction solution was cooled to 0 ° C., and 52.2 g (0.2 mol) of pentadecanoyl chloride and 30 ml of 0.2N aqueous sodium hydroxide solution were simultaneously added dropwise over 30 minutes. During that time, the reaction temperature was maintained at 0 to 5 ° C and the pH was maintained at 11 to 12. Then, the mixture was stirred for 2 hours while slowly raising the temperature to room temperature (25 ° C.) to obtain a disodium N-pentadecanoyl-L-aspartate solution. To the solution, 140 ml of 5N hydrochloric acid was added to adjust the pH of the solution to 1, and the precipitated crystals were separated by vacuum filtration.
After washing with water, it was dried under reduced pressure. The obtained crystals were washed with 500 ml of hexane, dried, and recrystallized with a solvent of ethanol: water = 1: 1 to give N-pentadecanoyl-L.
39.8 g (0.11 mol) of aspartic acid were obtained. The yield based on pentadecanoyl chloride charged was 55.6%. The physical properties of the obtained N-pentadecanoyl-L-aspartic acid were as follows.

¹ H-NMR (CD ₃ OD); δ (ppm) 0.89 (t, 3H) 1.28 (s, 26H) 1.55-1.65 (m, 2H) 2.23 (t , 2H) 2.72-2.92 (m, 1H) 4.74 (dd, 1H) IR (cm ^-1 ); 3353, 3310, 2926, 17
25,1296,1196,928 Elemental analysis (C ₁₉ H ₃₅ NO ₅ ); Measured value: Carbon 63.10%, Hydrogen 9.53%, Nitrogen 4.08
% Theoretical value: Carbon 63.84%, hydrogen 9.87%, nitrogen 3.92
% Melting point: 122.8-124.0 ° C

Production Example 5 Synthesis of N-pentadecanoylaspartic acid monosodium salt 20.0 g (0.056 mol) of N-pentadecanoyl-L-aspartic acid obtained by the above method was placed in a 500 ml two-necked flask. Add water, add 300 ml of water, stir, and then add 2.3 g of sodium hydroxide (0.057
An aqueous solution prepared by dissolving 50 mol of water in 50 ml of water,
Heat to 50 ° C. in a water bath to remove N-pentadecanoyl-L-
An aqueous solution of monosodium aspartate was obtained. This was cooled to room temperature and the precipitated crystals were filtered and dried under reduced pressure to give N-pentadecanoyl-L-aspartic acid monosodium salt (19.85 g, 0.052 mol). The yield based on the charged N-pentadecanoyl-L-aspartic acid was 93.5%.

Production Example 6 Synthesis of N-pentadecanoyl aspartic acid disodium salt 2.1 g (5.5 mmol) of 3 g of N-pentadecanoyl-L-aspartic acid monosodium salt obtained by the above method was added.
Put in a 00 ml flask, add 100 ml of water, stir, and then add sodium hydroxide 0.2
An aqueous solution prepared by dissolving 2 g (5.5 mmol) in 20 ml of water was added to obtain an aqueous disodium N-pentadecanoyl-L-aspartate solution. This was freeze-dried to obtain 2.19 g (5.5 mmol) of N-pentadecanoyl-L-aspartic acid disodium salt. Charged N
The yield based on pentadecanoyl-L-aspartic acid monosodium salt was 98.6%.

Examples 1 to 3 and Comparative Examples 1 to 8 Male C8H mice (body weight 18 to 24 g) aged 8 weeks were used.
About 2 × 3.5 cm of the back of each animal was shaved, and a 1% by weight ethanol solution of the N-acylamino acid compound shown in Table 1 was used as a test sample on the shaved back of the hair. .
1 ml was applied for 3 weeks and the state of hair growth was observed. To evaluate the hair-growth effect, a photograph was taken of the dorsal test area of the mouse, the area was measured from the photographed image using a planimeter, and the ratio of the area of the hair regeneration site to the area of the entire test area was determined as the hair recurrence rate. . The results are shown in Table 1 for each of N-acyl aspartic acid and N-acyl glutamic acid. According to this result, a particularly good hair-growth effect was observed in the N-acyl amino acid having an acyl group having an odd number of carbon atoms. The application of the test sample had no effect on general symptoms, skin conditions and body weight changes during the test period. The N-acyl amino acid compound used here is the above-mentioned Production Example 1
6 or one synthesized according to this was used.

[0026]

[Table 1]

[0027]

[Table 2]

Further, as examples of the present invention, various forms of the cosmetics of the present invention will be shown below together with their compositions. Example 4 Hair nourishment wt% Ethanol 78.0 N-pentadecanoyl aspartic acid 0.5 Olive oil 1.0 α-Tocopherol 0.5 Perfume 0.5 Purified water 19.5 Preservative (appropriate amount)

Example 5 Hair nourishment wt% Ethanol 60.0 N-Tridecanoylglutamic acid 0.5 Dipropylene glycol 3.0 Fragrance 0.5 Purified water 36.0 Preservative (appropriate amount)

Example 6 Hair Liquid Weight% Ethanol 40.0 N-pentadecanoyl aspartic acid 2.0 Glycerin 1.0 Polyoxyethylene glycol monoether 10.0 Fragrance 0.5 Purified water 46.5 Preservative (suitable amount )

Example 7 Hair Cream Weight% N-pentadecanoyl aspartic acid 10.0 Liquid paraffin 30.0 Sorbitan monooleate 2.0 Perfume 0.5 Purified water 57.5 Preservative (appropriate amount)

[0032]

INDUSTRIAL APPLICABILITY According to the present invention, by using an N-acyl amino acid having an odd-numbered carbon number acyl group or a salt thereof as an active ingredient, it has excellent hair growth promoting effect, moisturizing effect, subcutaneous blood flow increasing effect and the like. It is possible to obtain a cosmetic suitable for hair growth and skin.

Claims (4)

[Claims] 1. A cosmetic comprising an N-acyl amino acid having an odd number carbon number acyl group or a salt thereof as an active ingredient. 2. The cosmetic according to claim 1, wherein the N-acyl amino acid having an odd number carbon atom acyl group is obtained by using an acidic amino acid. 3. The cosmetic according to claim 2, wherein the acidic amino acid is glutamic acid or aspartic acid. 4. The N-acyl amino acid having an odd carbon number acyl group has an odd carbon number acyl group having an odd number of carbon atoms in the range of 11 to 19. Cosmetics.