Amino acid derivative composition, and cosmetic obtained by blending same

Abstract

The present invention provides: a composition characterized by containing an amino acid derivative represented by general formula (A), (B), or (C) or a salt thereof, and by the component represented by formula (A) constituting 75-95 mass %, the component represented by formula (B) constituting 5-20 mass %, and the component represented by formula (C) constituting 0-1.5 mass %; a cosmetic base comprising the composition and having excellent moisture retention and functionality while solving the problem of odors and degradation of the feel of use; and a cosmetic obtained by blending said composition. (In the formulas, R1 represents a hydrogen atom or an α-amino acid or a side chain of a salt thereof, and R2 represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium.)

Description

Amino acid derivative compositions and cosmetics containing the same

[0001] The present invention relates to a composition in which amino acid derivatives or salts thereof are combined in a specific ratio and are suitable for use as raw materials for cosmetics, and to cosmetics containing the same.

[0002] Amino acid derivatives are widely known as cosmetic raw materials with excellent functionality, and various studies have been conducted on them. For example, Japanese Patent No. 5625914 (Patent Document 1) discloses amino acid derivatives that can provide cosmetics that have good compatibility with skin and hair, high moisturizing properties, and a good feel when used. However, when these amino acid derivatives are incorporated into cosmetics at high concentrations, they can cause an amino acid-derived odor and a poor feel when used, so further improvements are needed.

[0003] Patent No. 5625914

[0004] An object of the present invention is to provide an amino acid derivative composition having excellent moisturizing properties and a cosmetic preparation containing the same, which solves the problems of odor and poor usability.

[0005] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that a composition containing amino acid derivatives represented by the following general formulas (A) to (C) or salts thereof in a specific ratio exhibits superior moisturizing effects than either of them alone. Furthermore, because cosmetics containing compositions containing the above amino acid derivatives or salts thereof have excellent moisturizing effects, it is possible to reduce the amount of the derivatives added while maintaining the same moisturizing effect, thereby solving problems such as odors and a poor feel when used. The present invention was completed based on these findings.

[0006] A first aspect of the present invention provides a composition containing an amino acid derivative represented by the following general formula (A), (B), or (C) or a salt thereof, wherein the component represented by formula (A) accounts for 75 to 95% by mass, the component represented by formula (B) accounts for 5 to 20% by mass, and the component represented by formula (C) accounts for 0 to 1.5% by mass:

[0007]

[0008]

[0009]

[0010] (In the above formulas (A), (B), and (C), R 1 represents a hydrogen atom or the side chain of an α-amino acid, R 2 represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium. 1 , R in formula (B) 1 and R of formula (C) 1 are the same.)

[0011] The second aspect of the present invention is a preferred embodiment of the first aspect of the present invention, characterized in that it does not contain an amino acid derivative represented by the following general formula (D) or a salt thereof, or if it does contain one, the amount is 0.1 mass % or less, and is particularly preferred in that it has a high moisturizing effect.

[0012]

[0013] (In the formula R 1 represents a hydrogen atom or the side chain of an α-amino acid or a salt thereof, R 2 represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

[0014] The third aspect of the present invention is a composition according to the first or second aspect of the present invention, characterized in that the amino acid is arginine or glycine. Arginine or glycine is preferred in that it provides an excellent feel when blended into cosmetics.

[0015] The composition containing the amino acid derivative or salt thereof of the present invention can be blended into cosmetics. A fourth aspect of the present invention is a cosmetic characterized by blending the composition of any one of the first to third aspects of the present invention. The fourth aspect of the present invention is a cosmetic that exhibits a high moisturizing effect, reduces odor derived from the amino acid derivative, and provides an excellent feeling when used.

[0016] The compositions of the present invention, which contain the amino acid derivatives represented by general formulas (A) to (C) or their salts in specific proportions, have a superior moisturizing effect compared to the respective compositions alone. Therefore, cosmetics incorporating these compositions can be formulated in smaller amounts while maintaining the same moisturizing effect as conventional amino acid derivatives or their salts formulated alone. This makes it possible to solve problems such as odor and poor usability that occur when amino acid derivatives or their salts are formulated in cosmetics.

[0017] The following describes an embodiment of the present invention, but the scope of the present invention is not limited to the embodiment described below.

[0018] Examples of amino acids that can be used as raw materials (starting materials) for producing the amino acid derivatives represented by the above-described general formulas (A) to (C) or salts thereof that constitute the composition of the present invention include acidic amino acids such as aspartic acid and glutamic acid, neutral amino acids such as isoleucine, leucine, valine, glycine, alanine, serine, threonine, phenylalanine, asparagine, glutamine, tyrosine, tryptophan, methionine, and cysteine, and basic amino acids such as lysine, arginine, and histidine. Basic or neutral amino acids are preferred, and arginine or glycine is even more preferred, as these are expected to provide an excellent feel when incorporated into cosmetics.

[0019] The amino acid derivatives or salts thereof represented by general formulas (A) to (C) constituting the composition of the present invention can be obtained by reacting the amino acid or salts thereof with glycidol (i.e., 2,3-epoxy-1-propanol) or 3-halo-1,2-propanediol, followed by acetalization and acid treatment. Alternatively, the amino acid or salts thereof can be obtained by reacting the amino acid or salts thereof with 4-[(2,3-epoxypropoxy)methyl]-2,2-dimethyl-1,3-dioxolane or 4-halo-methyl-2,2-dimethyl-1,3-dioxolane, followed by acid treatment.

[0020] In the reaction with glycidol, 3-halo-1,2-propanediol, 4-[(2,3-epoxypropoxy)methyl]-2,2-dimethyl-1,3-dioxolane, or 4-halo-methyl-2,2-dimethyl-1,3-dioxolane, the pH during the reaction is preferably 8 to 12, and more preferably 8 to 11. Examples of pH adjusters used during the reaction include alkaline agents such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, and potassium carbonate.

[0021] Examples of the solvent used in the reaction include water, dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. The reaction temperature is preferably 10°C to 90°C, and more preferably 20°C to 80°C.

[0022] The compounds synthesized by the above methods can be purified by means of column chromatography using silica gel, crystallization, or the like.

[0023] When an amino acid or a salt thereof is reacted with glycidol or 3-halo-1,2-propanediol, an intermediate for the amino acid derivative of the present invention having an acetal structure introduced therein can be obtained by reacting the amino acid or a salt thereof with various carbonyl compounds or dialkyloxy compounds under acidic conditions.

[0024] Examples of the carbonyl compound used in the reaction include acetone, methyl ethyl ketone, diethyl ketone, cyclopentanone, cyclohexanone, formaldehyde, acetaldehyde, and benzaldehyde.

[0025] Examples of the dialkoxy compound used in the reaction include 2,2-dimethoxypropane, 2-methoxy-2-ethoxypropane, 2,2-diethoxypropane, and α,α-dimethoxytoluene.

[0026] The pH during the reaction is preferably 1 to 5, more preferably 2 to 4, and examples of the pH adjuster include acids such as p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, and sulfuric acid.

[0027] Examples of the solvent used in the reaction include alcohol, acetone, and tetrahydrofuran. The reaction is preferably carried out at a temperature of 0 to 40°C, more preferably 10 to 30°C.

[0028] The intermediate of the amino acid derivative of the present invention having an acetal structure introduced therein, synthesized by the above method, can be purified by means of column chromatography using silica gel, crystallization, or the like.

[0029] The intermediate for the amino acid derivative of the present invention into which an acetal structure has been introduced, synthesized by the above method, and the reaction product of an amino acid or a salt thereof with 4-[(2,3-epoxypropoxy)methyl]-2,2-dimethyl-1,3-dioxolane or 4-halo-methyl-2,2-dimethyl-1,3-dioxolane can be subjected to acid treatment in the presence of water under acidic conditions to obtain the amino acid derivative or a salt thereof represented by general formulas (A) to (C) that constitute the composition of the present invention.

[0030] The pH during the reaction is preferably 1 to 5, more preferably 1 to 3. Examples of pH adjusters during the reaction include acids such as p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, and sulfuric acid.

[0031] The solvent used in the reaction includes water, alcohol, tetrahydrofuran, etc., and the reaction is preferably carried out at a temperature of 0 to 40°C, more preferably 10 to 30°C.

[0032] The amino acid derivatives or salts thereof represented by the above-described general formulas (A) to (C) which constitute the composition of the present invention, synthesized by the above-described method, can be purified by means of column chromatography using silica gel, crystallization, or the like.

[0033] The amino acid derivative may be in the form of a salt, such as a sodium salt, potassium salt, calcium salt, alkylamine salt, hydrochloride, sulfate, phosphate, or acetate.

[0034] The blending ratios of the composition of the present invention are 75 to 95 mass% of component (A), 5 to 20 mass% of component (B), and 0 to 1.5 mass% of component (C). Deviations from these ratios are not preferred because the moisturizing effect decreases, and more preferred ratios are 80 to 90 mass% of component (A), 8 to 18 mass% of component (B), and 0.5 to 1.5 mass% of component (C).

[0035] The composition of the present invention containing general formulas (A) to (C) preferably does not contain the amino acid derivative represented by general formula (D) or a salt thereof, or if it does contain it, the amount is preferably 0.1 mass % or less. This range is preferred because it shows a particularly high moisturizing effect when blended into cosmetics.

[0036] The mixture of amino acid derivatives or salts thereof of the present invention can be applied to cosmetics, and can contain any ingredients that are normally used in cosmetics depending on the intended use, as long as stability and other factors are not impaired.

[0037] As ingredients typically used in cosmetics, for example, oily ingredients, polymeric compounds such as surfactants, emulsifiers, and thickeners, whitening agents, texture improvers, drugs, ultraviolet absorbers, proteins, protein hydrolysates or derivatives thereof, amino acids or amino acid derivatives other than components (A) to (C), antioxidants, sequestering agents, pH adjusters, preservatives, moisturizers, pigments, colorants, fragrances, and the like can be appropriately blended.

[0038] Examples of the oily components, polymeric compounds such as surfactants, emulsifiers, and thickeners, whitening agents, texture improvers, drugs, ultraviolet absorbers, proteins, protein hydrolysates or derivatives thereof, amino acids or amino acid derivatives other than components (A) to (C), antioxidants, sequestering agents, pH adjusters, preservatives, moisturizers, pigments, colorants, and fragrances include those similar to those described in WO2022 / 080287.

[0039] The above-mentioned components commonly used in cosmetics can be used alone or in combination of two or more.

[0040] The present invention will now be described in detail with reference to synthesis examples and examples, although the present invention is not limited to these synthesis examples and examples.

[0041] Synthesis Example 1: Synthesis of N-glycerylarginine Arginine (10.45 g), ion-exchanged water (75 ml), and sodium hydroxide (0.60 g) were added to a recovery flask and heated to 40°C. Glycidol (1.11 g) was added over 1 hour, and the mixture was stirred for 3 hours. Subsequently, 17% hydrochloric acid was added to neutralize the mixture, and the mixture was concentrated under reduced pressure. Acetone (75 ml), sodium p-toluenesulfonate monohydrate (3.00 g), and 2,2-dimethoxypropane (9.00 g) were added to the resulting residue (12.31 g), and the mixture was stirred overnight at room temperature. A 25% aqueous sodium hydroxide solution was added, and the mixture was concentrated under reduced pressure. The resulting residue (20.54 g) was subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water = 10:10:3 solution, and concentrated under reduced pressure to obtain N-4-methyl-2,2-dimethyl-1,3-dioxolanyl arginine. Furthermore, 5% hydrochloric acid (3.83 g) was added to N-4-methyl-2,2-dimethyl-1,3-dioxolanyl arginine (0.75 g), and the mixture was stirred overnight at room temperature. Subsequently, 25% aqueous sodium hydroxide solution was added to neutralize the mixture, and the mixture was concentrated under reduced pressure. The resulting residue (0.56 g) was then subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water = 10:10:3 solution, and concentrated under reduced pressure to obtain N-glyceryl arginine (yield 22.8%) represented by the following structure.

[0042] The resulting product was analyzed by mass spectrometry. 1 H-NMR, １３ C-NMR measurement was carried out, and it was confirmed that it was N-glycerylarginine represented by the following structural formula. In the synthesis examples shown below, similar measurements were carried out on the obtained products, and it was confirmed that they were amino acid derivatives represented by the structural formulas and compound names shown in each synthesis example. Mass analysis of the products obtained in the synthesis examples below, 1 H-NMR and １３ The results of C-NMR measurements are shown in Tables 1 to 3.

[0043]

[0044] Synthesis Example 2: Synthesis of N,N-diglycerylarginine Arginine (2.09 g), ion-exchanged water (15 ml), and sodium hydroxide (0.96 g) were added to a recovery flask and heated to 40°C. Glycidol (1.78 g) was added over 1 hour, and the mixture was stirred for 3 hours. Subsequently, 17% hydrochloric acid was added to neutralize the mixture, and the mixture was concentrated under reduced pressure. Acetone (40 ml), sodium p-toluenesulfonate monohydrate (1.00 g), and 2,2-dimethoxypropane (5.50 g) were added to the resulting residue (5.11 g), and the mixture was stirred overnight at room temperature. 25% aqueous sodium hydroxide solution was added, and the mixture was concentrated under reduced pressure. The resulting residue (11.38 g) was subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water = 7:4:0.5 solution, and concentrated under reduced pressure to obtain N,N-di-(4-methyl-2,2-dimethyl-1,3-dioxolanyl)arginine. Furthermore, 5% hydrochloric acid (2.00 g) was added to N,N-di-(4-methyl-2,2-dimethyl-1,3-dioxolanyl)arginine (0.20 g), and the mixture was stirred overnight at room temperature. Subsequently, 25% aqueous sodium hydroxide solution was added to neutralize the mixture, and the mixture was concentrated under reduced pressure. The resulting residue (0.39 g) was then subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water = 10:10:3 solution, and concentrated under reduced pressure to obtain N,N-diglycerylarginine (yield 11.0%) represented by the following structure.

[0045]

[0046] Synthesis Example 3: Synthesis of N-(O-glyceryl)glycerylarginine Arginine (0.66 g) and ion-exchanged water (2.2 ml) were added to a recovery flask and heated to 50°C. Subsequently, 4-[(2,3-epoxypropoxy)methyl]-2,2-dimethyl-1,3-dioxolane (0.72 g) was added over 15 minutes, followed by stirring for 1.5 hours and concentration under reduced pressure. The resulting residue (1.48 g) was subjected to silica gel column chromatography, eluted with methanol, and concentrated under reduced pressure to obtain N-(O-4-methyl-2,2-dimethyl-1,3-dioxolanyl)glycerylarginine. Furthermore, 5% hydrochloric acid (1.00 g) was added to N-(O-4-methyl-2,2-dimethyl-1,3-dioxolanyl)glycerylarginine (0.36 g), and the mixture was stirred overnight at room temperature. The mixture was then neutralized with a 25% aqueous solution of sodium hydroxide and concentrated under reduced pressure. The resulting residue (0.31 g) was subjected to silica gel column chromatography, eluted with methanol, and concentrated under reduced pressure to obtain N-(O-glyceryl)glycerylarginine (yield 90.0%) represented by the following structure.

[0047]

[0048] Synthesis Example 4: Synthesis of N-glycerylglycine Glycine (10.0 g), ion-exchanged water (30 ml), N,N-dimethylformamide (10 ml), sodium hydroxide (2.40 g), and 4-chloromethyl-2,2-dimethyl-1,3-dioxolane (9.79 g) were added to a recovery flask and stirred overnight at 80°C. Subsequently, 17% hydrochloric acid was added to neutralize the mixture, followed by concentration under reduced pressure. The resulting residue (23.01 g) was subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water (6:4:1) solution, and concentrated under reduced pressure to obtain N-4-methyl-2,2-dimethyl-1,3-dioxolanylglycine. Furthermore, 5% hydrochloric acid (2.80 g) was added to N-4-methyl-2,2-dimethyl-1,3-dioxolanylglycine (0.54 g), and the mixture was stirred overnight at room temperature. The mixture was then neutralized with a 1% aqueous solution of sodium hydroxide and concentrated under reduced pressure. The resulting residue (0.79 g) was then subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water (6:4:1) solution, and concentrated under reduced pressure to obtain N-glycerylglycine (yield 21.2%) represented by the following structure.

[0049]

[0050] Synthesis Example 5: Synthesis of N,N-diglycerylglycine Glycine (2.50 g), ion-exchanged water (10 ml), and sodium hydroxide (4.00 g) were added to a recovery flask and the temperature was raised to 40°C. Glycidol (7.41 g) was then added over 1 hour, followed by stirring for 3 hours. 17% hydrochloric acid was added to neutralize the mixture, and the mixture was then concentrated under reduced pressure. Acetone (200 ml), sodium p-toluenesulfonate monohydrate (4.75 g), and 2,2-dimethoxypropane (50.00 g) were added to the resulting residue (18.28 g), and the mixture was stirred overnight at room temperature. 1% aqueous sodium hydroxide solution was added, followed by concentration under reduced pressure. The resulting residue (23.97 g) was subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water = 10:3:0.3 solution, and concentrated under reduced pressure to obtain N,N-di-(4-methyl-2,2-dimethyl-1,3-dioxolanyl)glycine. Furthermore, 5% hydrochloric acid (0.60 g) was added to N,N-di-(4-methyl-2,2-dimethyl-1,3-dioxolanyl)glycine (0.18 g), and the mixture was stirred overnight at room temperature. Subsequently, 1% aqueous sodium hydroxide solution was added to neutralize the mixture, and the mixture was concentrated under reduced pressure. The resulting residue (0.36 g) was subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water = 6:4:1 solution, and concentrated under reduced pressure to obtain N,N-diglycerylglycine (yield 30.2%) represented by the following structure.

[0051]

[0052] Synthesis Example 6: Synthesis of N-(O-glyceryl)glycerylglycine Glycine (0.38 g), 25% aqueous sodium hydroxide solution (0.16 g), and ion-exchanged water (1.5 ml) were added to a recovery flask and heated to 50°C. 4-[(2,3-epoxypropoxy)methyl]-2,2-dimethyl-1,3-dioxolane (0.94 g) was then added over 15 minutes, followed by stirring for 3 hours and concentration under reduced pressure. The resulting residue (1.17 g) was subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water (5:4:0.4) solution, and concentrated under reduced pressure to obtain N-(O-4-methyl-2,2-dimethyl-1,3-dioxolanyl)glycerylglycine. Furthermore, 5% hydrochloric acid (2.00 g) was added to N-(O-4-methyl-2,2-dimethyl-1,3-dioxolanyl)glycerylglycine (0.53 g) and the mixture was stirred overnight at room temperature. Subsequently, a 1% aqueous solution of sodium hydroxide was added to neutralize the mixture, followed by concentration under reduced pressure. The resulting residue (0.42 g) was subjected to silica gel column chromatography, eluted with a chloroform / methanol / ion-exchanged water=1:1:0.1 solution, and concentrated under reduced pressure to obtain N-(O-glyceryl)glycerylglycine (yield 91.0%) represented by the following structure:

[0053]

[0054] Mass spectrometry of the products obtained in Synthesis Examples 1 to 6 was carried out using an LCMS-2020 (manufactured by Shimadzu Corporation). The measurement results are shown in Table 1.

[0055]

[0056] The products obtained in Synthesis Examples 1 to 6 1 H-NMR was performed using a JNM-ECS400 (manufactured by JEOL Ltd.) The measurement results are shown in Table 2.

[0057]

[0058] The products obtained in Synthesis Examples 1 to 6 1３ C-NMR was performed using a JNM-ECS400 (manufactured by JEOL Ltd.) The measurement results are shown in Table 3.

[0059]

[0060] Test Example 1 [Moisture retention test] Each sample, which was blended in the proportions shown in Examples 1 to 12 and Comparative Examples 1 to 6 in Tables 4 and 5 below, was vacuum dried to about 40 mg (this weight was W ０ The weight of each sample was measured periodically and allowed to stand until it had absorbed enough moisture to prevent any weight change. The weight was then transferred to an environment of 25°C and 20% humidity (in a sealed container filled to the bottom with a saturated aqueous potassium acetate solution), and the weight after 24 hours (this weight was recorded as W １ From this, the amount of water retained per gram of dry sample, Δ (g / g), was calculated using the following formula: １ -W ０ ) / W ０

[0061]

[0062]

[0063] As shown in Tables 4 and 5, it was revealed that compositions containing the amino acid derivatives of the present invention or their salts, which are mixtures of the amino acid derivatives of the general formulas (A) to (C) or their salts in a specific ratio, exhibit a superior moisturizing effect (amount of moisture retained) compared to the amino acid derivatives of the general formulas (A) to (C) or their salts alone. In other words, the compositions containing the amino acid derivatives of the present invention or their salts can reduce the amount of the amino acid derivatives or their salts blended in cosmetics while maintaining the moisturizing ability, thereby making it possible to suppress odors and deterioration in the feel of use that are attributable to the amino acid derivatives.

[0064] Example 13: Lotion A lotion is prepared by thoroughly mixing the raw materials (1) to (6) in the composition shown in Table 6. In the tables following Table 6, the blending amounts are in parts by mass.

[0065]

[0066] Example 14 Emulsion The oil phase ingredients (1) to (9) and the aqueous phase ingredients (10) to (13) in the compositions shown in Table 7 are each heated to 70°C and dissolved to prepare an oil phase and an aqueous phase, respectively. The oil phase is then added to the aqueous phase and pre-emulsified, and the mixture is homogeneously emulsified using a homomixer. The mixture is then cooled to room temperature while stirring well to prepare an emulsion.

[0067]

[0068] Example 15 Cream The oil phase ingredients (1) to (5) and the aqueous phase ingredients (6) to (10) shown in Table 8 are each heated to 70°C and dissolved to prepare an oil phase and an aqueous phase, respectively. The oil phase is then added to the aqueous phase and pre-emulsified, and the mixture is homogeneously emulsified using a homomixer. The mixture is then cooled to room temperature while stirring thoroughly to prepare a cream.

[0069]

Claims

1. A composition comprising an amino acid derivative represented by the following general formula (A), (B), or (C) or a salt thereof, wherein the component represented by formula (A) is 75 to 95% by mass, the component represented by formula (B) is 5 to 20% by mass, and the component represented by formula (C) is 0 to 1.5% by mass. (In the above formulas (A), (B), and (C), R 1 represents a hydrogen atom or the side chain of an α-amino acid or a salt thereof, R 2 represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium. 1 , R in formula (B) 1 and R of formula (C) 1 are the same.) 2. The composition according to claim 1, characterized in that it does not contain an amino acid derivative represented by the following general formula (D) or a salt thereof, or if it does contain one, the amount is 0.1 mass % or less. (In the formula R 1 represents a hydrogen atom or the side chain of an α-amino acid or a salt thereof, R 2 represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.) 3. The composition according to claim 1 or 2, wherein the amino acid is arginine or glycine.

4. A cosmetic preparation characterized by containing the composition according to any one of claims 1 to 3.

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