Amino acid derivative compositions and cosmetics containing the same

Abstract

To provide a cosmetic base that solves the problem of odor attachment and degradation of feeling in use and exhibits excellent moisture retention and functionality, and a cosmetic incorporating composition.SOLUTION: A composition containing an amino acid derivative represented by general formulae (A) to (C) or salts thereof, wherein component (A) is 75-95 mass%, component (B) is 5-20 mass%, and component (C) is 0-1.5 mass%. (In the formulae, R1 represents a hydrogen atom or a side chain of an α-amino acid or a salt thereof, and R2 represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium).SELECTED DRAWING: None

Description

[Technical Field]

[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. [Background technology]

[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 are well-suited to skin and hair, have high moisturizing properties, and are pleasant to use. However, when these amino acid derivatives are incorporated into cosmetics at high levels, they can cause an amino acid-derived odor and a poor feel when used, so further improvements are needed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5625914 Summary of the Invention [Problem to be solved by the invention]

[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. [Means for solving the problem]

[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 their salts 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 their salts 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] The first aspect of the present invention provides a composition comprising an amino acid derivative of the following general formulas (A) to (C) or a salt thereof, wherein component (A) is 75 to 95% by mass, component (B) is 5 to 20% by mass, and component (C) is 0 to 1.5% by mass.

[0007] [ka]

[0008] [ka]

[0009] [ka]

[0010] (R in the formula 1 represents a hydrogen atom or the side chain of an α-amino acid or a salt thereof, and R 2 represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.

[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] [ka]

[0013] (R in the formula 1 represents a hydrogen atom or the side chain of an α-amino acid or a salt thereof, and 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 a preferred embodiment of the first or second aspect of the present invention, characterized in that the amino acid is arginine or glycine, which 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 according to any one of the first to third aspects of the present invention. The cosmetic of the fourth aspect of the present invention exhibits a high moisturizing effect, reduces odor originating from the amino acid derivative, and provides an excellent feeling when used. [Effects of the Invention]

[0016] The compositions containing the amino acid derivatives or salts thereof of the present invention in specific proportions have a superior moisturizing effect compared to either of them alone. Therefore, cosmetics containing these compositions can be formulated in smaller amounts while maintaining the same moisturizing effect as conventional amino acid derivatives or salts thereof. This makes it possible to solve problems such as odor and poor usability that occur when amino acid derivatives or salts thereof are formulated in cosmetics. DETAILED DESCRIPTION OF THE INVENTION

[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-halomethyl-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-halomethyl-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 solvents used in the reaction include water, dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. The reaction is preferably carried out at a temperature of 10 to 90°C, more preferably 20 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 of 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 intermediates of the amino acid derivatives of the present invention into which an acetal structure has been introduced, synthesized by the above method, and the reaction products of an amino acid or a salt thereof with 4-[(2,3-epoxypropoxy)methyl]-2,2-dimethyl-1,3-dioxolane or 4-halomethyl-2,2-dimethyl-1,3-dioxolane can be treated with an acid in the presence of water under acidic conditions to obtain the amino acid derivatives or salts 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] Examples of the solvent used in the reaction include water, alcohol, and tetrahydrofuran. The reaction is preferably carried out at a temperature of 0°C to 40°C, more preferably 10°C to 30°C.

[0032] The amino acid derivatives or salts thereof represented by the above-described general formulas (A) to (C) that 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, a potassium salt, a calcium salt, an alkylamine salt, a hydrochloride, a sulfate, a phosphate, or an 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, etc. may 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. [Example]

[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, followed by stirring for 3 hours. Subsequently, 17% hydrochloric acid was added to neutralize the mixture, followed by concentration 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 solution of sodium hydroxide was added, followed by concentration under reduced pressure. The resulting residue (20.54 g) was subjected to silica gel column chromatography, eluted with a 10:10:3 mixture of chloroform, methanol, and ion-exchanged water, and concentrated under reduced pressure to obtain N-4-methyl-2,2-dimethyl-1,3-dioxolanylarginine. Further, N-4-methyl-2,2-dimethyl-1,3-dioxolanyl arginine (0.75 g) and 5% hydrochloric acid (3.83 g) were added and stirred overnight at room temperature. After that, 25% aqueous sodium hydroxide solution was added to neutralize, and then 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, 13C-NMR measurement was carried out and it was confirmed that it was N-glyceryl arginine represented by the following structural formula. In the synthesis examples shown below, the obtained products were also measured in the same way and it was confirmed that they were amino acid derivatives represented by the structural formula and compound name 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] [ka]

[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, followed by stirring for 3 hours. Subsequently, 17% hydrochloric acid was added to neutralize the mixture, followed by concentration 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. A 25% aqueous solution of sodium hydroxide was added, followed by concentration 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. Further, N,N-di-(4-methyl-2,2-dimethyl-1,3-dioxolanyl)arginine (0.20 g) and 5% hydrochloric acid (2.00 g) were added and stirred overnight at room temperature. After that, 25% aqueous sodium hydroxide solution was added to neutralize, and then 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] [ka]

[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. 4-[(2,3-epoxypropoxy)methyl]-2,2-dimethyl-1,3-dioxolane (0.72 g) was then 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. Further, N-(O-4-methyl-2,2-dimethyl-1,3-dioxolanyl)glycerylarginine (0.36 g) and 5% hydrochloric acid (1.00 g) were added and stirred overnight at room temperature. After that, 25% aqueous sodium hydroxide solution was added to neutralize the mixture, and then the mixture was 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] [ka]

[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. The mixture was then neutralized with 17% hydrochloric acid and concentrated 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. Further, N-4-methyl-2,2-dimethyl-1,3-dioxolanylglycine (0.54 g) and 5% hydrochloric acid (2.80 g) were added, and the mixture was stirred overnight at room temperature. After that, 1% aqueous sodium hydroxide solution was added to neutralize the mixture, and the mixture was 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] [ka]

[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 heated to 40°C. Glycidol (7.41 g) was then added over 1 hour, followed by stirring for 3 hours. After neutralization with 17% hydrochloric acid, the mixture was 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. After addition of 1% aqueous sodium hydroxide, the mixture was concentrated 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. Further, N,N-di-(4-methyl-2,2-dimethyl-1,3-dioxolanyl)glycine (0.18 g) and 5% hydrochloric acid (0.60 g) were added, and the mixture was stirred overnight at room temperature. After that, 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] [ka]

[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. Further, N-(O-4-methyl-2,2-dimethyl-1,3-dioxolanyl)glycerylglycine (0.53 g) and 5% hydrochloric acid (2.00 g) were added, and the mixture was stirred overnight at room temperature. After that, the mixture was neutralized with 1% aqueous sodium hydroxide solution and then concentrated 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] [ka]

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

[0055] [Table 1]

[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] [Table 2]

[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] [Table 3]

[0060] Test Example 1 [Moisture retention test] Each sample, blended at the ratios shown in Examples 1 to 12 and Comparative Examples 1 to 6 in Tables 4 and 5, was vacuum-dried, and approximately 40 mg of each (referred to as W0) was dispensed into a weighing bottle (3.6 cm in diameter, 1.8 cm in height excluding the lid). Each sample in the weighing bottle was placed in a constant-humidity incubator (LTI-1200, manufactured by Tokyo Rikakikai Co., Ltd.) at a temperature of 25°C and a humidity of 75%. The weight was measured periodically, and the sample was left to stand until sufficient moisture absorption had occurred and the weight no longer changed. The sample was then transferred to an airtight container (filled to the bottom with a saturated potassium acetate solution) at a temperature of 25°C and a humidity of 20%. The weight after 24 hours (referred to as W1) was used to calculate the water retention amount Δ (g / g) per gram of dried sample using the following formula: (W1-W0) / W0

[0061] [Table 4]

[0062] [Table 5]

[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 specific ratios, exhibit superior moisturizing effects (water retention) 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, 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) having the composition shown in Table 6. In the tables following Table 6, the blending amounts are in parts by mass.

[0065] [Table 6] *1: This refers to the amount required to make the total blended amount 100 parts by mass. The same applies to the following tables.

[0066] Example 14 Emulsion The oil phase ingredients (1) to (9) and the aqueous phase ingredients (10) to (13) 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] [Table 7]

[0068] Example 15 Cream The oil phase ingredients (1) to (5) and the aqueous phase ingredients (6) to (10) shown in Table 8 are heated to 70°C and dissolved to prepare the oil phase and 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 the cream.

[0069] [Table 8]

Claims

1. A composition comprising an amino acid derivative represented by the following general formulas (A) to (C) or a salt thereof, wherein the component (A) is 75 to 95% by mass, the component (B) is 5 to 20% by mass, and the component (C) is 0 to 1.5% by mass: 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 (R in formula (A), formula (B) and formula (C) １ are the same group and represent a hydrogen atom or the side chain of arginine, and R ２ represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium.

2. 2. The composition according to claim 1, wherein the composition does not contain an amino acid derivative represented by the following general formula (D) or a salt thereof, or if it does contain an amino acid derivative or a salt thereof, the amount is 0.1 mass % or less. 【Chemistry 4】 (In the formula R １ represents a hydrogen atom or the side chain of arginine, R ２ represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium.

3. A cosmetic characterized by containing the composition described in claim 1 or claim 2.

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