Topical skin preparations

Abstract

To provide a skin external preparation that synergistically improves moisturizing effect by combining specific ingredients.SOLUTION: Provided is a skin external preparation containing the following (A) to (C): (A) at least one diester compound represented by the following formula (a) R1-(OCH2CH2)m-OOC-R-COO-(CH2CH2O)n-R2 (where, R1 and R2 independently represent a saturated or unsaturated, linear, branched or cyclic monovalent C1 to C12 hydrocarbon group; R represents a saturated or unsaturated, linear, branched or cyclic divalent C1 to C12 hydrocarbon group; and m and n independently represent an integer of 1 to 20, preferably 1 to 15, more preferably 2 to 11 ); (B) polyoxypropylene diglyceryl ether; and (C) oligomer ester composed of dihydric carboxylic acid and polyglycerol with an average degree of polymerization of 2 to 15.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a topical skin preparation. [Background technology]

[0002] In recent years, technological developments have been undertaken to enhance the added value of topical skin preparations, such as combining various ingredients. Generally, the functions required of topical skin preparations are diverse, but traditionally, various moisturizers have been considered and included to enhance moisturizing effects, and research is being conducted to further improve these effects by combining ingredients (Reference 1).

[0003] However, simply combining ingredients does not necessarily result in a synergistic improvement; the effects of such combinations are unpredictable, with some ingredients additively enhancing effects and others canceling them out. In particular, there is a very high need to incorporate ingredients that provide greater efficacy in smaller quantities into topical skin preparations. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2021-123540 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a topical skin preparation in which the moisturizing effect is synergistically improved by using specific ingredients in combination. [Means for solving the problem]

[0006] The means of solving the problems of the present invention is to provide a topical skin preparation containing the following (A) to (C). (A) The following formula (a) R 1 -(OCH2CH2) m-OOC-R-COO-(CH2CH2O) n -R 2 (a) (In the formula, R 1 and R 2 each independently represents a saturated or unsaturated, linear, branched or cyclic monovalent C1 to C12 hydrocarbon group; R represents a saturated or unsaturated, linear, branched or cyclic divalent C1 to C12 hydrocarbon group; m and n each independently represent an integer of 1 to 20, preferably 1 to 15, more preferably 2 to 11.) at least one diester compound represented by (B) Polyoxypropylene diglyceryl ether (C) An oligomer ester composed of a dicarboxylic acid and polyglycerin with an average degree of polymerization of 2 to 15 [Advantages of the Invention]

[0007] The external preparation for skin of the present invention exhibits an effect of synergistically improving the moisturizing effect by using specific components in combination. [Embodiments for Carrying Out the Invention]

[0008] Hereinafter, embodiments for carrying out the present invention will be described.

[0009] In the external preparation for skin of the present invention, two or more diester compounds including (A) at least one specific diester compound may be used in combination. Therefore, a single type of diester compound or a combination of different types of diester compounds can be used.

[0010] The (A) diester compound used in the present invention has the following formula (a) R 1 -(OCH2CH2) m -OOC-R-COO-(CH2CH2O) n -R 2 (a) (In the formula, R 1 and R 2represents, independently, a saturated or unsaturated, linear, branched or cyclic, monovalent C1 to C 12 hydrocarbon group; R represents a saturated or unsaturated, linear, branched or cyclic, divalent C1 to C 12 hydrocarbon group; m and n independently represent integers from 1 to 20, preferably from 1 to 15, more preferably from 2 to 11. It can be represented by).

[0011] R 1 and R 2 independently represent a saturated, linear, branched or cyclic, monovalent C1 to C 12 hydrocarbon group, more preferably a linear, branched or cyclic C1 to C 12 alkyl group, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group and n-dodecyl group, more preferably methyl group and ethyl group, particularly preferably ethyl group.

[0012] R represents a saturated, linear, branched or cyclic, divalent C1 to C 12 hydrocarbon group, more preferably a linear, branched or cyclic C1 to C 12 alkylene group, such as methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, n-hexylene group, cyclohexylene group, n-octylene group, 2-ethylhexylene group, n-decylene group and n-dodecylene group, more preferably cyclohexylene group, particularly preferably 1,4-cyclohexylene group.

[0013] m and n are more preferably 2 or 3 independently.

[0014] (A) Examples of diester compounds include bis(diethylene glycol monoethyl ether) 1,4-cyclohexanedicarboxylate, bis(triethylene glycol monoethyl ether) 1,4-cyclohexanedicarboxylate, bis(diethylene glycol monoethyl ether) adipate, bis(triethylene glycol monoethyl ether) adipate, and dicarbitol succinate. Bis(diethylene glycol monoethyl ether) 1,4-cyclohexanedicarboxylate (INCI name: cyclohexane1,4-dicarboxylate bis-ethoxydiglycol) and dicarbitol succinate (INCI name: bis-ethoxydiglycol succinate) are more preferred. Bis(diethylene glycol monoethyl ether) 1,4-cyclohexanedicarboxylate is commercially available under the name "Neosolue-Aqulio" (manufactured by Nippon Seika Co., Ltd.). Dicarbitol succinate (INCI name: bis-ethoxydiglycol succinate) is commercially available under the name "HAIAQUEOUSTERDCS" (manufactured by Higher Alcohol Industry Co., Ltd.).

[0015] (A) The diester compound may be a diester of a dicarboxylic acid and a polyoxyethylene monoalkyl ether.

[0016] (A) Diester compounds are Dicarboxylic acids represented by the following formula (a-1): HOOC-R-COOH (a-1) (wherein R is as defined above), and Polyoxyethylene monoalkyl ethers represented by the following formulas (a-2) and (a-3): R 1 -(OCH2CH2)m-OH (a-2) and HO-(CH2CH2O)nR 2 (a-3) (In the formula, R 1 and R 2 , as well as m and n, are defined as above. It may also be a diester.

[0017] Examples of dicarboxylic acids represented by formula (a-1) include: saturated linear dicarboxylic acids, e.g., succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and 1,10-dodecanedicarboxylic acid; saturated branched dicarboxylic acids, e.g., 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid; and saturated or unsaturated cyclic dicarboxylic acids, e.g., 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid. Saturated linear dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and 1,10-dodecanedicarboxylic acid, and saturated or unsaturated cyclic dicarboxylic acids, such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred. Succinic acid, adipic acid, and 1,4-cyclohexanedicarboxylic acid are more preferred, and 1,4-cyclohexanedicarboxylic acid is even more preferred.

[0018] The dicarboxylic acid represented by formula (a-1) may also be in the form of an acid anhydride.

[0019] Examples of polyoxyethylene monoalkyl ethers represented by formulas (a-2) and (a-3) include: diethylene glycol monoethyl ether and triethylene glycol monoethyl ether. Diethylene glycol monoethyl ether is preferred among these.

[0020] (A) Diester compounds can be prepared by reacting a dicarboxylic acid represented by formula (a-1) with polyoxyethylene monoalkyl ethers represented by formulas (a-2) and (a-3).

[0021] The reaction process described above is not limited and can be carried out according to known esterification methods. For example, the dicarboxylic acid represented by formula (a-1) and the polyoxyethylene monoalkyl ethers represented by formulas (a-2) and (a-3) can be reacted with or without a solvent at a temperature of, for example, 100 to 300°C, preferably 150 to 260°C. The molar ratio of the dicarboxylic acid represented by formula (a-1) to the polyoxyethylene monoalkyl ethers represented by formulas (a-2) and (a-3) may vary depending on the reaction conditions, but may be 0.1 to 1, preferably 0.2 to 0.8, more preferably 0.3 to 0.6, and even more preferably about 0.5. As a solvent, organic solvents such as toluene and heptane can be used. A catalyst may be used to accelerate the esterification reaction. As a catalyst, acid catalysts such as p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, and methanesulfonic acid can be used. If necessary, the (A) diester compound obtained by the above esterification reaction may be purified according to known purification methods. (A) The diester compound preferably has a purity of 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more.

[0022] The amount of component (A) incorporated into the topical skin preparation of the present invention is in the range of 0.01 to 15% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass, based on the total amount of the topical skin preparation.

[0023] The (B) polyoxypropylene diglyceryl ether used in the present invention is not particularly limited, and commercially available products can be used. Examples of commercially available products include SY-DP4, SY-DP9, SY-DP14T (all manufactured by Sakamoto Pharmaceutical Co., Ltd.), Unilube DGP-700, DGP-950 (manufactured by NOF Corporation), and the like.

[0024] The amount of component (B) incorporated into the topical skin preparation of the present invention is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, relative to the total amount of the topical skin preparation.

[0025] The divalent carboxylic acid used in the (C) divalent carboxylic acid and the oligomer ester composed of polyglycerin with an average degree of polymerization of 2 to 15 is not particularly limited as long as it is a divalent carboxylic acid containing a linear, branched, or cyclic structure. However, from the viewpoint of ease of synthesis and improvement of moisturizing effect, the number of carbon atoms in the divalent carboxylic acid is preferably 2 or more, more preferably 8 or more, even more preferably 12 or more, even more preferably 14 or more, preferably 26 or less, more preferably 24 or less, even more preferably 22 or less, and even more preferably 20 or less. Also, from a similar viewpoint, aliphatic divalent carboxylic acids are preferred. Examples of dicarboxylic acids having 2 to 26 carbon atoms include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 2,4-diethylpentanedioic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, octadecanediic acid, 8-ethyloctadecanediic acid, eicosanedioic acid, dimethyleicosanedioic acid, and cyclohexanedicarboxylic acid. These dicarboxylic acids can be used individually or in appropriate combinations of two or more.

[0026] Of these dicarboxylic acids, linear or branched dicarboxylic acids having 14 to 22 carbon atoms are preferred, and linear dicarboxylic acids having 14 to 20 carbon atoms are more preferred. Specifically, one or more selected from tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, 8-ethyloctadecanedioic acid, eicosanedioic acid, and dimethyleicosanedioic acid are preferred, and one or more selected from tetradecanedioic acid and eicosanedioic acid are more preferred.

[0027] Furthermore, as the polyglycerin that forms esters with divalent carboxylic acids, polyglycerin with an average degree of polymerization of 2 to 15, calculated from the hydroxyl value, is used. The average degree of polymerization of the polyglycerin is preferably 8 or higher, more preferably 9 or higher, and also preferably 15 or lower, more preferably 12 or lower, from the viewpoint of good solubility with aqueous components. Among these, polyglycerin containing an average degree of polymerization of 10 is preferred.

[0028] A method for producing an oligomeric ester of a divalent carboxylic acid and polyglycerin is described in Japanese Patent Publication No. 2007-137847. The degree of polymerization of the oligomeric ester of the present invention can be adjusted by the charging ratio of divalent carboxylic acid and polyglycerin. From the viewpoint of preventing the viscosity of the oligomeric ester from being too high and suppressing stickiness, the amount of divalent carboxylic acid per 1 molar equivalent of polyglycerin is preferably 0.3 molar equivalents or more, more preferably 0.7 molar equivalents or more, and also preferably 1.5 molar equivalents or less, more preferably 1.2 molar equivalents or less.

[0029] A preferred example of these oligomeric esters is (eicosanedioic acid / tetradecanedioic acid) decaglyceryl solution, which is an oligomeric ester composed of tetradecanedioic acid and / or eicosanedioic acid and polyglycerin with an average degree of polymerization of 10. Commercially available oligomeric esters can also be used, such as Neosolue-Aqua and Neosolue-AquaS (both manufactured by Nippon Seika Co., Ltd.).

[0030] The amount of component (C) in the topical skin preparation of the present invention is preferably 0.008 to 6% by mass, and more preferably 0.02 to 4% by mass, relative to the total amount of the topical skin preparation.

[0031] In addition to the components described above, the topical skin preparation of the present invention may contain optional components commonly used in cosmetics and quasi-drugs, to an extent that does not impair the effects of the present invention. Specifically, these may include oils, surfactants, thickeners, preservatives, fragrances, moisturizers, antioxidants, anti-inflammatory agents, antibacterial agents, and the like.

[0032] The dosage form of the topical skin preparation of the present invention is not particularly limited and may be any dosage form such as aqueous, oil-based, or emulsion type.

[0033] The topical skin preparation of the present invention can be prepared by conventional methods.

[0034] The topical skin preparation of the present invention can be used in the form of, for example, a lotion, emulsion, or ointment. [Examples]

[0035] The present invention will be specifically described below with reference to examples, but this will not limit the scope of the present invention. Unless otherwise specified, the amounts are given in mass percent.

[0036] [Method for testing moisturizing effect] The samples shown in Table 1 were prepared, and the water content of the stratum corneum and transepidermal water loss were measured.

[0037] [Measurement method] (1) Acclimation After washing the inner side of both forearms, the subjects dried them and rested for 15 minutes in a room adjusted to a temperature of 21±0.5℃ and humidity of 50±5% to allow for acclimatization. (2) Application A 3cm x 3cm area was marked on the inner side of both forearms, and 9 μL of the solution was dropped onto each area using a pipette and evenly spread with a finger wearing a finger cot. (3) Measurement The moisture content of the stratum corneum of the skin surface was measured using a SKICON-200EX before application, 15 minutes after application, and 1 hour after application, and transepidermal water loss was measured using a vaporometer. Relative values ​​for stratum corneum moisture content and transepidermal water loss were calculated with the pre-application value set to 1, and are shown in Table 1. Since stratum corneum moisture content and transepidermal water loss are easily affected by temperature, humidity, etc. on the day of measurement, all samples in a group were evaluated on the same day, and the pre-application measurement was also based on the measurement value at the application site of the sample as the relative value standard.

[0038] [Table 1]

[0039] As shown in Table 1, compared to Comparative Examples 1-3, which used each component individually, Example 1 showed a synergistic improvement in moisture content and a synergistic decrease in transepidermal water loss, even though each component was used in only one-third the amount. Therefore, the topical skin preparation of the present invention exhibited a synergistic effect of improving moisturizing properties.

[0040] [Example 2] Cream (1) Squalane 10.0 (mass%) (2) Stearic acid 2.0 (3) Hydrogenated palm kernel oil 0.5 (4) Hydrogenated soybean phospholipid 0.1 (5) Cetanol 3.6 (6) Lipophilic glyceryl monostearate 2.0 (7) Glycerin 10.0 (8) Phenoxyethanol 0.2 (9) Arginine (20% by mass aqueous solution) 15.0 (10) Cyclohexanedicarboxylic acid bisethoxydiglycol 0.5 (11) Polyoxypropylene diglyceryl ether 2.5 (12) Decaglyceryl (eicosanedioic acid / tetradecanediic acid) solution 1.0 (13) Purified water Amount to make up the total volume 100 (14) Carboxyvinyl polymer (1% by mass aqueous solution) 15.0

[0041] [Example 3] Emulsion (1) Squalane 10.0 (mass%) (2) Methylphenylpolysiloxane 4.0 (3) Hydrogenated palm kernel oil 0.5 (4) Hydrogenated soybean phospholipid 0.1 (5) Polyoxyethylene monostearate Sorbitan (20 E.O.) 1.3 (6) Sorbitan monostearate 1.0 (7) Glycerin 4.0 (8) Phenoxyethanol 0.2 (9) Carboxyvinyl polymer (1% by mass aqueous solution) 0.15 (10) Cyclohexanedicarboxylic acid bisethoxydiglycol 1.0 (11) Polyoxypropylene diglyceryl ether 2.5 (12) Decaglyceryl (eicosanedioic acid / tetradecanediic acid) solution 1.5 (13) Purified water Amount to make up the total volume 100 (14) L-arginine (1% by mass aqueous solution) 20.0

[0042] [Example 4] Lotion (1) Ethanol 15.0 (mass%) (2) Polyoxyethylene (40 E.O.) hydrogenated castor oil 0.3 (3)Fragrance 0.1 (4) Purified water Amount when the total volume is 100 (5) Citric acid 0.02 (6) Sodium citrate 0.1 (7) Glycerin 1.0 (8) Hydroxyethylcellulose 0.1 (9) Cyclohexanedicarboxylic acid bisethoxydiglycol 1.5 (10) Polyoxypropylene diglyceryl ether 1.5 (11) Decaglyceryl (eicosanedioic acid / tetradecanediic acid) solution 2.0

[0043] [Example 5] Serum (1) Purified water Amount (mass %) of the total amount, with the total amount being 100 (2) Glycerin 10.0 (3) Sucrose fatty acid ester 1.3 (4) Carboxyvinyl polymer (1% by mass aqueous solution) 17.5 (5) Sodium alginate (1% by mass aqueous solution) 15.0 (6) Polyglyceryl monolaurate 1.0 (7) Cyclohexanedicarboxylic acid bisethoxydiglycol 0.3 (8) Polyoxypropylene diglyceryl ether 0.7 (9) Decaglyceryl (eicosanedioic acid / tetradecanediic acid) solution 0.3 (10) Macadamia nut oil fatty acid phytosteryl 3.0 (11) N-lauroyl-L-glutamic acid Di(phytosteryl-2-octyldodecyl) 2.0 (12) Hydrogenated palm oil 2.0 (13) Squalane (derived from olive) 1.0 (14) Behenyl alcohol 0.75 (15) Beeswax 1.0 (16) Jojoba oil 1.0 (17) 1,3-Butylene glycol 10.0 (18) L-arginine (10% by mass aqueous solution) 2.0

[0044] [Example 6] Water-based gel (1) Carboxyvinyl polymer (1% by mass aqueous solution) 0.5% by mass (2) Purified water Amount to make up 100 of the total volume (3) Sodium hydroxide (10% by mass aqueous solution) 0.5 (4) Phenoxyethanol 0.2 (5) Cyclohexanedicarboxylic acid bisethoxydiglycol 0.7 (6) Polyoxypropylene diglyceryl ether 1.8 (7) Decaglyceryl (eicosanedioic acid / tetradecanediic acid) solution 0.3 (8)Fragrance 0.1 (9) Polyoxyethylene (60 E.O.) hydrogenated castor oil 0.1

Claims

[Claim 1] A topical skin preparation containing the following (A) to (C). (A) The following formula (a) R １ -(OCH ２ CH ２ ) ｍ -OOC-R-COO-(CH ２ CH ２ O) ｎ -R ２ (a) (wherein, R １ and R ２ each independently represents a saturated or unsaturated, linear, branched or cyclic monovalent C1-C12 hydrocarbon group; R represents a saturated or unsaturated, linear, branched, or cyclic, divalent C1 to C12 hydrocarbon group; m and n independently represent integers from 1 to 20, preferably from 1 to 15, and more preferably from 2 to 11. at least one diester compound represented by (B) PPG-14 polyglyceryl-2 ether and tocopherol (C) Oligomer ester composed of a divalent carboxylic acid and polyglycerin with an average degree of polymerization of 2 to 15.

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