Cosmetic raw materials and cosmetics containing said cosmetic raw materials

Abstract

To provide cosmetic ingredients that have excellent hyaluronic acid production promoting effects, are stable even during long-term storage, and exhibit little discoloration, odor change, or decrease in activity, as well as cosmetics containing such ingredients. [Solution] Cosmetic raw materials in which hydrogen atoms on the hydroxyl group, carboxyl group, or sulfonyl group of sugars, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, or sulfonic acids are substituted with a structure represented by general formula (I) or (II), and cosmetics containing such cosmetic raw materials. TIFF2026120932000057.tif3086 TIFF2026120932000058.tif2888

Description

[Technical Field]

[0001] The present invention relates to a cosmetic ingredient having an anti-wrinkle effect and a cosmetic product containing the cosmetic ingredient. [Background technology]

[0002] The formation of wrinkles associated with aging significantly impacts perceived age. Preventing or improving wrinkle formation is crucial for maintaining a youthful appearance. Furthermore, while shallow wrinkles are formed by epidermal dryness, deep wrinkles are primarily formed by a decrease in extracellular matrix (ECM) such as hyaluronic acid and collagen in the dermis (Non-Patent Literature 1). Therefore, improving the decrease in hyaluronic acid in the dermis is a useful method for preventing or improving the formation of deep wrinkles.

[0003] Therefore, numerous studies have been conducted on cosmetic ingredients that promote hyaluronic acid production in the dermis. However, cosmetic ingredients derived from plant extracts have been unsatisfactory due to the high number of impurities inherent in natural products and the large variation in effectiveness between batches, while cosmetic ingredients derived from synthetic active ingredients have problems with manufacturing costs, stability, and formulation. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] McCabe MC, Hill RC, Calderone K, Cui Y, Yan Y, Quan T, Fisher GJ, Hansen KC (2020)Alterations in extracellular matrix composition during aging and photoaging of the skin. Matrix Biol Plus. 8:100041. [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a cosmetic ingredient that has an excellent hyaluronic acid production promoting effect and also has high stability over time, as well as a cosmetic product containing the cosmetic ingredient. [Means for solving the problem]

[0006] In view of the above circumstances, the present inventors conducted diligent research and found that cosmetic ingredients in which hydrogen atoms on the hydroxyl group, carboxyl group, or sulfonyl group of sugars, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, or sulfonic acids are substituted with functional groups represented by the following general formulas (I) or (II) exhibit excellent hyaluronic acid production promoting effects and high stability. The present invention was completed based on these findings.

[0007] The first aspect of the present invention provides a cosmetic ingredient characterized in which a hydrogen atom on the hydroxyl group, carboxyl group, or sulfonyl group of a sugar, polyhydric alcohol or its derivative, hydroxy acid, unsaturated carboxylic acid, or sulfonic acid is substituted with a functional group represented by the following general formula (I) or (II).

[0008] [ka]

[0009] [ka] [In formulas (I) and (II), * indicates the bonding site between a hydrogen atom on a hydroxyl group, carboxyl group, or sulfonyl group and the oxygen atom to which it is bonded.]

[0010] Cosmetic ingredients characterized by the substitution of sugars, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, and sulfonic acids with the functional group represented by the above general formula (I) or (II) have superior hyaluronic acid production promoting effects and high long-term stability compared to conventional sugars, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, and sulfonic acids.

[0011] In particular, sugars consisting of glucose and maltose, xylitol, inositol, methylglycerin, glyceryl laurate, glyceryl stearylate, diglyceryl stearate, diglyceryl isostearate, diglyceryl diisostearate, ethyl ethylene glycol, polyhydric alcohols or derivatives thereof consisting of 1-proxy-2-propanol, hydroxy acids consisting of malic acid, mandelic acid, and salicylic acid, unsaturated carboxylic acids consisting of cinnamic acid, sorbic acid, crotonic acid, and fumaric acid, 1-naphthol-4-sulfonic acid, and 2-naphthol-6-sulfonic acid are preferred because they have a superior hyaluronic acid production promoting effect. Claim 2 corresponds to this particularly preferred embodiment.

[0012] The cosmetic ingredient of the present invention can be incorporated into cosmetics. Cosmetics containing the cosmetic ingredient of the present invention have a superior hyaluronic acid production promoting effect compared to conventional cosmetics containing sugars, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, and sulfonic acids, and consequently exhibit a superior anti-wrinkle effect (Claim 3). [Effects of the Invention]

[0013] The present invention provides a cosmetic ingredient characterized in which hydrogen atoms on the hydroxyl group, carboxyl group, or sulfonyl group of sugars, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, or sulfonic acids are substituted with a structure represented by the above general formula (I) or (II). Compared to the group of unsubstituted compounds, this cosmetic ingredient exhibits superior hyaluronic acid production promoting effects and high long-term stability. Therefore, by incorporating this cosmetic ingredient into cosmetics, it is possible to obtain cosmetics with excellent anti-wrinkle effects. [Modes for carrying out the invention]

[0014] The following are embodiments for carrying out the present invention, but the scope of the present invention is not limited to the embodiments shown below.

[0015] (Sugars) Examples of starting materials for the cosmetic ingredients of the present invention include monosaccharides, disaccharides, trisaccharides, and oligosaccharides. Examples of monosaccharides include glucose, fructose, galactose, xylose, allose, talose, altrose, rhoz, mannose, xylose, arabinose, lyxose, ribose, threose, erythrose, psicose, tagatose, sorbose, ribulose, xylulose, and erythrolose. Examples of disaccharides include lactose, trehalose, maltose, sucrose, cellobiose, lactulose, isomaltose, sophorose, turanose, maltulose, palatinose, mannobiose, melibiose, bicyanose, and xylobiose. Examples of trisaccharides include maltotriose, melegitose, and raffinose. Examples of other oligosaccharides include stachyose, amylose, cellulose, and agarose. In particular, glucose and maltose are desirable because they yield cosmetic ingredients with excellent hyaluronic acid production-promoting effects. Furthermore, any of the above monosaccharides, whether D-form, L-form, or DL-form, are included within the scope of the present invention.

[0016] (Polyhydric alcohols or their derivatives) As the polyhydric alcohol which is the starting material of the cosmetic raw material of the present invention, glycerin, xylitol, sorbitol, inositol, ketotriose, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,2-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 1,3-propanediol, pentaerythritol, methyl glycerin, 2-ethylhexyl glycerin, alkyl glycerins such as octadecyl glycerin, diglycerin, glycerin laurate, glycerin stearate, diglycerin stearate, diglycerin isostearate, diisostearate diglycerin, etc. mono- or polyglycerol fatty acid esters, Examples of polyhydric alcohol derivatives include ethyl ethylene glycol, 1-propoxy-2-propanol, 2-hexyloyl ethanol, and the like. Among them, xylitol, inositol, methyl glycerin, glycerin laurate, glycerin stearate, diglycerin stearate, diglycerin isostearate, diisostearate diglycerin, ethyl ethylene glycol, 1-propoxy-2-propanol are desirable because a cosmetic raw material having an excellent hyaluronic acid production promoting effect can be obtained.

[0017] (Hydroxy acid) As the hydroxy acid which is the starting material of the cosmetic raw material of the present invention, glycolic acid, lactic acid, 2-hydroxybutyric acid, 2-hydroxy-4-pentanoic acid, 3-hydroxypropionic acid, glyceric acid, tartronic acid, malic acid, tartaric acid, citric acid, mandelic acid, salicylic acid, etc. can be mentioned. Among them, malic acid, mandelic acid, salicylic acid are desirable because a cosmetic raw material having an excellent hyaluronic acid production promoting effect can be obtained.

[0018] (Unsaturated carboxylic acid) Examples of the unsaturated carboxylic acid which is the starting material of the cosmetic raw material of the present invention include acrylic acid, crotonic acid, 3-butenoic acid, methacrylic acid, tiglic acid, 4-pentenoic acid, 2-ethyl-2-butenoic acid, 10-undecenoic acid, oleic acid, 2,4-hexadienoic acid, propiolic acid, 2-butynoic acid, maleic acid, fumaric acid, mesaconic acid, 2-pentenedioic acid, caffeic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid and the like. Among them, caffeic acid, sorbic acid, crotonic acid and fumaric acid are desirable because a cosmetic raw material having an excellent hyaluronic acid production promoting effect can be obtained.

[0019] (Sulfonic acid) Examples of the sulfonic acid which is the starting material of the cosmetic raw material of the present invention include methanesulfonic acid, benzenesulfonic acid, tosylic acid, 10-camphorsulfonic acid, taurine, 1-naphthol-4-sulfonic acid, 2-naphthol-6-sulfonic acid and the like. Among them, 1-naphthol-4-sulfonic acid and 2-naphthol-6-sulfonic acid are desirable because a cosmetic raw material having an excellent hyaluronic acid production promoting effect can be obtained.

[0020] Hereinafter, the functional group represented by the general formula (I) or (II) is referred to as a "hydroxyisobutyl group".

[0021] The cosmetic raw material of the present invention, wherein the hydrogen atom on the hydroxyl group, carboxyl group or sulfonyl group of saccharides, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, sulfonic acids is substituted with the structure represented by the general formula (I) or (II) can be produced by various methods. For example, by reacting isobutylene oxide or halogenated tert-butyl alcohol with saccharides, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, sulfonic acids, a hydroxyisobutyl group can be introduced to the oxygen atom to which the hydrogen atom on the hydroxyl group, carboxyl group or sulfonyl group is bonded.

[0022] <0Examples of compounds into which the hydroxyisobutyl group of the present invention is introduced include, but are not limited to, isobutylene oxide or halogenated tert-butyl alcohol. Examples of halogenated tert-butyl alcohols include fluorinated tert-butyl alcohol, chloride tert-butyl alcohol, and bromide tert-butyl alcohol.

[0023] In the reaction of the aforementioned starting material with isobutylene oxide, depending on the reaction conditions, a mixture may be produced in which hydrogen atoms on the hydroxyl group, carboxyl group, or sulfonyl group are substituted with the structure represented by general formula (I) and the structure represented by general formula (II).

[0024] There are no particular restrictions on the amount of isobutylene oxide or halogenated tert-butyl alcohol used in the present invention, but for sugars, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, and sulfonic acids, the range is preferably 1.0 to 2.0 moles; for hydroxy acids, the range is preferably 1.0 to 3.0 moles; and for unsaturated carboxylic acids, the range is preferably 0.5 to 2.0 moles.

[0025] The reaction of the present invention can be carried out in various solvents. Examples of solvents include water, methanol, ethanol, isopropanol and other lower alcohols, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), dioxane, tetrahydrofuran (THF), N-methylpyrrolidone, or mixtures thereof, and there are no particular limitations.

[0026] The reaction temperature is not particularly limited, but it is preferably in the range of 30 to 50°C for sugars and sulfonic acids, preferably in the range of 30 to 90°C for polyhydric alcohols or their derivatives, preferably in the range of 60 to 90°C for hydroxy acids, and preferably in the range of 20 to 70°C for unsaturated carboxylic acids.

[0027] There are no particular restrictions on the pH of the reaction solvent, but for sugars, a pH range of 8 to 10 is preferred; for polyhydric alcohols or their derivatives, a pH range of 8 to 12 is preferred; for hydroxy acids, a pH range of 8 to 13 is preferred; for unsaturated carboxylic acids, a pH range of 4 to 6 is preferred; and for sulfonic acids, a pH range of 9 to 13 is preferred.

[0028] Examples of pH adjusting agents used during the reaction include hydrochloric acid, sulfuric acid, nitric acid, lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, malic acid, gluconic acid, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, potassium tert-butoxide, and triethylamine.

[0029] The cosmetic raw materials of the present invention, manufactured as described above, can be purified by means of column chromatography using silica gel, column chromatography using resins such as ion exchange resins, activated carbon treatment, extraction, distillation, crystallization, and other methods.

[0030] Specific examples of compounds substituted with a hydroxyisobutyl group include the following compounds, but the scope of the present invention is not limited to those listed below.

[0031] (1) Sugars 1-O-(2-hydroxyisobutyl)D-glucose, 1-O-(2-hydroxyisobutyl)D-galactose, 1-O-(2-hydroxyisobutyl)D-xylose, 1-O-heptyl-6-O-(2-hydroxyisobutyl)D-glucose, 1-O-hexadecyl-6-O-(2-hydroxyisobutyl)D-glucose, 1-O-(2-hydroxyisobutyl)D-maltose.

[0032] (2) Polyhydric alcohols or their derivatives 1-O-(2-hydroxyisobutyl)glycerin, 1-O-(2-hydroxyisobutyl)xylitol, 1-O-(2-hydroxyisobutyl)sorbitol, 1-O-(2-hydroxyisobutyl)inositol, 1-O-(2-hydroxyisobutyl)-3-O-methylglycerin, 1-O-(2-hydroxyisobutyl)-3-O-(2-ethylhexyl)glycerin, 1-O-(2-hydroxyisobutyl)-3-O-octadecylglycerin, 1-O-(2-hydroxyisobutyl)-3-O-lauroylglycerin, 1-O-(2-hydroxyisobutyl) (Droxyisobutyl)-3-O-stearoylglycerin, 1-O-(2-hydroxyisobutyl)diglycerin, 1-O-(2-hydroxyisobutyl)stearate diglycerin, 1-O-(2-hydroxyisobutyl)isostearate diglycerin, 1-O-(2-hydroxyisobutyl)diisostearate diglycerin, 1-O-(2-hydroxyisobutyl)-2-ethoxyethanol, 1-O-(2-hydroxyisobutyl)-2-hexyloylethanol, 1-propoxy-2-O-(2-hydroxyisobutyl)-2-propanol.

[0033] (3) Hydroxy acids 1-(2-hydroxyisobutyl) malate, 2-hydroxyisobutyl mandelate, 2-(2-hydroxyisobutyl) 2-hydroxy-1,2,3-tricarboxylic acid, 2-hydroxyisobutyl salicylate, 2-hydroxyisobutyl salicylate.

[0034] (4) Unsaturated carboxylic acids 2-hydroxyisobutyl sorbate, 2-hydroxyisobutyl cinnamate, 2-hydroxyisobutyl crotonic acid, 2-hydroxyisobutyl fumarate, 2-hydroxyisobutyl ferulate.

[0035] (5) Sulfonic acid 1-Naphthol-4-sulfonic acid 2-hydroxyisobutyl ester, 2-Naphthol-6-sulfonic acid 2-hydroxyisobutyl ester.

[0036] Among them, 1-O-(2-hydroxyisobutyl)D-glucose, 1-O-(2-hydroxyisobutyl)D-maltose, 1-O-(2-hydroxyisobutyl)xylitol, 1-O-(2-hydroxyisobutyl)inositol, 1-O-(2-hydroxyisobutyl)-3-O-methylglycerin, 1-O-(2-hydroxyisobutyl)-3-O-lauroylglycerin, 1-O-(2-hydroxyisobutyl)-3-O-stearoylglycerin, 1-O-(2-hydroxyisobutyl)diglyceryl stearate, 1-O-(2-hydroxyisobutyl)diglyceryl isostearate, 1-O-(2-hydroxyisobutyl)diisostearate, 1-O-(2-hydroxyisobutyl)-2-ethoxyethanol, 1-propoxy-2-O-(2-hydroxyisobutyl)- 2-propanol, 1-(2-hydroxyisobutyl) malate, 2-hydroxyisobutyl mandelate, 2-hydroxyisobutyl salicylate, 2-hydroxyisobutyl salicylate ether, 2-hydroxyisobutyl sorbate, 2-hydroxyisobutyl cinnamate, 2-hydroxyisobutyl crotonic acid, 2-hydroxyisobutyl fumarate, 2-hydroxyisobutyl 1-naphthol-4-sulfonic acid, and 2-hydroxyisobutyl 2-naphthol-6-sulfonic acid are preferred because they have an excellent hyaluronic acid production promoting effect, with 2-hydroxyisobutyl salicylate, 2-hydroxyisobutyl cinnamate, and 2-hydroxyisobutyl 1-naphthol-4-sulfonic acid being particularly preferred.

[0037] The cosmetic raw materials of the present invention also include salts. These salts are formed from carboxyl groups or sulfonyl groups of hydroxy acids, unsaturated carboxylic acids, or sulfonic acids. Specifically, examples include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, ammonium salts, triethanolamine salts, diethanolamine salts, monoethanolamine salts, 2-amino-2-methyl-1,3-propanediol salts, 2-amino-2-methyl-1-propanolamine salts, fatty acid amidoamine salts, and the like.

[0038] The cosmetic raw material of the present invention is suitably used as an ingredient in various cosmetics, such as topical skin preparations and hair cosmetics.

[0039] When incorporating the cosmetic raw material of the present invention into various cosmetics, the amount to be incorporated is preferably 1% to 20% by weight, and particularly preferably in the range of 3% to 10% by weight. If the amount is less than 1% by weight, the hyaluronic acid production promoting effect is often not sufficiently demonstrated, while if it exceeds 20% by weight, the effect commensurate with the amount incorporated is often not expected, and there is a risk of disrupting the formulation system.

[0040] In addition to the essential components, the cosmetics of the present invention may appropriately contain other commonly used ingredients, such as oily raw materials, surfactants, humectants, polymer compounds, antioxidants, whitening agents, pharmaceuticals, UV absorbers, metal ion chelating agents, proteins, protein hydrolysates or derivatives thereof, amino acids or derivatives thereof, pH adjusters, preservatives, and the like.

[0041] Examples of oily raw materials, surfactants, humectants, polymer compounds, antioxidants, whitening agents, other drugs, UV absorbers, metal ion chelating agents, proteins, protein hydrolysates or their derivatives, amino acids or their derivatives, pH adjusters, preservatives, etc., are similar to those listed in Publication WO2022 / 080287.

[0042] The formulation system of the cosmetic product of the present invention is arbitrary and can be any of the following: solution system, solubilization system, emulsion system, gel system, powder dispersion system, water-oil bilayer system, etc. The cosmetic raw materials of the present invention can be blended and manufactured according to the target product. [Examples]

[0043] Next, specific embodiments for carrying out the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited by these examples. Prior to the examples, an example of the production of the cosmetic raw material of the present invention is shown as a synthesis example.

[0044] Synthesis Example 1: Synthesis of 1-O-(2-hydroxyisobutyl)D-glucose D-glucose (0.90 g), sodium hydroxide (0.10 g), and deionized water (1.0 ml) were added to a round-bottom flask and stirred. Then, isobutylene oxide (0.54 g) was added and the mixture was stirred at 40°C for 5 hours. After the reaction was complete, ethanol (10 ml) was added and neutralization was carried out with 17% hydrochloric acid. The mixture was then concentrated under reduced pressure, and the resulting residue (1.30 g) was subjected to silica gel chromatography. Elution was performed with a mixture of chloroform / methanol / deionized water = 10 / 3 / 0.3, and the mixture was concentrated under reduced pressure to obtain the product shown in the following structural formula (0.15 g).

[0045] The obtained product was subjected to mass spectrometry. 1 H-NMR, 13 1C-NMR measurements were performed, and the results confirmed that the product is 1-O-(2-hydroxyisobutyl)D-glucose, represented by the following structural formula.

[0046] [ka]

[0047] Furthermore, in the synthesis examples shown below, the obtained products were subjected to mass spectrometry. 1 H-NMR, and 13¹¹C-NMR measurements were performed, and the results confirmed that each product is the compound represented by the structural formula and compound name shown in each synthesis example. Mass spectrometry was performed on the products obtained in the synthesis examples. 1 H-NMR and 13 The results of the 1C-NMR measurements are shown in Tables 1-7.

[0048] Synthesis Example 2: Synthesis of 1-O-(2-hydroxyisobutyl)D-galactose 1-O-(2-hydroxyisobutyl)D-galactose (0.11g), shown in the structural formula below, was obtained using the same method as in Synthesis Example 1, except that D-galactose (0.90g) was used instead of D-glucose.

[0049] [ka]

[0050] Synthesis Example 3: Synthesis of 1-O-(2-hydroxyisobutyl)D-xylose 1-O-(2-hydroxyisobutyl)D-xylose (0.18g), shown in the structural formula below, was obtained by the same method as in Synthesis Example 1, except that D-xylose (0.75g) was used instead of D-glucose.

[0051] [ka]

[0052] Synthesis Example 4: Synthesis of 1-O-heptyl-6-O-(2-hydroxyisobutyl)D-glucose 1-O-heptyl-6-O-(2-hydroxyisobutyl)D-glucose (0.05 g), shown in the structural formula below, was obtained using the same method as in Synthesis Example 1, except that 1-O-heptyl D-glucose (1.39 g) was used instead of D-glucose.

[0053] [ka]

[0054] Synthesis Example 5: Synthesis of 1-O-Hexadecyl-6-O-(2-hydroxyisobutyl)D-glucose 1-O-hexadecyl-6-O-(2-hydroxyisobutyl)D-glucose (0.12 g), shown in the structural formula below, was obtained by the same method as in Synthesis Example 1, except that 1-O-hexadecyl D-glucose (2.02 g) was used instead of D-glucose.

[0055] [ka]

[0056] Synthesis Example 6: Synthesis of 1-O-(2-hydroxyisobutyl)D-maltose 1-O-(2-hydroxyisobutyl)D-maltose (0.17g), shown in the structural formula below, was obtained using the same method as in Synthesis Example 1, except that D-maltose (1.71g) was used instead of D-glucose.

[0057] [ka]

[0058] Synthesis Example 7: Synthesis of 1-O-(2-hydroxyisobutyl)glycerin Glycerin (1.84 g), sodium hydroxide (0.16 g), and deionized water (2.0 ml) were added to a round-bottom flask and stirred. Then, isobutylene oxide (1.73 g) was added and the mixture was stirred at 40°C for 3 hours. After the reaction was complete, deionized water (20 ml) was added, followed by neutralization with 17% hydrochloric acid, and then the mixture was concentrated under reduced pressure. The resulting residue (2.41 g) was subjected to silica gel chromatography, eluted with a chloroform / methanol = 5 / 1 mixture, and concentrated under reduced pressure to obtain 1-O-(2-hydroxyisobutyl)glycerin (0.57 g), which is shown in the structural formula below.

[0059] [ka]

[0060] Synthesis Example 8: Synthesis of 1-O-(2-hydroxyisobutyl)xylitol 1-O-(2-hydroxyisobutyl)xylitol (0.35g), shown in the structural formula below, was obtained by the same method as in Synthesis Example 7, except that xylitol (3.04g) was used instead of glycerin.

[0061] [ka]

[0062] Synthesis Example 9: Synthesis of 1-O-(2-hydroxyisobutyl)sorbitol Except for using sorbitol (3.04 g) instead of glycerin, 1-O-(2-hydroxyisobutyl)sorbitol (1.72 g), shown in the structural formula below, was obtained by the same method as in Synthesis Example 7.

[0063] [ka]

[0064] Synthesis Example 10: Synthesis of 1-O-(2-hydroxyisobutyl)inositol 1-O-(2-hydroxyisobutyl)inositol (0.67g), shown in the structural formula below, was obtained by the same method as in Synthesis Example 7, except that inositol (3.04g) was used instead of glycerin.

[0065] [ka]

[0066] Synthesis Example 11: 1-O-(2-hydroxyisobutyl)-3-O-methylglycerin 3-O-methylglycerin (3.00 g), sodium hydroxide (0.56 g), deionized water (12 ml), and DMF (3.0 ml) were added to a round-bottom flask and stirred. Then, isobutylene oxide (2.02 g) was added and the mixture was stirred at 65°C for 16 hours. After the reaction was complete, the mixture was neutralized with 17% hydrochloric acid and then concentrated under reduced pressure. The resulting residue (5.57 g) was subjected to silica gel chromatography and eluted with a chloroform / methanol mixture of 50 / 1 to 25 / 1. The mixture was then concentrated under reduced pressure to obtain 1-O-(2-hydroxyisobutyl)-3-O-methylglycerin (0.56 g), which is shown in the structural formula below.

[0067] [ka]

[0068] Synthesis Example 12: Synthesis of 1-O-(2-hydroxyisobutyl)-3-O-(2-ethylhexyl)-glycerin 1-O-(2-hydroxyisobutyl)-3-O-(2-ethylhexyl)glycerin (2.30 g), represented by the following structural formula, was obtained by the same method as in Synthesis Example 11, except that 3-O-(2-ethylhexyl)glycerin (5.72 g) was used instead of 3-O-methylglycerin.

[0069] [ka]

[0070] Synthesis Example 13: Synthesis of 1-O-(2-hydroxyisobutyl)-3-O-octadecylglycerin Except for using 3-O-octadecylglycerin (9.65 g) instead of 3-O-methylglycerin, the same method as in Synthesis Example 11 was used to obtain 1-O-(2-hydroxyisobutyl)-3-O-octadecylglycerin (1.11 g), which is shown in the following structural formula.

[0071] [ka]

[0072] Synthesis Example 14: Synthesis of 1-O-(2-hydroxyisobutyl)-3-O-lauroylglycerin 3-O-lauroylglycerin (2.00 g), potassium tert-butoxide (0.25 g), and DMSO (6.0 ml) were added to a round-bottom flask and stirred. Then, isobutylene oxide (0.63 g) was added and the mixture was stirred at 80°C for 16 hours. After the reaction was complete, deionized water and ethyl acetate were added and liquid-liquid extraction was performed. The ethyl acetate layer was collected and concentrated under reduced pressure. The resulting residue (1.81 g) was subjected to silica gel chromatography and eluted with a hexane / ethyl acetate / methanol = 4 / 2 / 0.1 mixture. The mixture was concentrated under reduced pressure to obtain 1-O-(2-hydroxyisobutyl)-3-O-lauroylglycerin (0.09 g), which is shown in the structural formula below.

[0073] [ka]

[0074] Synthesis Example 15: Synthesis of 1-O-(2-hydroxyisobutyl)-3-O-stearoylglycerin 1-O-(2-hydroxyisobutyl)-3-O-stearoylglycerin (0.27g), shown in the structural formula below, was obtained by the same method as in Synthesis Example 14, except that 3-O-stearoylglycerin (2.62g) was used instead of 3-O-lauroylglycerin.

[0075] [ka]

[0076] Synthesis Example 16: Synthesis of 1-O-(2-hydroxyisobutyl)diglycerin Diglycerin (16.6 g), sodium hydroxide (0.80 g), and deionized water (10 ml) were added to a round-bottom flask and stirred. Then, isobutylene oxide (8.65 g) was added and the mixture was stirred at 40°C for 3 hours. After the reaction was complete, the mixture was neutralized with 17% hydrochloric acid and then concentrated under reduced pressure. The resulting residue (23.1 g) was subjected to silica gel chromatography, eluted with a chloroform / methanol = 7 / 1 mixture, and concentrated under reduced pressure to obtain (2-hydroxyisobutyl)diglycerin (5.95 g).

[0077] [ka]

[0078] Synthesis Example 17: Synthesis of 1-O-(2-hydroxyisobutyl)stearate diglyceryl stearate 1-O-(2-hydroxyisobutyl)diglycerin (0.24 g) synthesized in Synthesis Example 16 was mixed with triethylamine (0.12 g) and tetrahydrofuran (1 ml) and stirred under 0°C. Then, stearate chloride (0.30 g) was added and stirred under 0°C for 3 hours. After the reaction was complete, deionized water and ethyl acetate were added and liquid-liquid extraction was performed. The ethyl acetate layer was recovered and concentrated under reduced pressure. The resulting residue (0.39 g) was subjected to silica gel chromatography and eluted with a chloroform / methanol = 100 / 0~15 / 1 mixture. The mixture was concentrated under reduced pressure to obtain 1-O-(2-hydroxyisobutyl)stearate diglycerin (0.25 g) shown in the structural formula below.

[0079] [ka]

[0080] Synthesis Example 18: Synthesis of 1-O-(2-hydroxyisobutyl)isostearate diglyceryl Except for using isostearate chloride (0.30 g) instead of stearate chloride, the same method as in Synthesis Example 17 was used to obtain 1-O-(2-hydroxyisobutyl)isostearate diglyceryl (0.22 g), which is shown in the structural formula below.

[0081] [ka]

[0082] Synthesis Example 19: Synthesis of 1-O-(2-hydroxyisobutyl)diisostearate diglyceryl Except for using isostearate chloride (0.60 g) and triethylamine (0.24 g) instead of stearate chloride, the same method as in Synthesis Example 17 was used to obtain 1-O-(2-hydroxyisobutyl)diisostearate diglyceryl (0.15 g), which is shown in the structural formula below.

[0083] [ka]

[0084] Synthesis Example 20: Synthesis of 1-O-(2-hydroxyisobutyl)-2-ethoxyethanol 2-ethoxyethanol (3.00 g), potassium tert-butoxide (1.86 g), DMSO (12 ml), and deionized water (2.0 ml) were added to a round-bottom flask and stirred. Then, isobutylene oxide (2.38 g) was added and the mixture was stirred at 75°C for 16 hours. After the reaction was complete, deionized water and ethyl acetate were added and liquid-liquid extraction was performed. The ethyl acetate layer was collected and concentrated under reduced pressure. The resulting residue (2.59 g) was subjected to silica gel chromatography and eluted with a hexane / ethyl acetate = 5 / 1 to 3 / 1 mixture. The mixture was concentrated under reduced pressure to obtain 1-O-(2-hydroxyisobutyl)-2-ethoxyethanol (0.56 g), which is shown in the structural formula below.

[0085] [ka]

[0086] Synthesis Example 21: Synthesis of 1-O-(2-hydroxyisobutyl)-2-hexyloylethanol 1-O-(2-hydroxyisobutyl)-2-hexyloylethanol (0.20 g), shown in the following structural formula, was obtained by the same method as in Synthesis Example 20, except that 2-hexyloylethanol (4.83 g) was used instead of 2-ethoxyethanol.

[0087] [ka]

[0088] Synthesis Example 22: Synthesis of 1-propoxy-2-O-(2-hydroxyisobutyl)-2-propanol 1-propoxy-2-O-(2-hydroxyisobutyl)-2-propanol (3.04 g), shown in the structural formula below, was obtained by the same method as in Synthesis Example 20, except that 1-propoxy-2-propanol (3.90 g) was used instead of 2-O-ethoxyethanol.

[0089] [ka]

[0090] Synthesis Example 23: Synthesis of 1-(2-hydroxyisobutyl) malate ester Malic acid (20.0 g), sodium bicarbonate (10.0 g), DMF (40 ml), and deionized water (60 ml) were added to a round-bottom flask and stirred. Then, isobutylene oxide (16.1 g) was added and the mixture was stirred at 80°C for 16 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. Isopropanol (300 ml) was added to the obtained residue (49.4 g), and the mixture was filtered. The filtrate was concentrated under reduced pressure. The obtained residue (20.3 g) was subjected to silica gel chromatography and eluted with a mixture of chloroform / methanol / deionized water = 7 / 3 / 0.5. The mixture was concentrated under reduced pressure to obtain 1-(2-hydroxyisobutyl) malic acid (10.1 g), which is shown in the structural formula below.

[0091] [ka]

[0092] Synthesis Example 24: Synthesis of 2-hydroxyisobutyl mandelate Except for using mandelic acid (22.7 g) instead of malic acid, the same method as in Synthesis Example 23 was used to obtain 2-hydroxyisobutyl mandelic acid (9.83 g), which is shown in the structural formula below.

[0093] [ka]

[0094] Synthesis Example 25: Synthesis of 2-(2-hydroxyisobutyl) ester of 2-hydroxy-1,2,3-tricarboxylic acid Except for using sodium 2-hydroxy-1,2,3-tricarboxylate (3.90 g) instead of malic acid and sodium bicarbonate, the 2-(2-hydroxyisobutyl) ester (1.18 g) of 2-hydroxy-1,2,3-tricarboxylate, shown in the structural formula below, was obtained by the same method as in Synthesis Example 23.

[0095] [ka]

[0096] Synthesis Example 26: Synthesis of 2-hydroxyisobutyl salicylate Sodium salicylate (0.80 g) and DMF (10 ml) were added to a round-bottom flask and stirred at 50°C. Then, isobutylene oxide (0.79 g) was added and stirred at 83°C for 7 hours. After the reaction was complete, deionized water and ethyl acetate were added and liquid-liquid extraction was performed. The ethyl acetate layer was recovered and concentrated under reduced pressure. The resulting residue (0.03 g) was subjected to silica gel chromatography and eluted with a hexane / ethyl acetate = 10 / 0 to 5 / 1 mixture. Concentration under reduced pressure was performed to obtain 2-hydroxyisobutyl salicylate (0.01 g), shown in the structural formula below.

[0097] [ka]

[0098] Synthesis Example 27: Synthesis of 2-hydroxyisobutyl salicylate Sodium salicylate (0.80 g), DMF (2 ml), deionized water (4 ml), sodium hydroxide (1.00 g), and 1-chloro-2-methyl-2-propanol (1.63 g) were added to a round-bottom flask, and the mixture was stirred at 70°C for 16 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. 17% hydrochloric acid was added to the resulting residue (3.70 g), followed by deionized water and ethyl acetate, and liquid-liquid extraction was performed. The ethyl acetate layer was recovered and concentrated under reduced pressure. The resulting residue (1.01 g) was subjected to silica gel chromatography, eluted with a hexane / ethyl acetate = 10 / 0~5 / 5 mixture, and concentrated under reduced pressure to obtain 2-hydroxyisobutyl salicylate (0.63 g), shown in the structural formula below.

[0099] [ka]

[0100] Synthesis Example 28: Synthesis of 2-hydroxyisobutyl sorbate Sorbic acid (3.00 g), sodium bicarbonate (1.13 g), and DMF (6.0 ml) were added to a round-bottom flask and stirred. Then, isobutylene oxide (2.89 g) was added and the mixture was stirred at 60°C for 16 hours. After the reaction was complete, deionized water and ethyl acetate were added and liquid-liquid extraction was performed. The ethyl acetate layer was collected and concentrated under reduced pressure. The resulting residue (1.66 g) was subjected to silica gel chromatography and eluted with a hexane / ethyl acetate = 3 / 1 mixture. The mixture was concentrated under reduced pressure to obtain 2-hydroxyisobutyl sorbate (1.40 g), which is shown in the structural formula below.

[0101] [ka]

[0102] Synthesis Example 29: Synthesis of 2-hydroxyisobutyl cinnamate Except for using cinnamic acid (3.97 g) instead of sorbic acid, the same method as in Synthesis Example 28 was used to obtain 2-hydroxyisobutyl cinnamate (2.18 g), shown by the following structural formula.

[0103] [ka]

[0104] Synthesis Example 30: Synthesis of 2-hydroxyisobutyl crotonic acid Except for using crotonic acid (2.31 g) instead of sorbic acid, the same method as in Synthesis Example 28 was used to obtain 2-hydroxyisobutyl crotonic acid (0.47 g), shown by the structural formula below.

[0105] [ka]

[0106] Synthesis Example 31: Synthesis of 2-hydroxyisobutyl fumarate Except for using fumaric acid (3.11 g) instead of sorbic acid, the same method as in Synthesis Example 28 was used to obtain 2-hydroxyisobutyl fumarate (0.55 g), which is shown in the structural formula below.

[0107] [ka]

[0108] Synthesis Example 32: Synthesis of 2-hydroxyisobutyl ferulate Except for using ferulic acid (5.24 g) instead of sorbic acid, the same method as in Synthesis Example 28 was used to obtain 2-hydroxyisobutyl ferulic acid (2.07 g), shown by the structural formula below.

[0109] [ka]

[0110] Synthesis Example 33: Synthesis of 1-naphthol-4-sulfonic acid 2-hydroxyisobutyl ester 1-Naphthol-4-Sulfonate sodium (2.46 g), sodium hydroxide (0.44 g), and ion-exchanged water (10 ml) were added to a round-bottom flask and stirred. Then, isobutylene oxide (0.87 g) was added and the mixture was stirred at 40°C for 5 hours. After the reaction was complete, ion-exchanged water (50 ml) was added, followed by neutralization with 17% hydrochloric acid, and then the mixture was concentrated under reduced pressure. Methanol (15 ml) heated to 60°C was added to the obtained residue (4.29 g), and the mixture was filtered. The filtrate was concentrated under reduced pressure. The obtained residue (2.67 g) was washed with an acetonitrile / ion-exchanged water mixture (10 / 1) cooled to 0°C, and then dried under reduced pressure to obtain 1-Naphthol-4-Sulfonate 2-hydroxyisobutyl ester (1.59 g), which is shown in the structural formula below.

[0111] [ka]

[0112] Synthesis Example 34: Synthesis of 2-hydroxyisobutyl 2-naphthol-6-sulfonic acid Except for using sodium 2-naphthol-6-sulfonate (2.46 g) instead of sodium 1-naphthol-4-sulfonate, the same method as in Synthesis Example 33 was used to obtain 2-naphthol-6-sulfonic acid 2-hydroxyisobutyl ester (1.68 g), which is shown in the following structural formula.

[0113] [ka]

[0114] Mass spectrometry was performed on the products obtained in synthesis examples 1 to 34 using LCMS-2020 (Shimadzu Corporation). The measurement results are shown in Table 1.

[0115] [Table 1] *Ionization was performed using electrospray ionization (ESI).

[0116] Products obtained in synthesis examples 1-34 1 1H-NMR was performed using a JNM-ECS400 (manufactured by JEOL Ltd.). The measurement results are shown in Tables 2-4.

[0117] [Table 2]

[0118] [Table 3]

[0119] [Table 4]

[0120] Products obtained in synthesis examples 1-34 1313C-NMR was performed using JNM-ECS400 (manufactured by JEOL Ltd.). The measurement results are shown in Tables 5 to 7.

[0121]

Table 5

[0122]

Table 6

[0123]

Table 7

[0124] Test Example 1 [Hyaluronic Acid Production Promoting Effect] Normal human dermal fibroblasts (NHDF) were prepared with D-MEM containing 5% (v / v) fetal bovine serum to a cell density of 2.5×10 4 cells / well and pre-incubated on a 96-well plate for 24 hours. After removing the medium, samples prepared with serum-free D-MEM were then added to each well and cultured for 48 hours. After the culture, the amount of hyaluronic acid in the supernatant was quantified by ELISA. The measurement was performed with N = 3.

[0125] When the samples were measured at a concentration of 10 mM or less, the hyaluronic acid production amount was compared with the Control group, and the results (% values when the Control group was set to 100%) are shown in Tables 8 to 10 based on the following criteria. <100% : ± 100 - 120% : + 120 - 150% : ++ 150% < : +++

[0126]

Table 8

[0127]

Table 9

[0128] [Table 10]

[0129] The results in Tables 8-10 clearly demonstrate that the cosmetic raw material of the present invention has an excellent hyaluronic acid production promoting effect.

[0130] Test Example 2 [Stability Test] 1% aqueous solutions of various test samples were each adjusted to pH 6 with dilute potassium hydroxide aqueous solution, placed in 50 mL screw-cap tubes, sealed tightly, and stored at 50°C for 4 weeks. The odor and color of the stored samples were evaluated according to the following methods and criteria, and the results are shown in Tables 11 and 12.

[0131] Odor: Evaluated by 10 panelists based on the following criteria. 3: Almost odorless. 2: There is a slight odor. 1: A strong, unpleasant odor is detected.

[0132] Coloring: Evaluated by 10 panelists based on the following criteria. 3: Almost no change compared to immediately after preparation. 2. Compare with the color immediately after preparation. 1: Stronger discoloration compared to immediately after preparation.

[0133] Based on these evaluation results, the odor and color evaluation results were classified as follows. ◎: Total score of 10 people is 25 or higher ○: The total score of 10 people is between 20 and 24 △: Total score of 10 people is between 16 and 19 ×: The total score of 10 people is 15 or less.

[0134] [Table 11]

[0135] [Table 12]

[0136] The results in Tables 11 and 12 clearly show that the cosmetic raw material of the present invention has excellent long-term stability.

[0137] Example 47 Cream The raw materials for the oil phase (1) to (5) and the raw materials for the aqueous phase (6) to (10) shown in Table 13 were heated to 70°C and dissolved to prepare the oil phase and aqueous phase, respectively. Then, the oil phase was added to the aqueous phase and pre-emulsified. After uniform emulsification using a homomixer, the mixture was cooled to room temperature while stirring well to prepare the cream. In the tables from Table 13 onward, the amounts are expressed in parts by mass.

[0138] [Table 13] * This refers to the amount required to make a total blend of 100 parts by mass. The same applies to the following table.

[0139] Example 48 Cream The oil phase ingredients (1) to (2) and the aqueous phase ingredients (3) to (10) shown in Table 14 are heated to 70°C and dissolved to prepare the oil and aqueous phases, respectively. Then, the oil phase is added to the aqueous phase for preliminary emulsification, and after uniform emulsification using a homomixer, the mixture is cooled to room temperature while stirring well to prepare the cream. This cream is used as a cosmetic for the skin.

[0140] [Table 14]

[0141] Example 49 Emulsion The raw materials for the oil phase (1) to (9) and the raw materials for the aqueous phase (10) to (13) shown in Table 15 were heated to 70°C and dissolved to prepare the oil phase and aqueous phase, respectively. Then, the oil phase was added to the aqueous phase for preliminary emulsification, and after uniform emulsification using a homomixer, the emulsion was prepared by cooling to room temperature while stirring well.

[0142] [Table 15]

[0143] Example 50 Emulsion The raw materials for the oil phase (5) to (10) and the raw materials for the aqueous phase (1) to (4) and (11) to (12) shown in Table 16 were heated to 70°C and dissolved to prepare the oil phase and aqueous phase, respectively. Then, the oil phase was added to the aqueous phase to perform preliminary emulsification, and after uniform emulsification with a homomixer, the emulsion was prepared by cooling to room temperature while stirring well.

[0144] [Table 16]

[0145] Example 51: Lotion A lotion can be prepared by mixing the raw materials (1) to (6) shown in Table 17 while stirring well.

[0146] [Table 17]

[0147] Example 52: Lotion A lotion can be prepared by mixing the raw materials (1) to (6) shown in Table 18 while stirring well.

[0148] [Table 18]

Claims

1. Cosmetic ingredients in which hydrogen atoms on the hydroxyl group, carboxyl group, or sulfonyl group of sugars, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, or sulfonic acids are substituted with functional groups represented by general formula (I) or (II). 【Chemistry 1】 【Chemistry 2】 [In formulas (I) and (II), * indicates the bonding site between a hydrogen atom on a hydroxyl group, carboxyl group, or sulfonyl group and the oxygen atom to which it is bonded.]

2. The cosmetic ingredient according to claim 1, characterized in that the aforementioned sugars, polyhydric alcohols or their derivatives, hydroxy acids, unsaturated carboxylic acids, and sulfonic acids are selected from sugars consisting of glucose and maltose, xylitol, inositol, methylglycerin, glyceryl laurate, glyceryl stearylate, diglyceryl stearate, diglyceryl isostearate, diglyceryl diisostearate, ethyl ethylene glycol, polyhydric alcohols or their derivatives consisting of 1-propoxy-2-propanol, hydroxy acids consisting of malic acid, mandelic acid, and salicylic acid, unsaturated carboxylic acids consisting of cinnamic acid, sorbic acid, crotonic acid, and fumaric acid, and sulfonic acids consisting of 1-naphthol-4-sulfonic acid and 2-naphthol-6-sulfonic acid.

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

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