JP5602456B2 - Ascorbic acid derivative - Google Patents

Description

（式中、Ｒ１及びＲ２は、それぞれ同一又は異なっていてもよい、炭素数１〜２２の直鎖、分岐鎖又は環状の炭化水素基を表す） The present invention relates to an ascorbic acid derivative represented by the general formula (1) and a cosmetic or skin external preparation containing the ascorbic acid derivative.

(Wherein R1 and R2 each represent a linear, branched or cyclic hydrocarbon group having 1 to 22 carbon atoms, which may be the same or different)

  Ascorbic acid is widely known to have functions such as an antioxidant action, a melanin production inhibitory action, and a collagen production promoting action. However, ascorbic acid is very unstable to heat and oxidation, and its use in the cosmetic field has been hindered. As a solution to this problem, various ascorbic acid derivatives in which the hydroxyl group at the 2-position or 3-position of ascorbic acid is derivatized are known. Among them, 3-O-alkyl-ascorbic acid obtained by alkylating the hydroxyl group at the 3-position of ascorbic acid (Patent Documents 1 and 2) is an element possessed by ascorbic acid such as an antioxidant action, a melanin production inhibitory action, and a collagen production promoting action. It exhibits the original functions and is also excellent in stability, and is preferably blended in cosmetics and skin external preparations. This 3-O-alkyl-ascorbic acid is known to have excellent storage stability at pH 3.0 to 6.0 when blended into water-based cosmetics (Patent Document 3). From pH 6.0 Stability was insufficient at high pH. In order to improve this, an ascorbic acid derivative in which both the hydroxyl groups at positions 2 and 3 are etherified with an epoxy compound, or one of the hydroxyl groups at positions 2 and 3 is etherified with an epoxy compound and one is alkyl etherified. Ascorbic acid derivatives are known (Patent Document 4). However, a compound in which both of the hydroxyl groups at the 2 and 3 positions are alkyl etherified is not known.

JP 61-207312 A JP 06-228557 A JP 03-153609 WO2009 / 0253328

  Provided is an ascorbic acid derivative having a physiological activity equivalent to that of 3-O-alkyl-ascorbic acid and excellent in stability in an aqueous solution.

  As a result of intensive studies to solve the above problems, the present inventors have surprisingly found that 2,3-di-O-alkyl-ascorbic acid is physiologically equivalent to 3-O-alkyl-ascorbic acid. It has been found that it has activity and is more stable in aqueous solution.

  The ascorbic acid derivative of the present invention has a physiological activity equivalent to that of a conventional ascorbic acid derivative, and is more excellent in stability in an aqueous solution. Specifically, 3-O-alkyl-ascorbic acid shows a high residual rate even in an aqueous solution having a pH of 6.0 or more, which has been problematic. Moreover, although it was discovered by the present inventors that 3-O-alkyl-ascorbic acid significantly decreases the pH of the aqueous solution over time, the ascorbic acid derivative of the present invention has a small change in pH. In cosmetic formulations, changes in pH are not preferred because they may change the viscosity and appearance of the formulation, and those with little pH change are desired. Although it is possible to suppress the decrease in pH by increasing the buffer concentration, increasing the buffer concentration is not preferable in terms of touch and causes the precipitation of ionic compounds due to the salting out effect. The ascorbic acid derivative of the present invention is superior to the conventional ascorbic acid derivative in this respect as well.

（式中、Ｒ１及びＲ２は、それぞれ同一又は異なっていてもよい、炭素数１〜２２の直鎖、分岐鎖又は環状の炭化水素基を表す） The ascorbic acid derivative of the present invention is a compound represented by the following general formula (1).

(Wherein R1 and R2 each represent a linear, branched or cyclic hydrocarbon group having 1 to 22 carbon atoms, which may be the same or different)

  As the ascorbic acid used in the present invention, any of L-form, D-form and DL-form may be used, but L-form is most preferred from the viewpoint of availability.

  Specific examples of the linear, branched or cyclic hydrocarbon group having 1 to 22 carbon atoms constituting R1 or R2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , T-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-docosyl group, 2-ethylhexyl Group, 2-butyloctyl group, 2-butyldecyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldecyl group, 2-hexyldecyl group, 2 Octyldodecyl group, 2-decyl tetradecyl group, 2-dodecyl-hexadecyl group and the like. Among these, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, and an ethyl group is most preferable in terms of exerting a whitening effect and a collagen production promoting effect.

  The production method of the ascorbic acid derivative of the present invention is not particularly limited and can be produced by a known production method. Specifically, for example, it can be produced as follows. In the presence of a base, an alkylating agent such as alkyl halide or dialkyl sulfate is reacted with ascorbic acid obtained by cyclic acetalization of the 5,6-position hydroxyl group such as 5,6-O-isopropylidene-L-ascorbic acid, The target compound can be obtained by alkylating the hydroxyl group at the 3-position and then hydrolyzing the acetal at the 5- and 6-positions in the presence of an acid. Alternatively, the desired compound can also be obtained by reacting L-ascorbic acid directly with an alkylating agent such as alkyl chloride or dialkyl sulfate in the presence of a base. The ascorbic acid derivative of the present invention thus obtained may be used as it is in cosmetics and external preparations for skin, but may be used after being appropriately purified by extraction, washing, recrystallization, adsorption purification, distillation, column purification, etc. May be.

  The blending amount of the ascorbic acid derivative of the present invention into the cosmetic or external skin preparation is not particularly limited, but is preferably 0.01 to 50% by weight, more preferably 0.05 to 20% by weight. Moreover, since the ascorbic acid derivative of the present invention is excellent in stability in an aqueous solution, it can be preferably blended in a formulation containing water. The pH of the formulation is preferably 4.0 to 7.0.

  The ascorbic acid derivative of the present invention can be used synergistically when used in combination with known antioxidants, whitening agents, collagen production promoters, and the like.

  For cosmetics or skin external preparations containing the ascorbic acid derivative of the present invention, additive components generally blended into cosmetics or skin external preparations as necessary, for example, oily bases, moisturizers, feel improvers, Surfactant, polymer, thickener / gelator, solvent, propellant, antioxidant, reducing agent, oxidizing agent, antibacterial agent, preservative, chelating agent, pH adjuster, acid, alkali, powder, inorganic Salt, UV absorber, whitening agent, vitamins and derivatives thereof, anti-inflammatory agent, anti-inflammatory agent, hair growth agent, blood circulation promoter, stimulant, hormones, anti-wrinkle agent, anti-aging agent, squeeze agent, cooling sensation Agent, warming sensation agent, wound healing promoter, stimulus relaxation agent, analgesic agent, cell activator, plant / animal / microbe extract, antipruritic agent, exfoliating / dissolving agent, antiperspirant, refreshing agent, astringent, enzyme, Nucleic acids, fragrances, pigments, colorants, dyes, pigments, water, and the like can be blended.

  Examples of oily bases include cetanol, myristyl alcohol, oleyl alcohol, lauryl alcohol, cetostearyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, jojoba alcohol, chimyl alcohol, ceralkyl alcohol, batyl alcohol, hexyldecanol, isostearyl alcohol, Higher alcohols such as 2-octyldodecanol and dimer diol; aralkyl alcohols and derivatives such as benzyl alcohol; lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, undecylenic acid, 12-hydroxystearic acid, Palmitooleic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, docosahexaenoic acid, eicosapentaenoic acid, isohexa Higher fatty acids such as cannic acid, anteisohenicosanoic acid, long-chain branched fatty acid, dimer acid, hydrogenated dimer acid, and metal soaps such as aluminum salts, calcium salts, magnesium salts, zinc salts, potassium, sodium salts, etc. And nitrogen-containing derivatives such as amides; liquid paraffin (mineral oil), heavy liquid isoparaffin, light liquid isoparaffin, α-olefin oligomer, polyisobutene, hydrogenated polyisobutene, polybutene, squalane, olive-derived squalane, squalene, petrolatum, solid Type hydrocarbons such as candelilla wax, carnauba wax, rice wax, wax, beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, petrolatum, fisher Tropsch wax, polyethylene wax, waxes such as ethylene / propylene copolymer; palm oil, palm oil, palm kernel oil, safflower oil, olive oil, castor oil, avocado oil, sesame oil, tea oil, evening primrose oil, wheat germ oil, macadamia nut Oil, hazelnut oil, cucumber oil, rosehip oil, meadow foam oil, persic oil, tea tree oil, peppermint oil, corn oil, rapeseed oil, sunflower oil, wheat germ oil, linseed oil, cottonseed oil, soybean oil, peanut oil, rice bran Vegetable oils such as oil, cacao butter, shea fat, hydrogenated coconut oil, hydrogenated castor oil, jojoba oil, hydrogenated jojoba oil; animal properties such as beef tallow, milk fat, horse fat, egg yolk oil, mink oil, turtle oil Fats and oils; animal waxes such as whale wax, lanolin, orange luffy oil; liquid lanolin, reduced lanoli Lanolins such as adsorption purified lanolin, lanolin acetate, liquid lanolin acetate, hydroxy lanolin, polyoxyethylene lanolin, lanolin fatty acid, hard lanolin fatty acid, lanolin alcohol, lanolin alcohol acetate, acetic acid (cetyl lanolyl) ester; lecithin, phosphatidylcholine, Phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingophospholipids such as sphingomyelin, phospholipids such as phosphatidic acid, lysolecithin; hydrogenated soybean phospholipid, partially hydrogenated soybean phospholipid, hydrogenated egg yolk phospholipid, Phospholipid derivatives such as partially hydrogenated egg yolk phospholipids; cholesterol, dihydrocholesterol, lanosterol, dihydrolanosterol, phytoster Sterols such as oleol and cholic acid; sapogenins; saponins; cholesteryl acetate, cholesteryl nonanoate, cholesteryl stearate, cholesteryl isostearate, cholesteryl oleate, di-N-lauroyl-L-glutamate (cholesteryl / behenyl / octyldodecyl) ), N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / behenyl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / octyldodecyl), N Acyl sarcosine alkyl esters such as lauroyl sarcosine isopropyl, cholesteryl 12-hydroxystearate, macadamia nut oil fatty acid cholesteryl, macadamia nut oil fatty acid phyto Sterol esters such as steryl, phytosteryl isostearate, soft lanolin fatty acid cholesteryl, hard lanolin fatty acid cholesteryl, long chain branched fatty acid cholesteryl, long chain α-hydroxy fatty acid cholesteryl; phospholipid / cholesterol complex, phospholipid / phytosterol complex, etc. Lipid complex; octyldodecyl myristate, hexyldecyl myristate, octyldodecyl isostearate, cetyl parmitate, octyldodecyl palmitate, cetyl octanoate, hexyl decyl octanoate, isotridecyl isononanoate, isononyl isononanoate, isononanoate Isotridecyl acid, isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octeodecanoate Ludodecyl, oleyl oleate, octyldodecyl oleate, octyldodecyl ricinoleate, lanolin fatty acid octyldodecyl, hexyldecyl dimethyloctanoate, octyldodecyl erucate, isostearic acid hydrogenated castor oil, ethyl oleate, ethyl avocado oil, isopropyl myristate , Isopropyl palmitate, octyl palmitate, isopropyl isostearate, lanolin fatty acid isopropyl, diethyl sebacate, diisopropyl sebacate, dioctyl sebacate, diisopropyl adipate, dibutyl octyl sebacate, diisobutyl adipate, dioctyl succinate, triethyl citrate, etc. Monoalcohol carboxylic acid esters; cetyl lactate, diisostearyl malate, monoisostearyl Oxyacid esters such as acid hydrogenated castor oil; glyceryl trioctanoate, glyceryl trioleate, glyceryl triisostearate, glyceryl diisostearate, glyceryl tri (caprylic / capric), tri (caprylic / capric / myristin) Acid / stearic acid) glyceryl, hydrogenated rosin triglyceride (hydrogenated ester gum), rosin triglyceride (ester gum), glyceryl behenate, trimethylolpropane trioctanoate, trimethylolpropane triisostearate, neopentyl glycol dioctanoate , Neopentyl glycol dicaprate, 2-butyl-2-ethyl-1,3-propanediol dioctanoate, propylene glycol dioleate, pentaerythrtetraoctanoate Chill, hydrogenated rosin pentaerythrityl, triethylhexanoic acid ditrimethylolpropane, (isostearic acid / sebacic acid) ditrimethylolpropane, triethylhexanoic acid pentaerythrityl, (hydroxystearic acid / stearic acid / rosinic acid) dipentaerythrityl, diisostearic acid di Glyceryl, polyglyceryl tetraisostearate, polyglyceryl-10 nonaisostearate, deca (erucic acid / isostearic acid / ricinoleic acid) polyglyceryl-8, (hexyldecanoic acid / sebacic acid) diglyceryl oligoester, glycol distearate (ethylene glycol distearate) , Dineopentanoic acid 3-methyl-1,5-pentanediol, dineopentanoic acid 2,4-diethyl-1,5-pentane Polyhydric alcohol fatty acid esters such as ol; dimer dilinoleate diisopropyl, dimer dilinoleate diisostearyl, dimer dilinoleate di (isostearyl / phytosteryl), dimer dilinoleate (phytosteryl / behenyl), dimer dilinoleate (Phytosteryl / isostearyl / cetyl / stearyl / behenyl), dimer dilinoleic acid dimer dilinoleyl, diisostearic dimer dilinoleyl, dimer dilinoleyl hydrogenated rosin condensate, dimer dilinoleic acid hydrogenated castor oil, hydroxyalkyl die Dimer acid or dimer diol derivative such as merlinoleyl ether; coconut oil fatty acid monoethanolamide (cocamide MEA), coconut oil fatty acid diethanolamide (cocamide DEA), Lauri Acid monoethanolamide (lauramide MEA), lauric acid diethanolamide (lauramide DEA), lauric acid monoisopropanolamide (lauramide MIPA), palmitic acid monoethanolamide (partamide MEA), palmitic acid diethanolamide (partamide DEA), coconut oil Fatty acid alkanolamides such as fatty acid methylethanolamide (cocamidomethyl MEA); dimethicone (dimethylpolysiloxane), highly polymerized dimethicone (highly polymerized dimethylpolysiloxane), cyclomethicone (cyclic dimethylsiloxane, decamethylcyclopentasiloxane), phenyltrimethicone , Diphenyldimethicone, phenyldimethicone, stearoxypropyldimethylamine, (aminoethylaminopropylmethicone / dimethicone) Polymer, dimethiconol, dimethiconol crosspolymer, silicone resin, silicone rubber, amino-modified silicone such as aminopropyl dimethicone and amodimethicone, cation-modified silicone, polyether-modified silicone such as dimethicone copolyol, polyglycerin-modified silicone, sugar-modified silicone, carvone Acid-modified silicone, phosphoric acid-modified silicone, sulfuric acid-modified silicone, alkyl-modified silicone, fatty acid-modified silicone, alkyl ether-modified silicone, amino acid-modified silicone, peptide-modified silicone, fluorine-modified silicone, cation-modified and polyether-modified silicone, amino-modified and poly-modified Ether-modified silicone, alkyl-modified and polyether-modified silicone, polysiloxane-oxyalkylene copolymer Silicones such as body; perfluorodecane, perfluorooctane, fluorine-based oils such as perfluoropolyether may be mentioned as preferred.

  As the humectant / feel improver, glycerin, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, Polyols such as trimethylolpropane, pentaerythritol, hexylene glycol, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymer and polymers thereof; diethylene glycol monoethyl ether (Ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether, etc. (Eicosane diacid / tetradecanedioic acid) water-soluble esters such as polyglyceryl-10, tetradecanedioic acid polyglyceryl-10, and cyclohexanedicarboxylic acid bisethoxydiglycol; sugars such as sorbitol, xylitol, erythritol, mannitol, maltitol Alcohols; glucose, fructose, galactose, mannose, threose, xylose, arabinose, fucose, ribose, deoxyribose, maltose, trehalose, lactose, raffinose, gluconic acid, glucuronic acid, cyclodextrins (α-, β-, γ- Cyclodextrins and modified cyclodextrins such as maltosylation and hydroxyalkylation), β-glucan, chitin, chitosan, heparin and derivatives, pectin, arabino Sugars and derivatives thereof such as galactan, dextrin, dextran, glycogen, ethyl glucoside, glucosylethyl methacrylate polymer or copolymer; hyaluronic acid, sodium hyaluronate; sodium chondroitin sulfate; mucoitin sulfate, caroline sulfate, keratosulfate, dermatan Sulfuric acid; white jellyfish extract; white jellyfish polysaccharide; fucoidan; tuberose polysaccharide, naturally derived polysaccharide; organic acids such as citric acid, tartaric acid, lactic acid and their salts; urea; 2-pyrrolidone-5-carboxylic acid and its sodium Salt: betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, tyrosine, β-alanine, threonine, glutamic acid, glutamine, aspa Amino acids such as gin, aspartic acid, cysteine, cystine, methionine, leucine, isoleucine, valine, tryptophan, histidine, taurine and the salts thereof; collagen, fish-derived collagen, atelocollagen, gelatin, elastin, collagenolytic peptide, hydrolyzed collagen, Hydroxypropylammonium chloride hydrolyzed collagen, elastin degrading peptide, keratin degrading peptide, hydrolyzed keratin, conchiolin degrading peptide, hydrolyzed conchiolin, silk proteolytic peptide, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soy proteolytic peptide, wheat protein Degraded peptides, hydrolyzed wheat protein, casein-degraded peptides, acylated peptides and other protein peptides and their derivatives; palmitoyl oligopeptides , Acylated peptides such as palmitoyl pentapeptide, palmitoyl tetrapeptide; silylated peptides; lactic acid bacteria culture solution, yeast extract, eggshell membrane protein, bovine submandibular gland mucin, hypotaurine, sesameignan glycoside, glutathione, albumin, milk Chin; choline chloride, phosphorylcholine; placenta extract, aerostin, collagen, aloe extract, hamamelis water, loofah water, chamomile extract, licorice extract, comfrey extract, silk extract, Izayoi rose extract, yarrow extract, eucalyptus extract, merirot extract Preferred are ceramides such as animal and plant extract components such as natural ceramides (types 1, 2, 3, 4, 5, 6), hydroxyceramide, pseudoceramide, glycosphingolipid, ceramide, and sugar-ceramide-containing extracts. All It is.

Preferred examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a polymer surfactant. There is no restriction | limiting in particular in HLB of surfactant, It can use from about 1 low thing to about 20 high thing, It is also preferable to combine a low thing and a high thing of HLB. Examples of preferable surfactants include fatty acid salts such as potassium laurate and potassium myristate; alkyl sulfates such as sodium lauryl sulfate, triethanolamine lauryl sulfate, and ammonium lauryl sulfate; laureth Polyoxyethylene alkyl sulfates such as sodium sulfate and laureth sulfate triethanolamine; cocoyl methyl taurine sodium, cocoyl methyl taurine potassium, lauroyl methyl taurine sodium, myristoyl methyl taurine sodium, lauroyl methyl alanine sodium, lauroyl sarcosine sodium, lauroyl sarcosine triethanol Acyl N-methyl amino acid salts such as amines and sodium methylalanine lauroylglutamate; Cocoyl Glue Acyl amino acid salts such as sodium minate, triethanolamine cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium stearoyl glutamate, ditriethanolamine palmitoyl aspartate, cocoylalanine triethanolamine; polyoxyethylene alkyl ethers such as sodium laureth acetate Acetic acid salt; Succinic acid ester salt such as sodium lauroyl monoethanolamide succinate; Fatty acid alkanolamide ether carboxylate; Acyl lactate; Polyoxyethylene fatty amine sulfate; Fatty acid alkanolamide sulfate; Hardened coconut oil fatty acid sodium glyceryl sulfate Fatty acid glyceride sulfate such as alkylbenzene polyoxyethylene sulfate; α-olefin Olefin sulfonates such as sodium sulfonate; alkylsulfosuccinates such as disodium lauryl sulfosuccinate and dioctyl sodium sulfosuccinate; disodium laureth sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, lauryl polypropylene glycol sulfosuccinic acid Alkyl ether sulfosuccinates such as sodium; alkylbenzene sulfonates such as sodium tetradecylbenzenesulfonate and tetraethanolamine tetraethanol; alkylnaphthalenesulfonates; alkanesulfonates; α-sulfo fatty acid methyl ester salts; Acyl isethionate; alkyl glycidyl ether sulfonate; alkyl sulfoacetate; laurethrin Alkyl ether phosphates such as sodium, sodium dilaureth phosphate, sodium trilaureth phosphate, sodium monooles phosphate; alkyl phosphate salts such as potassium lauryl phosphate; sodium caseinate; alkyl aryl ether phosphate; fatty acid amide ether phosphorus Phospholipids such as phosphatidylglycerol, phosphatidylinositol, and phosphatidic acid; silicone anionic surfactants such as carboxylic acid-modified silicone, phosphate-modified silicone, and sulfate-modified silicone; and nonionic surfactants, laureth (Polyoxyethylene lauryl ether), ceteth (polyoxyethylene cetyl ether), steareth (polyoxyethylene stearyl ether), behenez (polyoxyethylene) Nbehenyl ethers), isosteares (polyoxyethylene isostearyl ethers), octyldecesses (polyoxyethylene octyldodecyl ethers) and other polyoxyethylene alkyl ethers with various polyoxyethylene addition numbers; polyoxyethylene alkylphenyl ethers; Polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil monoisostearate, polyoxyethylene hydrogenated castor oil triisostearate, polyoxyethylene hydrogenated castor oil monopyroglutamic acid monoisostearate diester, poly Castor oil such as oxyethylene hydrogenated castor oil maleic acid and hydrogenated castor oil derivatives; polyoxyethylene phytosterol; polyoxyethylene cholesterol; polyoxy Polyoxyethylene lanolin; polyoxyethylene reduced lanolin; polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene 2-decyltetradecyl ether, polyoxyethylene polyoxypropylene monobutyl ether, polyoxyethylene lanolin; Oxyethylene / polyoxypropylene hydrogenated lanolin, polyoxyethylene / polyoxypropylene alkyl ethers such as polyoxyethylene / polyoxypropylene glycerin ether; polyoxyethylene / polyoxypropylene glycol; (poly) such as PPG-9 diglyceryl Glycerin polyoxypropylene glycol; glyceryl stearate, glyceryl isostearate, glyceryl palmitate, myristate group Glyceryl fatty acid partial esters such as ceryl, glyceryl oleate, glyceryl coconut fatty acid, mono-cotton oil fatty acid glycerin, glyceryl monoerucate, glyceryl sesquioleate, α, α'-oleic acid pyroglutamic acid glycerin, monostearic acid glycerin malic acid; Polyglyceryl stearate-2, 3, 4, 5, 6, 8, 10, polyglyceryl distearate-6, 10, polyglyceryl tristearate, polyglyceryl decastearate-10, polyglyceryl isostearate -2, 3, 4, 5, 6, 8, 10, diglycostyl diisostearate (diglyceryl diisostearate), 3, 10, polyglyceryl-2 triisostearate, polyglyceryl tetraisostearate Ril-2, polyglyceryl-10 decaisostearate, polyglyceryl-2 oleate, 3,4, 5,6, 8,8, dioleate polyglyceryl-6, trioleate polyglyceryl-2, dekaoleic acid Polyglyceryl fatty acid esters such as polyglyceryl-10; ethylene glycol monofatty acid esters such as ethylene glycol monostearate; propylene glycol monofatty acid esters such as propylene glycol monostearate; pentaerythritol partial fatty acid esters; sorbitol partial fatty acid esters; maltitol moieties Fatty acid ester; maltitol ether; sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monos Sorbitan fatty acid esters such as allate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate; sucrose fatty acid ester, methyl glucoside fatty acid ester, trehalose undecylenate, etc. Partial derivatives of sugar derivatives; alkyl glucosides such as caprylyl glucoside; alkyl polyglycosides; lanolin alcohols; reduced lanolin; polyoxyethylene distearate, polyethylene glycol diisostearate, polyoxyethylene monooleate, polyoxyethylene di- Polyoxyethylene fatty acid mono- and diesters such as oleate; polyoxyethylene propylene glycol fatty acid ester; polyoxyethylene Polyoxyethylene glycerin fatty acid esters such as polyoxyethylene monooleate such as polyglycerin monostearate, polyoxyethylene glycerin monoisostearate, polyoxyethylene glycerin triisostearate; polyoxyethylene sorbitan monooleate, polyoxy Polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tetraoleate; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monooleate, polyoxyethylene sorbitol penta Polyoxyethylene sorbitol fatty acid esters such as oleate and polyoxyethylene sorbitol monostearate Polyoxyethylene methyl glucoside fatty acid ester; Polyoxyethylene alkyl ether fatty acid ester; Polyoxyethylene animal and vegetable oils such as polyoxyethylene sorbitol beeswax; Alkyl such as isostearyl glyceryl ether, chimyl alcohol, ceralkyl alcohol, batyl alcohol Glyceryl ethers; polyhydric alcohol alkyl ethers; polyoxyethylene alkylamines; tetrapolyoxyethylene / tetrapolyoxypropylene-ethylenediamine condensates; natural surfactants such as saponins and sophorolipids; polyoxyethylene fatty acid amides; coconut oil Fatty acid monoethanolamide (cocamide MEA), coconut oil fatty acid diethanolamide (cocamide DEA), lauric acid monoethanolamide (laura) De-MEA), lauric acid diethanolamide (lauramide DEA), lauric acid monoisopropanolamide (lauramide MIPA), palmitic acid monoethanolamide (partamide MEA), palmitic acid diethanolamide (partamide DEA), palm oil fatty acid methylethanolamide (cocamidomethyl) Fatty acid alkanolamides such as MEA); alkyldimethylamine oxides such as lauramine oxide, cocamamine oxide, stearamine oxide, and behenamine oxide; alkylethoxydimethylamine oxide; polyoxyethylene alkyl mercaptan; poly such as dimethicone copolyol Silicone such as ether-modified silicone, polysiloxane-oxyalkylene copolymer, polyglycerin-modified silicone, sugar-modified silicone Nonionic surfactants, etc .; for cationic surfactants, alkyltrimethylammonium chlorides such as behentrimonium chloride, steartrimonium chloride, cetrimonium chloride, lauryltrimonium chloride; alkyls such as stearyltrimonium bromide Trialkylammonium bromide; dialkyldimethylammonium chloride such as distearyldimonium chloride and dicocodimonium chloride; fatty acid amidoamines and salts thereof such as stearamidepropyldimethylamine and stearamideethyldiethylamine; alkyl ether amines such as stearoxypropyldimethylamine; Salt or quaternary salt thereof; ethyl sulfate long chain branched fatty acid (12-31) aminopropylethyldimethylammonium, ethyl lanolin sulfate Fatty acid amide-type quaternary ammonium salts such as aminopropylethyldimethylammonium fatty acid; polyoxyethylene alkylamine and its salts or quaternary salts; alkylamine salts; fatty acid amidoguanidinium salts; alkyl etheraminemonium salts; Benzalkonium salt; Pyridinium salt such as cetylpyridinium chloride; Imidazolinium salt; Alkylisoquinolinium salt; Dialkyl morpholinium salt; Polyamine fatty acid derivatives; Aminopropyl dimethicone and amodimethicone Silicone-based cationic surfactants such as amino-modified silicone, cation-modified silicone, cation-modified and polyether-modified silicone, amino-modified and polyether-modified silicone;
In amphoteric surfactants, N-alkyl-N, N-dimethylamino acid betaines such as lauryl betaine (lauryldimethylaminoacetic acid betaine); fatty acid amide alkyl-N, N-dimethylamino acids such as cocamidopropyl betaine and lauramidopropyl betaine Betaines; imidazoline-type betaines such as sodium cocoamphoacetate and sodium lauroamphoacetate; alkylsulfobetaines such as alkyldimethyltaurine; sulfate-type betaines such as alkyldimethylaminoethanol sulfate; phosphate-type betaines such as alkyldimethylaminoethanol phosphate; Sphingophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, sphingomyelin, lysolecithin, hydrogenated soybean phospholipid, partially hydrogenated Phospholipids such as soybean phospholipid, hydrogenated egg yolk phospholipid, partially hydrogenated egg yolk phospholipid, and hydroxylated lecithin; silicone-based amphoteric surfactants; polymer surfactants such as polyvinyl alcohol, sodium alginate, starch derivatives, Preferred are tragacanth gum, acrylic acid / alkyl methacrylate copolymer; and various silicone surfactants.

  Polymers, thickeners and gelling agents include guar gum, locust bean gum, queens seed, carrageenan, galactan, arabic gum, tara gum, tamarind, far selelain, karaya gum, troarooi, cara gum, tragacanth gum, pectin, pectic acid and sodium Salt such as salt, salt such as alginic acid and sodium salt, mannan; starch such as rice, corn, potato, wheat; xanthan gum, dextran, succinoglucan, curdlan, hyaluronic acid and its salt, xanthan gum, pullulan, gellan gum, chitin , Chitosan, agar, gypsum extract, chondroitin sulfate, casein, collagen, gelatin, albumin; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropi Cellulose, carboxymethylcellulose and its salts such as sodium, methylhydroxypropylcellulose, sodium cellulose sulfate, cellulose dialkyldimethylammonium sulfate, crystalline cellulose, cellulose powder such as cellulose powder; soluble starch, carboxymethyl starch, methylhydroxypropyl starch, Starch-based polymers such as methyl starch, starch derivatives such as hydroxypropyltrimonium chloride, octenyl succinate corn starch and aluminum; alginic acid derivatives such as sodium alginate and propylene glycol alginate; polyvinylpyridone (PVP), polyvinyl alcohol (PVA), Vinyl pydridone-vinyl alcohol copolymer, polyvinyl methyl ether Polyethylene glycol, polypropylene glycol, polyoxyethylene / polyoxypropylene copolymer; amphoteric methacrylic acid such as (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, (acrylates / stearyl acrylate / ethylamine methacrylate oxide) copolymer, etc. Ester copolymer; (Dimethicone / vinyl dimethicone) crosspolymer, (alkyl acrylate / diacetone acrylamide) copolymer, (alkyl acrylate / diacetone acrylamide) copolymer AMP; Polyvinyl acetate partial saponification product, maleic acid copolymer; Vinylpyrrolidone / dialkylaminoalkyl methacrylate copolymer; acrylic resin alkanolamine; polyester, water-dispersible polyester; Kurylamide; Polyacrylic acid ester copolymer such as polyethyl acrylate, carboxyvinyl polymer, polyacrylic acid and its sodium salt, acrylic acid / methacrylic acid ester copolymer; acrylic acid / alkyl methacrylate Polymer: Cationized cellulose such as polyquaternium-10, diallyldimethylammonium chloride / acrylamide copolymer such as polyquaternium-7, acrylic acid / diallyldimethylammonium chloride copolymer such as polyquaternium-22, and acrylic acid such as polyquaternium-39・ Diallyldimethylammonium chloride / acrylamide copolymer, acrylic acid / cationized methacrylic acid ester copolymer, acrylic acid / cationized methacrylic acid amide copolymer, polyquaternium Acrylic acid / methyl acrylate / methacrylamidopropyltrimethylammonium chloride copolymer such as 47, methacrylic acid choline ester polymer; cationized polysaccharides such as cationized oligosaccharide, cationized dextran, guar hydroxypropyltrimonium chloride; Polyethyleneimine; Cationic polymer; Polymer of 2-methacryloyloxyethyl phosphorylcholine such as polyquaternium-51 and copolymer with butyl methacrylate copolymer; Acrylic resin emulsion, polyethyl acrylate emulsion, polyacrylalkyl ester emulsion, Polymer emulsions such as polyvinyl acetate resin emulsion, natural rubber latex, synthetic latex; nitrocellulose; polyurethanes and various copolymers; various silicones Various silicone-based copolymers such as acrylic-silicone graft copolymers; various fluoropolymers; 12-hydroxystearic acid and its salts; dextrin fatty acid esters such as dextrin palmitate and dextrin myristate; silicic anhydride, Smoke-like silica (ultrafine silicic anhydride), aluminum magnesium silicate, magnesium magnesium silicate, metal soap, dialkyl phosphate metal salt, bentonite, hectorite, organically modified clay mineral, sucrose fatty acid ester, fructooligosaccharide fatty acid ester It is mentioned as preferable.

  Solvents and propellants include ethanol, 2-propanol (isopropyl alcohol), butanol, isobutyl alcohol and other lower alcohols; propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, isopentyl diol and other glycols Diethylene glycol monoethyl ether (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether Glycol ethers such as ethylene glycol monoethyl ether Glycol ether esters such as acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate; Glycol esters such as diethoxyethyl succinate, ethylene glycol disuccinate; benzyl alcohol, benzyloxyethanol, propylene carbonate, dialkyl carbonate , Acetone, ethyl acetate, N-methylpyrrolidone; toluene; fluorocarbon, next-generation flon; propellants such as LPG, dimethyl ether, carbon dioxide, and the like are preferable.

  Antioxidants include tocopherol derivatives such as tocopherol (vitamin E) and tocopherol acetate; BHT, BHA; gallic acid derivatives such as propyl gallate; vitamin C (ascorbic acid) and / or derivatives thereof; erythorbic acid and derivatives thereof; Preferred are sulfites such as sodium sulfite; bisulfites such as sodium bisulfite; thiosulfates such as sodium thiosulfate; metabisulfites; thiotaurine, hypotaurine; thioglycerol, thiourea, thioglycolic acid, cysteine hydrochloride As mentioned. Preferred examples of the reducing agent include thioglycolic acid, cysteine, cysteamine and the like. Preferred examples of the oxidizing agent include aqueous hydrogen peroxide, ammonium persulfate, sodium bromate, and percarbonate.

  Antibacterial agents or antiseptics include parabens (hydroxybenzoic acid esters) such as methylparaben, ethylparaben, propylparaben and butylparaben; phenoxyethanol; 1,2-pentanediol, 1,2-hexanediol, 1,2-octane 1,2-alkanediols such as diol; alkyl glyceryl ethers such as 2-ethylhexyl glyceryl ether (ethylhexyl glycerin); salicylic acid; sodium benzoate; isothiazoline derivatives such as methyl chloroisothiazolinone and methylisothiazolinone; Dehydroacetic acid and its salts; phenols; halogenated bisphenols such as triclosan, acid amides, quaternary ammonium salts; trichlorocarbanide, zinc pyrithione, benzoyl chloride Luconium, benzethonium chloride, sorbic acid, chlorhexidine, chlorhexidine gluconate, halocarban, hexachlorophene, hinokitiol; other phenols such as phenol, isopropylphenol, cresol, thymol, parachlorophenol, phenylphenol, sodium phenylphenol; phenylethyl alcohol , Photosensitizers, antibacterial zeolite, and silver ion are preferable, but when used as an antibacterial agent or antiseptic agent for antiseptic purposes, phenoxyethanol; 1 from the viewpoint of safety of cosmetics or skin external preparations; 1,2-alkanediols such as 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol; alkyl glyceres such as 2-ethylhexyl glyceryl ether It is more preferred to use ethers.

  Examples of chelating agents include edetate (ethylenediaminetetraacetate) such as EDTA, EDTA2Na, EDTA3Na, and EDTA4Na; hydroxyethylethylenediaminetriacetate such as HEDTA3Na; pentetate (diethylenetriaminepentaacetate); phytic acid; Phosphonic acid and its sodium salt; sodium oxalate; polypolyamino acids such as polyaspartic acid and polyglutamic acid; sodium polyphosphate, sodium metaphosphate, phosphoric acid; sodium citrate, citric acid, alanine, dihydroxyethylglycine Gluconic acid, ascorbic acid, succinic acid, and tartaric acid are preferable. pH adjusters / acids / alkalis include citric acid, sodium citrate, lactic acid, sodium lactate, glycolic acid, succinic acid, acetic acid, sodium acetate, malic acid, tartaric acid, fumaric acid, phosphoric acid, hydrochloric acid, sulfuric acid, monoethanol Amine, diethanolamine, triethanolamine, isopropanolamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, arginine, hydroxylation Sodium, potassium hydroxide, aqueous ammonia, guanidine carbonate, and ammonium carbonate are preferable.

  Examples of powders include mica, talc, kaolin, sericite, montmorillonite, kaolinite, mica, muscovite, phlogopite, synthetic mica, red mica, biotite, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, silica Barium acid, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, bentonite, smectite, clay, mud, Metal soap (e.g. zinc myristate, calcium palmitate, aluminum stearate), calcium carbonate, bengara, yellow iron oxide, black iron oxide, ultramarine, bitumen, carbon black, titanium oxide, fine particles and ultrafine Titanium oxide, zinc oxide, fine and ultrafine zinc oxide, alumina, silica, fumed silica (ultrafine silica), titanium mica, fish scale foil, boron nitride, photochromic pigment, synthetic fluorophlogopite, fine particle composite powder Body, gold, aluminum, etc., various sizes and shapes of inorganic powders, and these are treated with various surface treatment agents such as hydrogen silicone, cyclic hydrogen silicone, or other silane or titanium coupling agents Inorganic powders such as hydrophobized or hydrophilized powders; starch, cellulose, nylon powder, polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, polyester powder, Benzoguanamine resin powder, polyethylene terephthalate, polymethyl Organic powders and surface-treated powders of various sizes and shapes, such as methacrylate powder, polyethylene terephthalate / aluminum / epoxy powder, urethane powder, silicone powder, Teflon (registered trademark) powder, organic-inorganic composite powder Is preferable. Inorganic salts include sodium chloride-containing salts such as salt, common salt, rock salt, sea salt, natural salt; potassium chloride, aluminum chloride, calcium chloride, magnesium chloride, bittern, zinc chloride, ammonium chloride; sodium sulfate, aluminum sulfate, Aluminum sulfate / potassium sulfate (alum), aluminum sulfate / ammonium sulfate, barium sulfate, calcium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, copper sulfate; sodium phosphates such as 1Na, 2Na and 3Na phosphates, phosphoric acid Potassium, calcium phosphates and magnesium phosphates are preferred.

Examples of ultraviolet absorbers include paraaminobenzoic acid, paraaminobenzoic acid monoglycerin ester, N, N-dipropoxyparaaminobenzoic acid ethyl ester, N, N-diethoxyparaaminobenzoic acid ethyl ester, and N, N-dimethylparaaminobenzoic acid ethyl ester. Benzoic acid-based ultraviolet absorbers such as esters, N, N-dimethylparaaminobenzoic acid butyl ester, N, N-dimethylparaaminobenzoic acid ethyl ester; Anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; Salicylic acid And salicylic acid-based purple such as sodium salt, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate Line absorber: Octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p- Methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate (octyl paramethoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate (sinoxate), Cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate (octocrine), glyceryl mono-2-ethylhexanoyl-diparamethoxy Nameto, cinnamic acid UV absorbers such as ferulic acid and its derivatives; 2,4-dihydroxybenzophenone, 2,2'-
Dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone (oxybenzone-3), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl -Benzophenone ultraviolet absorbers such as benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone; 3- (4'-methylbenzylidene) -d, l- Camphor, 3-benzylidene-d, l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t- Octylphenyl) benzotriazole; 2- (2′-H Dioxy-5'-methylphenylbenzotriazole;dibenzalazine;dianisoylmethane; 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one; di- such as 4-t-butylmethoxydibenzoylmethane Benzoylmethane derivatives; octyl triazone; urocanic acid derivatives such as urocanic acid and ethyl urocanate; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 1- (3,4-dimethoxyphenyl) -4, Hydantoin derivatives such as 4-dimethyl-1,3-pentanedione, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, phenylbenzimidazolazole sulfonic acid, terephthalylidene dicamphulsulfonic acid, drometrizol trisiloxane, anthranyl Methyl, rutin and its derivatives, oryzanol and derivatives thereof as preferred.

  Examples of whitening agents include hydroquinone glycosides such as arbutin and α-arbutin and esters thereof; ascorbic acid phosphate salts such as ascorbic acid, sodium ascorbate phosphate and magnesium ascorbate phosphate, ascorbic acid Ascorbic acid fatty acid esters such as tetraisopalmitic acid ester, ascorbic acid alkyl ethers such as ascorbic acid ethyl ether, ascorbic acid glucosides such as ascorbic acid-2-glucoside and fatty acid esters thereof, ascorbic acid sulfate ester, tocopheryl ascorbyl phosphate Ascorbic acid derivatives such as kojic acid, ellagic acid, tranexamic acid and its derivatives, ferulic acid and its derivatives, placenta extract, glutathione, oryzanol, butylreso Shinoru, oil-soluble Kamomiraekisu, oil-soluble licorice extract, Nishikawa willow extract, be mentioned as saxifrage extract, and the like plant extracts are preferred.

  Vitamins and their derivatives include vitamin A such as retinol, retinol acetate, retinol palmitate; thiamine hydrochloride, thiamine sulfate, riboflavin, riboflavin acetate, pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine dipalmitate, Flavin adenine dinucleotide, cyanocobalamin, folic acid, nicotinic acid such as nicotinic acid amide / benzyl nicotinate, vitamin B group such as choline; vitamin C such as ascorbic acid and its sodium salt; vitamin D; α, Vitamin Es such as β, γ, δ-tocopherol; other vitamins such as pantothenic acid and biotin; ascorbic acid phosphates such as ascorbic acid phosphate sodium salt and ascorbic acid phosphate magnesium salt; Ascorbic acid fatty acid esters such as corobic acid tetraisopalmitic acid ester, ascorbyl stearate, ascorbyl palmitate and ascorbyl dipalmitate, ascorbic acid alkyl ethers such as ascorbic acid ethyl ether, ascorbic acid glucosides such as ascorbic acid-2-glucoside and Ascorbic acid derivatives such as fatty acid esters and tocopheryl phosphate ascorbyl; vitamin derivatives such as tocopherol nicotinate, tocopherol acetate, tocopherol acetate, tocopherol linoleate, tocopherol phosphate, tocopherol phosphate etc., tocotrienol, and other various vitamin derivatives Is preferable.

  Anti-inflammatory and anti-inflammatory agents include glycyrrhizic acid and its derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, guaiazulene, allantoin, indomethacin, zinc oxide, hydrocortisone acetate, prednisone, diphedramine hydrochloride, chlorpheniramine maleate; peach leaf extract A plant extract such as a koji leaf extract is preferable. Plant growth and tinctures such as assembly extract, red pepper tincture, ginger tincture, ginger extract, cantalis tincture; capsaicin, nonyl acid valenylamide, gingeron, ictamol, tannic acid Borneol, cyclandelate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin, γ-oryzanol, cephalanthin, vitamin E and nicotinic acid tocopherol, acetic acid tocopherol and other derivatives, γ-oryzanol, nicotinic acid, nicotinic acid amide, nicotinic acid benzyl Derivatives such as ester, inositol hexanicotinate, nicotine alcohol, allantoin, photosensitizer 301, photosensitizer 401, capronium chloride, pentadecanoic acid monoglyceride, Preferable examples include flavonol derivatives, stigmasterol or stigmasteranol, its glycosides, and minoxidil. Preferred hormones include estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone and the like. Other remedies such as anti-wrinkle agents, anti-aging agents, squeeze agents, cooling sensations, warming sensation agents, wound healing promoters, irritation relievers, analgesics, cell activators include retinols, retinoic acids, retinoin Acid tocopheryl; derivatives such as lactic acid, glycolic acid, gluconic acid, fruit acid, salicylic acid and glycosides / esterified products thereof, α- or such as hydroxycapric acid, long chain α-hydroxy fatty acid, long chain α-hydroxy fatty acid cholesteryl β-hydroxy acids and derivatives thereof; γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid; carnitine; carnosine; creatine; ceramides, sphingosines; caffeine, xanthine and the like; and coenzyme Q10, carotene, lycopene , Astaxanthin, lutein, α-lipoic acid, platinum nanocolloid, fullerenes, etc. Antioxidant / active oxygen scavengers; catechins; flavones such as quercetin; isoflavones; gallic acid and ester sugar derivatives; polyphenols such as tannin, sesamin, protoanthocyanidin, chlorogenic acid, apple polyphenol; rutin and glycosides, etc. Derivatives of hesperidin and glycosides; lignan glycosides; licorice extract-related substances such as grabrizine, glabrene, liquiritin, and isoliquiritin; lactoferrin; shogaol, gingerol; fragrance substances such as menthol, camphor, cedrol, and derivatives thereof Preferred examples include capsaicin, vanillin and the like and derivatives; insect repellents such as diethyltoluamide; and complexes of physiologically active substances and cyclodextrins.

  Plant / animal / microbe extracts include iris extract, ashitaba extract, asunalo extract, asparagus extract, avocado extract, achacha extract, almond extract, altea extract, arnica extract, aloe extract, apricot extract, apricot kernel extract, ginkgo biloba extract , Incheon extract, Fennel extract, Turmeric extract, Oolong tea extract, Peony extract, Ages extract, Echinacea leaf extract, Enmeo extract, Ogon extract, Oat extract, Auren extract, Barley extract, Panax ginseng extract, Hypericum extract, Odori extract , Dutch mustard extract, orange extract, dried sea water, seaweed extract, oyster leaf extract, oyster extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolysis Luc, Cascon extract, Chamomile extract, Oil-soluble chamomile extract, Carrot extract, Kawara mugi extract, Oat extract, Calcade extract, Licorice extract, Oil-soluble Licorice extract, Kiwi extract, Kiou extract, Cyprid extract, Quina extract, Cucumber extract, Kiri leaf extract, Guanosine, guava extract, cucumber extract, gardenia extract, kumazasa extract, clara extract, walnut extract, chestnut extract, grapefruit extract, clematis extract, black rice extract, brown sugar extract, black vinegar, chlorella extract, mulberry extract, gentian extract, Gentian pepper extract, tea Extract, yeast extract, kokuboku extract, coffee extract, burdock extract, rice extract, rice fermented extract, rice bran fermented extract, rice germ oil, comfrey extract, Lagen, Cowberry extract, Saishin extract, Psycho extract, Saitai extract, Saffron extract, Salvia extract, Salmon extract, Sasa extract, Hawthorn extract, Sansha extract, Salamander extract, Shiitake extract, Giant extract, Shikon extract, Perilla extract, Linden extract, Shimosukeso Extract, jatoba extract, peonies extract, ginger cucumber extract, ginger root extract, white birch extract, white jellyfish extract, horsetail extract, stevia extract, stevia fermented product, west river willow extract, horse chestnut extract, hawthorn extract, elderberry extract, yarrow extract , Mint extract, sage extract, mallow extract, nematode extract, essence extract, Sakuhakuhi extract, Diou extract, Dai Extract, peanut extract, thyme extract, dandelion extract, lichen extract, tea extract, clove extract, chigaya extract, chimpi extract, tea tree oil, tea tea extract, red pepper extract, red snapper extract, red snapper extract, red spruce extract, red spruce extract, tomato Extract, natto extract, carrot extract, garlic extract, wild rose extract, hibiscus extract, bacmond extract, lotus extract, parsley extract, birch extract, honey, hamamelis extract, parietalia extract, hyacinth extract, bisabolol, cypress extract, bifidobacteria extract, Loquat extract, dandelion extract, burdock extract, bukkuri extract, butcher bloom extract, grape extract, grape seed extract, propolis, loofah extract, Safflower extract, peppermint extract, body extract, button extract, hop extract, squid extract, pine extract, maroonnier extract, mizubasho extract, mukuroji extract, melissa extract, mozuku extract, peach extract, cornflower extract, eucalyptus extract, yukinoshita extract, yuzu extract, lily extract, Yokuinin extract, mugwort extract, lavender extract, green tea extract, eggshell membrane extract, apple extract, rooibos tea extract, litchi extract, lettuce extract, lemon extract, forsythia extract, forsythia extract, rose extract, rosemary extract, roman chamomile extract, royal jelly Extracts such as an extract and a bitumen extract are preferred.

  Examples of the antipruritic agent include diphenhydramine hydrochloride, chlorpheniramine maleate, camphor, substance-P inhibitor, and the like. Examples of the exfoliating / dissolving agent include salicylic acid, sulfur, resorcin, selenium sulfide, pyridoxine and the like. Examples of the antiperspirant include chlorohydroxyaluminum, aluminum chloride, zinc oxide, and zinc paraphenol sulfonate. Examples of the refreshing agent include menthol and methyl salicylate. Examples of the astringent include citric acid, tartaric acid, lactic acid, aluminum sulfate / potassium sulfate, and tannic acid. Examples of enzymes include superoxide dismutase, catalase, lysozyme chloride, lipase, papain, pancreatin, protease, and the like. Preferred nucleic acids include ribonucleic acid and salts thereof, deoxyribonucleic acid and salts thereof, and adenosine triphosphate disodium.

  As perfumes, acetyl cedrene, amylcinnamaldehyde, allyl amyl glycolate, β-ionone, iso-Esuper, isobutyl quinoline, Iris oil, Iron, indole, ylang ylang oil, undecanal, undecenal, γ-undecalactone, Estragole, eugenol, oak moss, opoponax resinoid, orange oil, eugenol, auranthiol, galac solid, carvacrol, L-carvone, camphor, cannon, carrot seed oil, clove oil, methyl cinnamate, geraniol, geranyl nitrile , Isobornyl acetate, geranyl acetate, dimethylbenzyl carvinyl acetate, styrylyl acetate, cedolyl acetate, terpinel acetate, pt-butylcyclohexyl acetate, vetiberyl acetate, benzyl acetate, vinegar Linalyl, isopentyl salicylate, benzyl salicylate, sandalwood oil, santalol, cyclamenaldehyde, cyclopentadecanolide, methyl dihydrojasmonate, dihydromilsenol, jasmine absolute, jasmine lactone, cis-jasmon, citral, citronenol, citronellal, Cinnamon bark oil, 1,8-cineole, cinnamaldehyde, stylax resinoid, cedarwood oil, cedrene, cedrol, celery seed oil, thyme oil, damascon, damassenone, thymol, tuberose absolute, decanal, decalactone, terpineol, γ-terpinene, Tripral, Nellore, Nonanal, 2,6-Nonadienol, Nonalactone, Patchouli alcohol, Vanilla absolute , Vanillin, basil oil, patchouli oil, hydroxycitronellal, α-pinene, piperitone, phenethyl alcohol, phenylacetaldehyde, petitglen oil, hexylcinnamaldehyde, cis-3-hexenol, peruvian valsum, vetiver oil, vetiverol, peppermint oil, Pepper oil, heliotropin, bergamot oil, benzyl benzoate, borneol, milresinoid, musk ketone, methylnonylacetaldehyde, γ-methylyonone, menthol, L-menthol, L-menthol, eucalyptus oil, β-yonone, lime oil, lavender oil, Synthetic and natural fragrances such as D-limonene, linalool, rilal, rireal, lemon oil, rose absolute, rose oxide, rose oil, rosemary oil, various essential oils, and various blended fragrances It is mentioned as preferred.

As pigments / colorants / dyes / pigments, brown 201, black 401, purple 201, purple 401, blue 1, blue 2, blue 201, blue 202, blue 203, blue 204 , Blue 205, Blue 403, Blue 404, Green 201, Green 202, Green 204, Green 205, Green 3, Green 401, Green 402, Red 102, Red 104-1 , Red 105-1, Red 106, Red 2, Red 201, Red 202, Red 203, Red 204, Red 205, Red 206, Red 207, Red 208, Red 213 Red 214, Red 215, Red 218, Red 219, Red 220, Red 221, Red 223, Red 225, Red 226, Red 227, Red 228, Red 230 No. 1, Red 230-2, Red 231, Red 232, Red 3, Red 401, Red 404, Red 405, Red 501, Red 502, Red 503, Red 504, Red 505, red 506, orange 201, orange 203, orange 204, orange 205, orange 206, orange 207, orange 401, orange 402, orange 403, yellow 201, yellow 202- No. 1, yellow 202-2, yellow 203, yellow 204, yellow 205, yellow 4, yellow 401, yellow 402, yellow 403-1, yellow 404, yellow 405, yellow 406 Legal dyes such as Yellow No. 407 and Yellow No. 5; Other acidic dyes such as Acid Red 14; Arianor Sienna Brown, Arianor Madder Red, Arianor
Basic dyes such as Steel Blue and Arianor Straw Yellow; HC Yellow 2, HC Yellow 5, HC Red 3, 4-hydoxypropylamino-3-nitrophenol, N, N'-bis (2-hydroxyethyl) -2-nitro-p-
Nitro dyes such as phenylenediamine, HC Blue 2 and Basic Blue 26; disperse dyes; inorganic white pigments such as titanium dioxide and zinc oxide; inorganic red pigments such as iron oxide (Bengara) and iron titanate; and γ-iron oxide Inorganic brown pigments; inorganic yellow pigments such as yellow iron oxide and ocher; inorganic black pigments such as black iron oxide and low-order titanium oxide; inorganic purple pigments such as mango violet and cobalt violet; chromium oxide and chromium hydroxide Inorganic green pigments such as cobalt titanate; inorganic blue pigments such as ultramarine and bitumen; titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil Pearl powder such as aluminum powder, copper powder, metal powder pigment such as gold; surface treatment inorganic and metal powder pigment; red 01, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401, Blue 404 Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1 organic pigments such as zirconium, barium or aluminum lakes; Surface treatment organic pigments; Naphthoquinones such as chlorophyll, curcumin, cochineal, shikonin, bixin, flavo Natural pigments and dyes such as amines, betacyanidine, henna, hemoglobin, lycopene, riboflavin, rutin; p-phenylenediamine, toluene-2,5-diamine, o-, m-, or p-aminophenol, m-phenylene Oxidative dye intermediates and couplers such as diamine, 5-amino-2-methylphenol, resorcin, 1-naphthol, 2,6-diaminopyridine and their salts; auto-oxidizing dyes such as indoline; Can be mentioned.

  Preferred examples of water include normal water, purified water, hard water, soft water, natural water, deep sea water, electrolytic alkaline ionized water, electrolytic acidic ionized water, ionic water, and clustered water.

  In addition to these, cosmetic raw material standards, blending ingredient standard by cosmetic varieties, Japan Cosmetic Industry Association ingredient display name list, INCI dictionary (The International Cosmetic Ingredient Dictionary and Handbook), quasi-drug raw material standards, Japanese pharmacopoeia, pharmaceutical additives Ingredients listed in standards, official food additives, etc., and Japanese and foreign patent publications and patent publications (including publications and republications) in which the international patent classification IPC belongs to the classification of A61K7 and A61K8 It is possible to contain known cosmetic ingredients, pharmaceutical ingredients, food ingredients, etc., such as the ingredients described, in known combinations, blending ratios and blending amounts.

  As the types of cosmetics or skin external preparations containing the ascorbic acid derivative of the present invention, skin external preparations such as hair cosmetics, basic cosmetics, makeup cosmetics, aromatic cosmetics, body cosmetics, and ointments are preferable. As mentioned. The cosmetic / skin external preparation of the present invention can be produced according to a usual method.

  The cosmetic or skin external preparation containing the ascorbic acid derivative of the present invention will be described in more detail. Examples of the hair cosmetic include oil shampoo, cream shampoo, conditioning shampoo, dandruff shampoo, hair color shampoo, and rinse. Shampoo such as integrated shampoo; rinse, treatment, hair pack, hair foam, hair mousse, hair spray, hair mist, hair wax, hair gel, water grease, set lotion, color lotion, hair tonic, hair liquid, pomade, tic, hair cream , Hair blow, split hair coat, hair oil, permanent wave agent, straight perm agent, oxidation hair dye, hair bleach, hair color pre-treatment, hair color after treatment, perm Les treatment, permanent after-treatments, hair manicure, and as hair growth agents are preferred.

  Basic cosmetics include soft lotion, astringent lotion, cleansing lotion, multi-layer lotion, etc .; emollient lotion, moisture lotion, milky lotion, nourishing lotion, nourishing milk, skin moisture, moisturizer -Emulsions such as emulsion, massage lotion, cleansing lotion, protect emulsion, sun protect, sun protector, UV care milk, sunscreen, makeup lotion, horny smoother, elbow lotion, hand lotion, body lotion; emollient cream, nutritional cream, nari Thing cream, burnishing cream, moisture cream, night cream, massage cream, cleansing cream, makeup cream, base cream Cream, sun makeup cream, suntan cream, hair removal cream, deodorant cream, shaving cream, keratin softening cream, etc .; gel such as moisture gel; essence such as moisturizing essence, whitening essence, UV protection essence; liposome Liposome cosmetics such as beauty essence and liposome lotion; Peel-off packs, powder packs, washing packs, oil packs, cleansing masks and other packs and masks; cleansing foams, cleansing creams, cleansing milks, cleansing lotions, cleansing gels, cleansing oils , Cleansing mask, washing powder, face washing powder, etc .; cosmetic soap, transparent soap, medicated soap, liquid soap, shaving soap, synthetic cosmetic soap Soap can be mentioned as preferred.

  Examples of makeup cosmetics that may be preferably used include white powder, dusts, foundations, lipsticks, lip gloss, blushers, eyeliner, mascara, eye shadow, eyebrow, eyebrow, nail enamel, enamel remover, and nail treatment.

  Preferred examples of the aromatic cosmetics include perfume, perfume, parfum, eau de parfum, eau de toilette, eau de cologne, perfumes, fragrance powder, perfume soap, body lotion and bath oil.

  Body cosmetics such as body shampoos; deodorant lotions, deodorant powders, deodorant sprays, deodorant sticks and other deodorant cosmetics; decoloring agents, hair removal / hair removal agents; bathing agents; insect repellents A repeller is preferred.

  Moreover, as a skin external preparation, it can be used with dosage forms, such as an ointment, a patch, a lotion agent, a liniment agent, and a liquid coating agent. It can also be used as an oral cosmetic such as toothpaste and mouthwash.

  The cosmetic or skin external preparation containing the ascorbic acid derivative of the present invention includes an oil-in-water (O / W) type, a water-in-oil (W / O) type, a W / O / W type, and an O / W type. / O type emulsified cosmetics, oily cosmetics, solid cosmetics, liquid cosmetics, paste cosmetics, stick cosmetics, volatile oil cosmetics, powder cosmetics, jelly cosmetics, gels Preferable examples include dosage forms such as cosmetics, pastes, emulsified polymer cosmetics, sheet cosmetics, mist cosmetics, and spray cosmetics.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples.

Example 1 Synthesis of 2,3-di-O-ethyl-L-ascorbic acid 100 g of 5,6-O-isopropylidene-L-ascorbic acid was added to a 300 mL reactor equipped with a stirrer, thermometer and gas introduction tube. (0.47 mol), 146 g (0.94 mol) of diethyl sulfate, and 200 g of acetone were adjusted to pH 10 with 48% sodium hydroxide, and the pH was adjusted to 8 to 10 with 48% sodium hydroxide under a nitrogen atmosphere. The reaction was carried out at 50 ° C. for 10 hours. After acetone was distilled off from the obtained reaction solution, 300 g of toluene and 200 g of water were charged, the target product was extracted into the toluene phase, and washed with water three times. The toluene phase was concentrated under reduced pressure, 100 g of methanol, 60 g of water and 2 g of concentrated hydrochloric acid were added and stirred at 50 ° C. for 5 hours, and then adjusted to pH 7 with 48% sodium hydroxide. To this liquid was added 100 g of toluene for liquid separation, and then the aqueous phase was concentrated under reduced pressure to obtain 56 g of the desired crude product. The obtained crude product (5.0 g) was further purified using a silica gel column chromatography method to obtain the desired 2,3-di-O-ethyl-L-ascorbic acid (3.0 g) as a white solid.

The structure of the compound obtained in Example 1 was identified by nuclear magnetic resonance spectrum (apparatus: JNM-AL, 300 MHz, measurement: ¹ H-NMR, solvent: CD ₃ OD manufactured by JEOL Ltd.). The results are shown in Table 1. In addition, the structural formula of the compound obtained in Example 1 is shown in Chemical Formula 3, and the assignment number of ¹ H-NMR is also written in the formula.

Physiological activity evaluation 1 Whitening evaluation Using mouse-derived B16 melanoma cultured cells, the melanin production inhibitory effect of the compound of Example 1 was examined. For comparison, 3-O-ethyl-L-ascorbic acid was used. The measurement method was as follows, and the results are shown in Table 2.

(Measuring method)
After suspending mouse-derived B16 melanoma cultured cells in D-MEM medium containing 2 mM theophylline and 10% FBS, 2 × 10 ⁴ cells were seeded per well in a 12-well cell culture plate, and a CO ₂ incubator (95% The cells were cultured for 24 hours at 37 ° C. in air and 5% carbon dioxide. Thereafter, the test sample was replaced with a medium in which the test sample was dissolved in advance (the sample concentration in the medium was 0.1 w / v%), and the culture was further continued for 3 days. The medium was then removed, washed with phosphate buffer, the cells were lysed with 1N sodium hydroxide solution, and the melanin content was measured by measuring the absorbance at 405 nm. When the amount of melanin when the test sample was added was X and the amount of melanin when the test sample was not added was Y, the melanin production inhibition rate was calculated by the following formula.

Melanin production inhibition rate (%) = (1−X / Y) × 100

Physiological activity evaluation 2 Whitening evaluation The whitening action of the compound of Example 1 was examined using a melanocyte-containing human three-dimensional epidermis model. For comparison, 3-O-ethyl-L-ascorbic acid was used. The measurement method was as follows, and the results are shown in Table 3.

(Measuring method)
To the melanocyte-containing human three-dimensional epidermis model (LabCyte MELANO-MODEL, manufactured by J-TEC), add 50 μL of the phosphate buffer solution (concentration: 1.0 w / v%) of the test sample to the surface (corneal layer side) of the epidermis model. The cells were cultured in a CO2 incubator at 37 ° C. Thereafter, the medium was changed and the sample was added every 1 to 2 days and cultured for 14 days. Thereafter, the degree of blackness of the skin model was visually evaluated.

  From the results of Tables 2 and 3, it was found that the compound of Example 1 which is an ascorbic acid derivative of the present invention has a whitening effect equivalent to that of 3-O-ethyl-L-ascorbic acid.

Bioactivity Evaluation 3 Collagen Production Promotion Evaluation Using cultured human skin fibroblasts, the collagen production promotion action of the compound of Example 1 was examined. For comparison, 3-O-ethyl-L-ascorbic acid was used. The measurement method was as follows, and the results are shown in Table 4.

(Measuring method)
Cultured human skin fibroblasts were suspended in D-MEM medium containing 10% FBS, and then seeded at 1.0 × 10 ⁴ cells per well in a 48-well cell culture plate, and CO ₂ incubator (95% air (5% carbon dioxide) and cultured at 37 ° C. for 2 days. After replacing with a serum-free medium and culturing for 24 hours, the medium was replaced with a medium in which the concentration of the test sample in the medium was 5 ppm (w / v) or 15 ppm (w / v), and further cultured for 2 days. The type I procollagen C-terminal peptide in the culture supernatant was quantified by an enzyme immunoassay (ELISA method) using a commercially available kit (Procollagen type I C-peptide EIA Kit manufactured by Takara Bio Inc.). The results are shown as relative values when the amount of collagen produced when no test sample is added (control) is taken as 100%.

  From the results of Table 4, it was found that the compound of Example 1, which is an ascorbic acid derivative of the present invention, has a collagen production promoting action equivalent to 3-O-ethyl-L-ascorbic acid.

Examples 2 to 5 Stability test A lotion containing the compound of Example 1 was prepared (Table 5). The pH of the skin toner was adjusted to 4.0-7.0. As a comparison, cosmetics using 3-O-ethyl-L-ascorbic acid instead of the compound of Example 1 were prepared (Table 6). About these lotions, pH and residual rate after 1-month storage at 50 degreeC were measured. The residual rate was measured using a liquid chromatograph and expressed as a relative value with respect to the initial peak area. The results are shown in Tables 5 and 6. From the results, the compound of Example 1 had a higher residual rate at pH 6.0 to 7.0 and excellent stability than 3-O-ethyl-L-ascorbic acid. In addition, 3-O-ethyl-L-ascorbic acid was greatly reduced in pH at pH 6.0 to 7.0, whereas the compound of Example 1 had little pH reduction and excellent pH stability. I understood.

High-performance liquid chromatographic conditions 2,3-di-O-ethyl-L-ascorbic acid (column: octadecylsilylated silica gel column, elution solvent: 0.01M sodium dihydrogen phosphate aqueous solution / acetonitrile = 7/3, UV absorption detection : 245 nm)
3-O-ethyl-L-ascorbic acid (column: octadecylsilylated silica gel column, elution solvent: 0.01 M aqueous sodium dihydrogen phosphate / acetonitrile = 96/4, ultraviolet absorption detection: 245 nm)

Example 6 Emulsion An emulsion having the following formulation was prepared. This emulsion showed an appropriate viscosity, was excellent in spreading, and was excellent in use feeling.

Component Blending amount (% by weight)
--------------------------------------
Part A cetanol 0.20
Squalane 0.05
Soybean oil 0.05
Behenez-30 0.05
Ethylhexyl methoxycinnamate 0.05
Tocopherol 0.05
Part B stearoxyhydroxypropylmethylcellulose 0.40
Purified water 20.00
Part C Compound of Example 1 0.50
Hydroxyethyl ethylenediamine triacetate 0.01
Hyaluronic acid Na 0.03
Sorbitol 6.00
Succinic acid 0.03
Sodium succinate proper amount diglycerin 0.15
Apple polyphenol 0.02
Phenoxyethanol 0.20
Methylparaben 0.15
Purified water Total amount of 100 --------------------------------------
(Preparation method)
Part A was heated to about 70 ° C. and dissolved uniformly. Part B was stirred to obtain a viscous liquid. Add part C heated to about 70 ° C. to part A, stir to emulsify, then cool and add part B at about 50 ° C., stir to dissolve uniformly, and pH 6.0 with Na succinate. did.

Example 7 Cream A cream having the following formulation was prepared. This cream showed an appropriate viscosity, was excellent in spreading, and was excellent in use feeling.

Component Blending amount (% by weight)
--------------------------------------
Part A batyl alcohol 2.00
Squalane 2.00
Glyceryl tri-2-ethylhexanoate 3.00
Stearic acid 1.00
Macadamia nut oil fatty acid phytosteryl 1.00
Natural vitamin E 0.05
Behenyl alcohol 2.00
Lipophilic glyceryl monostearate1.00
Ethylparaben 0.15
Methyl polysiloxane 0.50
Polyoxyethylene cetyl ether 2.00
Phytocompo-PP (Nippon Seika) 0.50
Part B (acryloyldimethyltaurate ammonium /
Methenic acid behenes-25) cross polymer 0.20
Purified water 20.00
Part C Compound of Example 1 2.00
Succinic acid 0.01
Sodium succinate proper amount 1,3-butylene glycol 0.15
Hydrolyzed collagen 0.20
Hydroxyethane diphosphonic acid solution 0.03
Concentrated glycerin 0.20
Methylparaben 0.10
Purified water Total amount of 100 --------------------------------------
(Preparation method)
Part A was heated to about 70 ° C. and dissolved uniformly. Part B was stirred to obtain a viscous liquid. Part C was heated to about 70 ° C. and dissolved uniformly. C part was added to A part, stirred and emulsified and then cooled. Part B was added at about 50 ° C. and stirred to dissolve uniformly, and the pH was adjusted to 6.0 with Na succinate.

Example 8 Emulsion An emulsion having the following formulation was prepared. This emulsion showed an appropriate viscosity, was excellent in spreading, and was excellent in use feeling.

Component Blending amount (% by weight)
--------------------------------------
Part A sorbitan stearate 0.50
PEG-10 stearate 0.50
Polysorbate 60 0.50
Cetyl octanoate 3.70
Cetanol 1.20
Dimethicone (10cs) 1.00
Ethylparaben 0.10
Part B (acryloyldimethyltaurate ammonium / VP) copolymer 0.05
Stearoxyhydroxypropylmethylcellulose 0.10
Xanthan gum 0.10
Carbomer 0.15
Hydroxide K 0.06
Purified water 20.00
Part C Compound of Example 1 0.50
1,3-butylene glycol 3.00
Cyclohexanedicarboxylic acid bisethoxydiglycol 1.00
Glycerin 1.00
Phenoxyethanol 0.20
Methylparaben 0.15
Phytic acid 0.50
Citric acid 0.01
Na citrate 0.09
Purified water Total amount of 100 --------------------------------------
(Preparation method)
Part A was heated to about 70 ° C. and dissolved uniformly. Part B was stirred to obtain a viscous liquid. Part C was heated to about 70 ° C. and dissolved uniformly. C part was added to part A, emulsified with a homomixer and then cooled. Part B was added at about 50 ° C., stirred and dissolved uniformly, and adjusted to pH 6.0 with sodium citrate.

Example 9 Lotion Toner lotion having the following formulation was prepared. This lotion was excellent in use feeling and moisturizing feeling.

Component Blending amount (% by weight)
--------------------------------------
Part A xanthan gum 0.30
Carbomer 0.20
Tremoist-TP (Nippon Seika) 0.20
Purified water 20.00
Part B (eicosanedioic acid / tetradecanedioic acid) polyglyceryl 1.00
BG 1.00
Glycerin 2.00
Ubiquinone 0.03
IOTG (Japan Seika) 0.03
Tetraoleic acid Solves-60 0.12
PEG-60 hydrogenated castor oil 0.03
PEG-30 glyceryl isostearate 0.03
Methylparaben 0.20
Fragrance Trace amount ethanol 7.00
Part C Compound of Example 1 0.50
Ascorbic acid 2-glucoside 2.00
Citric acid 0.01
Sodium citrate appropriate amount glutamic acid diacetate 4Na 0.80
Purified water Total amount of 100 --------------------------------------
(Preparation method)
Part A was stirred to obtain a viscous liquid. Part B was heated to about 70 ° C. and dissolved uniformly. Part B was added to part C at about 50 ° C. and stirred to dissolve uniformly. Further, part A was added and stirred to dissolve uniformly, and the pH was adjusted to 7.0 with sodium citrate.

Example 10 Lotion Toner lotion having the following formulation was prepared. This lotion was excellent in use feeling and moisturizing feeling.

Component Blending amount (% by weight)
--------------------------------------
Part A Glycerin 2.00
Methylparaben 0.10
Phenoxyethanol 0.20
Ethanol 5.00
Part B Compound of Example 1 0.50
Arbutin 3.00
Glycine 0.20
BG 2.00
Polyethylene glycol 1500 2.00
Polyglutamic acid solution 1.00
Anhydrous sodium sulfite 0.20
Citric acid 0.01
Sodium citrate appropriate amount edetic acid 3Na 0.10
Purified water Total amount of 100 --------------------------------------
(Preparation method)
A part and B part were stirred and dissolved uniformly. Next, part B was added to part A, stirred and dissolved uniformly, and adjusted to pH 5.0 with sodium citrate.

Example 11 Lotion Toner lotion having the following formulation was prepared. This lotion was excellent in use feeling and moisturizing feeling.

Component Blending amount (% by weight)
--------------------------------------
Part A stearoxyhydroxypropyl methylcellulose 0.60
Tremoist-TP (Nippon Seika) 0.20
Purified water 20.00
Part B Compound of Example 1 0.50
Ascorbyl ethyl (Nippon Seika) 1.00
Ethanol 7.00
BG 7.00
Glycerin 5.00
Methylparaben 0.10
Phenoxyethanol 0.20
Citric acid 0.10
Sodium citrate appropriate amount Penteto acid 5Na 0.10
Purified water Total amount of 100 --------------------------------------
(Preparation method)
Part A was stirred to obtain a viscous liquid. Part B was heated to about 70 ° C. and dissolved uniformly. Part A was added to part B at about 50 ° C., and the mixture was stirred and dissolved uniformly. The pH was adjusted to 4.0 with Na citrate.

Claims (3)

Cosmetic or skin external preparation characterized by containing an L-ascorbic acid derivative represented by the following general formula (1)

(Wherein R1 and R2 represent an ethyl group ) The cosmetic or skin external preparation according to claim 1, wherein the cosmetic or skin external preparation is used for whitening. The cosmetic or skin external preparation according to claim 1, which is for promoting collagen production.