CN101316574A - Skin care cosmetic and skin and agent for preventing skin roughness containing biosurfactants - Google Patents

Skin care cosmetic and skin and agent for preventing skin roughness containing biosurfactants Download PDF

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Publication number
CN101316574A
CN101316574A CNA200680044160XA CN200680044160A CN101316574A CN 101316574 A CN101316574 A CN 101316574A CN A200680044160X A CNA200680044160X A CN A200680044160XA CN 200680044160 A CN200680044160 A CN 200680044160A CN 101316574 A CN101316574 A CN 101316574A
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mel
skin
biosurfactant
oil
pachylosis
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北川优
铃木道子
山本周平
曽我部敦
北本大
井村知弘
福冈德马
森田友岳
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National Institute of Advanced Industrial Science and Technology AIST
Toyobo Co Ltd
Toyo Textile Co Ltd
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National Institute of Advanced Industrial Science and Technology AIST
Toyo Textile Co Ltd
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Abstract

A cosmetic aiming at preventing skin roughness/skin care which contains biosurfactants, in particular, MEL-A, MEL-B and MEL-C.

Description

The skin nursing cosmetic material and the pachylosis improving agent that comprise biosurfactant
Technical field
The present invention relates to biosurfactant or its premixing product are used for skin nursing/pachylosis improvement, especially biosurfactant is used as cosmetics, further relate to the cosmetic material that skin nursing/pachylosis improves, it comprises biosurfactant or its premixing product.More particularly, the present invention relates to a kind of cosmetic material, it is characterized in that: biosurfactant is mannose erythrose alcohol ester (hereinafter to be referred as " MEL "), mannose erythrose alcohol ester A (hereinafter to be referred as " MEL-A ") for example, mannose erythrose alcohol ester B (hereinafter to be referred as " MEL-B ") or mannose erythrose alcohol ester C (hereinafter to be referred as " MEL-C "); Or mannose mannose alcohol ester (hereinafter to be referred as " MML ").In addition, the present invention relates to a kind of pachylosis improving agent.
Background technology
Scurf is meant that skin is in drying regime, observes the exfoliation of horn cell on skin.The formation of this class scurf owing to lipid between horn cell for example cholesterol, ceramide and fatty acid stripping and be attributable to ultraviolet and the horn cell degeneration of detergent and epidermis cell in propagation/keratinization balance disorderly and to cause the horny layer permeability barrier to form incomplete.In order to prevent or treat the purpose of aforementioned scurf, people have replenished between cutin between cytolipin composition or synthetic cutin the cytolipin analog in the subtend skin and have studied.
The intercellular substance of biosynthetic lamella (Lamella) granule below exactly being arranged in horny layer discharges in cell spinous layer and granulosa, extends to form lamellar structure, and expands in intercellular substance, produces lipid between aforesaid horn cell.The lamella granule is made up of glycosyl ceramide, cholesterol, ceramide, phospholipid or the like; Yet, between horn cell, almost seldom comprise glycosyl ceramide in the lipid.That is to say, it is believed that, glycosyl ceramide in the lamella granule is by β-ceramide glucoside enzyme hydrolysis, and change ceramide into, and this ceramide forms lamellar structure, cause formation improvement, serve as the barrier that prevents scurf as the horny layer permeability barrier of lipid between horn cell.It is reported that the ceramide enriching substance can effectively overcome the pachylosis that causes owing to detergent, and can improve pachylosis (non-patent literature 1) efficiently.
Plant extraction liquid mainly is made up of glycosyl ceramide, but still is not the substitute of gratifying ceramide.Many reactions steps are arranged, and its large-scale production cost is very high between its synthesis stage.
MEL is the natural surfactant that yeast produces, and has before reported its various physiological actions (non-patent literature 2).Recently, had been found that by substituting the mannose mannose alcohol ester (MML) (patent documentation 1) that erythritol obtains with mannitol.It has been recognized that their purposes and their antibacterial action (patent documentation 4) and surface tension reduction effects (patent documentation 5) in external prepared product and cosmetics as antiinflammatory and anti-allergic agent (patent documentation 2), and hair growth medicine (patent documentation 3) bald as treatment; Yet MEL still is unknown as the purposes of the substitute that effectively improves pachylosis.
Patent documentation 1:JP 2005-104837-A
Patent documentation 2:JP 2005-68015-A
Patent documentation 3:JP 2003-261424-A
Patent documentation 4:JP Sho-57-145896-A
Patent documentation 5:JP Sho-61-205450
Non-patent literature 1: skin and beauty treatment, 36:210,2004
Non-patent literature 2:Journal of Bioscience and Bioengineering 94:187,2002
Summary of the invention
The problem that the present invention solves
The composition that ceramide can be used as in the cosmetics is used to improve pachylosis, but because the extraction product in synthetic product or the plant is very expensive, only uses ceramide at present on a small quantity.Main purpose of the present invention provides the external prepared product of skin, and it uses the substitute of the biosurfactant of microorganisms as ceramide.That is to say, the invention provides biosurfactant,, obtain the improvement of scurf thus, and it is the lipid components that obtains easily, as the external prepared product of skin by its formation that has improved the horny layer permeability barrier.
The method of dealing with problems
Owing to carried out thorough research to addressing the above problem, it is found that, after joining biosurfactant in the pachylosis model (making by the three-dimensional skin model of sodium lauryl sulphate (SDS) defat), biosurfactant plays the effect of the substitute of ceramide; By (produce) application at the scurf position, further proved the purposes of biosurfactant by skin with the SDS handler.In brief, it is found that biosurfactant not only can be used as emulsifying agent and uses, and uses but also can substitute ceramide; Finish the present invention thus.
The present invention relates to following skin nursing cosmetic material and pachylosis improving agent.
(1) skin nursing is made up and is expected that it comprises at least a biosurfactant.
(2) according to the skin nursing cosmetic material of (1), it is used to improve pachylosis.
(3) according to the skin nursing cosmetic material of (1), it is used for the improved effect pachylosis by surfactant.
(4) according to the skin nursing cosmetic material of (1), wherein biosurfactant is mannose erythrose alcohol ester (MEL) and/or mannose mannose alcohol ester (MML).
(5) according to the skin nursing of (1) material of making up, wherein biosurfactant is to be selected from least a among mannose erythrose alcohol ester A (MEL-A), mannose erythrose alcohol ester B (MEL-B) and the mannose erythrose alcohol ester C (MEL-C).
(6) according to the skin nursing cosmetic material of (1), wherein biosurfactant is mannose erythrose alcohol ester B (MEL-B).
(7) according to the skin nursing cosmetic material of (1), wherein biosurfactant is mannose erythrose alcohol ester C (MEL-C).
(8) according to the skin nursing cosmetic material of (1), wherein biosurfactant is mannose erythrose alcohol ester A (MEL-A).
(9) a kind of pachylosis improving agent, it is made up of at least a biosurfactant.
Effect of the present invention
Have been found that in the present invention the MELs and the MML (being the biosurfactant by microorganisms) that can use such as MEL-A, MEL-B and MEL-C replace ceramide, be used for skin nursing and pachylosis and improve.Biosurfactant of the present invention can the large-scale production by cultivating microorganism.By using this ceramide substitute, can expect pachylosis improvement/skin nursing effect and emulsification.Thus, can obtain effectively to improve the external preparation for skin prepared product of pachylosis.Especially, MEL-B and MEL-C are highly hydrophilic, and can be prepared into stable emulsifying agent.Biosurfactant can use with the form of premixing product.
MELs preferably, because thereby MELs can be combined in cosmetic material and the external prepared product that is used for skin by being dissolved in oil base or the lipophilic component, and can be by MEL is incorporated in the liposome, with aqueous solution (skin astringent for example, moisture retention liquid) form preparation, it can be introduced in the skin with flying colors.Liposome can use with the form of non-aqueous solution.Will all not be formed in the liposome by all MELs, the MELs of liposome form can be mixed with the MELs or the monomer M ELs of sheet-shaped.
Biosurfactant of the present invention is particularly useful as skin nursing cosmetic material and is used as the cosmetic material that improves pachylosis; It also uses valid medicine and medicine, for example treating skin disease agent, described dermatosis for example moderate to pachylosis, acne, eczema, asteatosis, old xeroderma and the skin pruritus of severe.
Biosurfactant can be as expecting the composition of combination with washing with making up, this is that biosurfactant also has washing (-)off properties because except pachylosis improvement/skin nursing effect.
Brief description of drawings
Fig. 1 is the design sketch of MEL in pachylosis model (use three-dimensional skin model to make, and handle with SDS) by survival rate (absorbance of first hairpin) expression;
Fig. 2 is expression when the emulsifiable paste that comprises MEL-A is applied on people's arm top skin of the roughening with SDS processing, the figure of moisture recovering effect in the horny layer;
Fig. 3 is the design sketch in pachylosis model (use three-dimensional skin model to make, and handle with SDS) by MEL-A, the MEL (OL) of survival rate (absorbance of first hairpin) expression and MEL (MY); MEL-A=is by cultivating the MEL that produces with soybean oil; MEL (MY)=by cultivate the MEL that produces with methyl myristate; MEL-A (OL)=by cultivate the MEL that produces with olive oil;
Fig. 4 is the design sketch in pachylosis model (use three-dimensional skin model to make, and handle with SDS) by the MEL-B of survival rate (absorbance of first hairpin) expression and MEL-C; MEL-B more can improve the improvement of pachylosis than MEL-A; In the drawings, MEL-A (OL) is to use the MEL-A of olive oil as feedstock production, MEL-B (OL) is to use the MEL-B of olive oil as feedstock production, MEL-A (SB) is to use the MEL-A of soybean oil as feedstock production, MEL-B (SB) is to use the MEL-B of soybean oil as feedstock production, and MEL-C (SB) is to use the MEL-C of soybean oil as feedstock production;
Fig. 5 is expression when the emulsifiable paste that comprises MEL-B is applied on people's arm top skin of the roughening with SDS processing, moisture recovering effect figure in the horny layer;
Fig. 6 is the figure of the dispersion stabilization of expression MEL-B and MEL-C.Aspect aqueous dispersion stability, MEL-B and MEL-C are outstanding than MEL-A; Almost do not observe muddy the variation, this is because still keep stable suspended state after 6 hours; With
Fig. 7 is expression when using three-dimensional skin model that MEL-B liposome aqueous solution and MEL-B suspension are carried out the as a result figure of pachylosis when testing, and has checked effect.
Implement best mode of the present invention
" biosurfactant " of this paper is the generic name that produces, has the material of surface activity effect and emulsification by organism, it not only demonstrates outstanding surface activity and high biological degradability, and because have various physiological actions, thereby demonstrate the behavior that is different from those synthetic surfactants and the probability of function.
" premixing product " are meant the material that has also added dispersant and obtain except adding functional materials, thereby perhaps with solvent dilution wieldy material when making cosmetics.Biosurfactant of the present invention can provide with the form of premixing product, has wherein mixed dispersant and solvent, as the cosmetic material or the cosmetics additive that are used for pachylosis improvement/skin nursing.
Ceramide is the sphingolipid that occupies about 50% iuntercellular lipid in horny layer.The previous ceramide that is obtained by Medulla Bovis seu Bubali that usually uses, but because the spreading of bovine spongiform encephalopathy need be used for the ceramide that obtains from plant of cosmetics.
The effect of class ceramide is the effect that improves colour of skin decline and the decline of cosmetics adaptability of main iuntercellular composition ceramide in keratodermatitis.Independent biosurfactant has the pachylosis improvement/skin nursing effect of class ceramide; By making up, can improve the effect of biosurfactant with ceramide.
An advantage with biosurfactant of class ceramide effect is that large-scale production easily also can be used with the emulsifying agent form.Therefore, biosurfactant of the present invention has more purposes than existing ceramide.
For biosurfactant, can use trehalose lipid, rhamnolipid, sophorolipid, surface activity element, spiculisporic acid, latex, MEL, MML or the like, but the preferred biosurfactant that forms lamellar structure that uses.Among these biosurfactants, preferred MEL and MML, more preferably MEL-A, MEL-B or MEL-C, especially preferably MEL-B or MEL-C.
The biosurfactant that forms lamellar structure comprises MEL and MML, particularly including MEL.
In one embodiment of the invention, preferred MELs comprises by the MEL-A of formula (I) representative, by the MEL-B of formula (II) representative and three types of MEL-C of being represented by formula (III); Can be used alone or in combination these.More preferably by the MEL-A of formula (I) representative and the MEL-B that represents by formula (II), the most preferably MEL-B that represents by formula (II).
MML is by formula (IV) representative (in formula, any one of in mannose 4 and 6 or two acetyl group can be replaced by hydroxyl).
R 1And R 2Have 1 to 19 carbon atom separately, preferred 1 to 17, and more preferably 7 to 15.
R 1And R 2Can be identical or different, and comprise C 1To C 19Alkyl, C 2To C 19Thiazolinyl, C 5To C 19Dialkylene and C 8To C 19Trialkenyl.
In formula (I), (II), (III) with (IV), R 1And R 2Preferred group comprise C 1To C 19Alkyl, for example CH 3(CH 2) 6, CH 3(CH 2) 8, CH 3(CH 2) 10CH 3(CH 2) 12, CH 3(CH 2) 14, CH 3(CH 2) 16And CH 3(CH 2) 18Formula (I), (II) or (III) in MEL and the MML in the formula (IV), wherein R 1And R 2Be C 1To C 19Alkyl, can followingly obtain: for example first carboxylic acid for example formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid, lauric acid, myristic acid, Palmic acid, stearic acid, oleic acid and palmitoleic acid or its ester (mono alkyl ester are unified in saturated carboxylic acid or insatiable hunger with raw material, single, two-, triglyceride, comprise that perhaps these satisfied fatty acid or insatiable hunger close the oils and fats of mono fatty acid) join in the culture medium.When insatiable hunger is closed carboxylic acid for example oleic acid or palmitoleic acid are as raw material, introduce insatiable hunger and close carboxylic acid or the product during its beta oxidation, thus for R 1And R 2, alkyl becomes major part, and thiazolinyl becomes a small amount of part.Equally, formula (I), (II) or (III) in MEL and the MML in the formula (IV), wherein R 1And R 2Be C 2To C 19Thiazolinyl, C 5To C 19Dialkylene or C 8To C 19Trialkenyl, can followingly obtain: the linoleic acid, linolenic acid, arachidonic acid, EPA, DHA or its ester (mono alkyl ester that raw material are for example had two or more pairs of keys, single, two-, triglyceride, perhaps comprise the oils and fats of its highly unsaturated fatty acid) join in the culture medium.For example, when linoleic acid is used as raw material, for R 1And R 2, thiazolinyl becomes major part, and dialkylene becomes a small amount of part.When linolenic acid is used as raw material, for R 1And R 2, dialkylene becomes major part, and thiazolinyl or trialkenyl become a small amount of part.
These biosurfactants can be used separately, maybe two or more biosurfactants can be used in combination.
Figure A20068004416000101
In formula (I) in (IV), R 1And R 2Can be identical or different, and the expression hydrogen atom; Straight or branched C 1To C 19, preferred C 1To C 17, and more preferably C 7To C 15Alkyl; Straight or branched C 2To C 19, preferred C 2To C 17, and more preferably C 7To C 15Thiazolinyl; Straight or branched C 5To C 19, preferred C 5To C 17, and more preferably C 7To C 15Dialkylene; Perhaps straight or branched C 8To C 19, preferred C 8To C 17, and more preferably C 8To C 15Trialkenyl.
Be not particularly limited for the method for preparing biosurfactant, can randomly select to use the fermentation method of microorganism.For example, can prepare MELs (MEL-A, MEL-B and MEL-C) by cultivating Pseudozymaantarctica NBRC 10736 according to standard method.Can use Pseudozyma antarctica, pleomorphism Saccharomycodes (Pseudozyma sp.) or the like as microorganism.As everyone knows, can from any microorganism, easily obtain the MEL mixture.Use the silica gel chromatography can purification MEL mixture, isolate MEL-A, MEL-B and MEL-C.The microorganism that Pseudozyma antarctica and Pseudozyma tsukubaensis are considered to produce MEL-B can be used these microorganisms.Pseudozymahubeiensis is considered to produce the microorganism of MEL-C, can use this microorganism.Be not particularly limited for having the microorganism of producing the MEL ability, can suitably select according to purpose.
Culture medium for the fermenting and preparing biological surfactant, can use the common culture medium of forming by N source (for example yeast extract and peptone), C source (for example glucose and fructose), inorganic salt (for example Chile saltpeter, dipotassium hydrogen phosphate and magnesium sulfate heptahydrate) and can use to wherein adding one or two or more non-water-bed thing oils and fats such as olive oil, soybean oil, Oleum helianthi, Semen Maydis oil, Canola oil and Oleum Cocois and hydrocarbon those culture medium of liquid paraffin and the tetradecane for example for example.
Can choose wantonly and set fermentation condition for example pH value, temperature and time cycle, and the culture medium after the fermentation can directly be used as biosurfactant of the present invention.If necessary, after the fermentation, in essence of the present invention does not have impaired scope, can with optional operational example as filter, centrifugal, extraction, purification and sterilization be applied to culture medium, and can dilute, concentrate and dry resulting extract.
Be not particularly limited for Vegetable oil lipoprotein, and can suitably select according to purpose as raw material; These can comprise soybean oil, Oleum Brassicae campestris, Semen Maydis oil, Oleum Arachidis hypogaeae semen, Oleum Gossypii semen, safflower oil, Oleum sesami, olive oil and Petiolus Trachycarpi oil.Among them, just enhance productivity (volume of production, speed of production and productive rate), preferred especially soybean oil.Can use separately or two or more are used in combination these.
Be not particularly limited for inorganic nitrogen-sourced, and can suitably select according to purpose; Example comprises ammonium nitrate, urea, Chile saltpeter, ammonium chloride and ammonium sulfate.
Method for collection and purifying biological surfactant is not particularly limited, and can suitably select according to purpose; For example by culture medium is centrifugal collecting oil content, and, concentrate with organic solvent ethyl acetate extraction for example, thus the collection of biological surfactant.
For extracting solvent, can use separately by water and organic solvent alcohol (lower alcohol methanol, dehydrated alcohol and ethanol or polyhydric alcohol propylene glycol and 1 for example for example for example for example, the 3-butanediol), ketone for example acetone, ether, diox, acetonitrile, ester for example ethyl acetate, dimethylbenzene, benzene and chloroform mix the mixing material that obtains, perhaps two or more mixing materials are used in combination, can also use those solvents that obtain by with each solvent extractable matter combination.
Be not particularly limited for extracting method.Usually, extraction can be in room temperature to the boiling temperature of solvent, carry out under normal pressure.After the extraction, can use and filter or ion exchange resin is drawn, decolouring or purified extract, with preparation solution, ointment, gel or powder.Under many circumstances, can directly use the product that obtains, but if necessary, for example deodorization is handled or decolouring can to carry out purification process to it in the scope that does not influence the product effect.For deodorization means and decolouring means, can use activated-charcoal column, and can choose the common means of selecting and being applicable to extraction of substance usually wantonly.If necessary, can use the silicagel column purification to obtain the high-purity biosurfactant.
For surfactant, preferred MEL-A, MEL-B and MEL-C, more preferably MEL-B and MEL-C, especially preferably MEL-B.
Be used as the biosurfactant of the present invention of the cosmetic material of skin nursing/pachylosis improvement, can prepare by aforesaid microbial fermentation.
Join the amount of the biosurfactant in the material of making up, can change, can not decide without exception, do not have in the weakened scope but can be in pachylosis improvement/skin nursing effect according to the type of its applied cosmetic material.Usually, with respect to various cosmetic material, preferred amount is 0.001 to 50 quality %, and more preferably 0.1 to 20 quality % is more preferably 1 to 15 quality %, preferred especially 3 to 10 quality %.Herein, the type of service that joins the biosurfactant in the material of making up is chosen wantonly.For example, can directly use the biosurfactant that from culture medium, extracts, maybe can use highly purified biosurfactant, maybe can be suspended in the water or be dissolved in organic solvent and for example use afterwards biosurfactant in the ethanol.
Can be by in oil-soluble substrate or oil-soluble composition, dissolving, thus biosurfactant is incorporated in the material of making up, and preferably in water system is made up material with the combination of liposome form, described water system make up for example facial astringent of material and moisture retention liquid.Preferably make up this biosurfactant with the liposome form, this is to merge because of it and Skin Cell, thereby has improved its absorbance.Be not particularly limited for the method for preparing liposome; Can use any known preparation method, for example alcohol injection or Bang Hamu (Bangham) method.
Be not particularly limited for using biosurfactant to prepare the make up method of material of the present invention, biosurfactant can be dissolved in nonionic surfactant, lower alcohol, polyhydric alcohol or natural oil for example in olive oil, squalane, fatty acid or the higher alcohol.
The example of nonionic surfactant comprises that sorbitan fatty acid esters (for example, dehydrated sorbitol mono-fatty acid ester, sorbitan list isostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, NOFABLE SO-992 NOFABLE SO-902, sorbitan trioleate, diglycerol sorbitan five-2-ethylhexanoate, diglycerol sorbitan four-2-ethylhexanoate); Glycerol/polyglyceryl fatty acid ester (for example, single Oleum Gossypii semen fatty glyceride, glycerol list eruciate, glycerol sesquioleate, glyceryl monostearate, α, α '-oleic acid pyroglutamic acid glyceride, monostearate malic acid glyceride); Methyl glycol fatty acid ester (for example, propylene glycolmonostearate); Solidify castor oil derivative; With the glycerol alkyl ether.
Example based on the hydrophilic nonionic surfactant of POE (for example comprises the POE-sorbitan fatty acid esters, the POE-dehydrated sorbitol mono-fatty acid ester, the POE-sorbitan monostearate, POE-dehydrated sorbitol mono-fatty acid ester, POE-sorbitan four oleates); POE-Sorbitol fatty acid ester (for example, POE-is sorbityl monododecanoate, POE-sorbitol monooleate, POE-Sorbitol five oleates, POE-Sorbitol monostearate); POE-fatty acid glyceride (for example, POE-glyceryl monostearate, POE-glycerol list isostearate, POE-glycerol three isostearates, POE-monoleate); POE-fatty acid ester (for example, POE-distearate, the single dioleate of POE-, diglycol stearate); POE-alkyl ether (for example, POE-lauryl ether, POE-oleyl ether, POE-stearoyl ether, POE-mountain Yu base ether, POE-2-octyl group lauryl ether, POE-cholestane alcohol ether); The block polyether type (for example, Pluronic); POE/POP-alkyl ether (for example, POE/POP-cetyl ether, POE/POP-2-decyl myristyl ether, POE/POP-single-butyl ether, POE/POP-hydrogenated lanolin, POE/POP-glycerin ether); Four-POE/, four-POP-ethylenediamine condensation substance (for example, tetronic acid (Tetronic)); POE-Oleum Ricini curing castor oil derivative (for example, the POE-Oleum Ricini, POE-solidifies Oleum Ricini, POE-solidifies Oleum Ricini list isostearate, POE-solidifies Oleum Ricini three isostearates, and POE-solidifies Oleum Ricini pyroglutamic acid ester list isostearic acid diester, and POE-solidifies the Oleum Ricini maleate); POE-Cera Flava lanolin derivative (for example, POE-Sorbitol Cera Flava); Alkanolamide (for example, palm oil fatty acid diglycollic amide, lauric monoethanolamide, fatty acid isopropanol amide); The POE-methyl glycol fatty acid ester; The POE-alkylamine; The POE-fatty acid amide; Fatty acid cane sugar ester; Alkyl ethoxy dimethyl amine oxide; With three oleyl phosphate esters.
The example of lower alcohol comprises ethanol, propanol, isopropyl alcohol, isobutanol and the tert-butyl alcohol.
Examples of polyhydric alcohols comprises dihydroxylic alcohols (for example, ethylene glycol, propylene glycol, trimethylene, 1,2-butanediol, 1,3 butylene glycol, tetramethylene glycol, 2,3-butanediol, pentamethylene glycol, 2-butylidene-1,4-glycol, hexanediol, ethohexadiol); Trihydroxylic alcohol (for example, glycerol, trimethylolpropane); Tetrahydroxylic alcohol (for example, tetramethylolmethane for example 1,2,6-hexanetriol); Pentabasis alcohol (for example, xylitol); Hexahydroxylic alcohols (for example, Sorbitol, mannitol); Polyhydric alcohol polymer (for example, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, TEG, two glycerol, Polyethylene Glycol, triglycerin, four glycerol, polyglycereol); Dihydroxylic alcohols alkyl ether (for example, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyleneglycol monophenylether, glycol monomethyl is ether, glycol monomethyl-2-methyl hexyl ether, the ethylene glycol isoamyl oxide, ethylene glycol benzyl ether, glycol isopropyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve); Dihydroxylic alcohols alkyl ether (for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, propylene glycol diisopropyl ether, dipropylene glycol methyl ether, the dipropylene glycol ether, the dipropylene glycol butyl ether); Diatomic alcohol ether acid ester (for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, the ethyleneglycol monophenylether acetas, ethylene glycol bisthioglycolate adipate ester, ethylene glycol bisthioglycolate succinate, the diethylene glycol monoethyl ether acetas, butyl carbitol acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, the propylene glycol monopropyl ether acetas, propylene glycol monophenyl ether acetas); Glycerol monoalkyl ether (for example .alpha.-hexadecylglyceryl ether, selachyl alcohol, deep-sea alcohol (bathyl alcohol)); Sugar and sugar alcohol (for example, Sorbitol, maltose alcohol, maltotriose, mannitol, sucrose, erithritol, glucose, fructose, the sugar of starch degradation, maltose, xylose, the reductive alcohol of starch degradation sugar); Glysolid; Tetrahydrofurfuryl alcohol; The POE-tetrahydrofurfuryl alcohol; The POP-butyl ether; The POP/POE-butyl ether; Three polypropylene oxide glycerin ethers; The POP-glycerin ether; POP-glycerin ether phosphate ester; POP/POE-tetramethylolmethane ether, and polyglycereol.
The example of oils comprises animals and plants oils, American Avocado Tree oil for example, olive oil, Oleum sesami, Camellia oil, Radix Oenotherae erythrosepalae oil, turtle oil, macadimia nut oil, Semen Maydis oil, ermine oil, Oleum Brassicae campestris, egg oil, almond oil (parsic oil), wheat germ oil, Flos Camelliae Japonicae caul-fat, Oleum Ricini, Semen Lini oil, safflower oil, Oleum Gossypii semen, perilla oil, soybean oil, Oleum Arachidis hypogaeae semen, Oleum Camelliae, kaya seed oil, Testa oryzae oil, Oleum Verniciae fordii, Jojoba oil, cocoa butter, fractionated coconut oil, house oil, Petiolus Trachycarpi oil, Cortex cocois radicis core oil, Adeps Bovis seu Bubali, Adeps caprae seu ovis, leaf fat, lanoline, spermaceti, Cera Flava, Carnauba wax, vegetable wax, candelilla wax and squalane, it solidifies oils, and mineral oil is liquid paraffin and vaseline and synthetic triglycerin tripalmitin for example for example.
The example of fatty acid comprises lauric acid, myristic acid, Palmic acid, oleic acid, linoleic acid, linolenic acid, stearic acid, mountain Yu's acid, 12-hydroxy stearic acid, isostearic acid, undecynic acid, alphitolic acid (tolic acid), eicosapentaenoic acid and docosahexenoic acid.The example of higher alcohol comprises lauryl alcohol, spermol, octadecanol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, jojoba alcohol, lanolin alcohol, batilol, 2-decyl tetradecyl alchohol, cholesterol, plant sterol and i-octadecanol.The example of synthetic ester comprises the cetyl caprylate, Wickenol 142, isopropyl myristate, myristic acid myristyl ester, isopropyl palmitate, butyl stearate, lauric acid hexyl ester, decyl oleate, dimethyl is sad, cetyl lactate and myristyl lactate.Organosilyl example comprises the chain polysiloxanes, and for example dimethyl polysiloxane and methyl phenyl silicone, cyclic polysiloxanes be the tridimensional network of decamethyl cyclopolysiloxane and silicones for example.
Skin nursing cosmetic material package of the present invention is drawn together emulsion, beautifying liquid, emulsifiable paste, astringent, skin tonic oil, cleansing oil, bath oil or facial cleanser, makeup removing liquid, shampoo and body shaping soap.
With regard to easy usability, MELs of the present invention, particularly MEL-A, MEL-B and MEL-C, outstanding than ceramide, this is because of their easy preparations and has emulsification.
Embodiment
Among the embodiment the present invention will be described in more detail below; Yet the present invention is not limited to these embodiment.
(evaluation methodology of pachylosis improvement effect)
According to test skin (Test Skin) LSE-002 or 003 test kit (Toyobo Co., Ltd.) main points of the workbook of being had taking-up tissue.The ring that to guarantee the medicament exposure portion is attached to the LSE tissue surface, and 0.1% sodium lauryl sulphate (SDS) aqueous solution is added in the ring, then it is at room temperature left standstill 5 minutes.Subsequently, use aspirator to remove SDS, use pipet to spray 3 milliliters of tests (assay) culture medium, with the washing tissue.By these operations,, thereby make dry skin with the composition stripping of preserving moisture in the horny layer.
Subsequently, will purifying waste water or each 80 μ L (oil skin lotion of Fenatty of skin lotion as trier; FANCL Corporation) is added on LSE (living skin equivalent, the skin equivalent of the living) tissue surface, then it at room temperature left standstill 60 minutes.Then, use aspirator that trier is extracted out and removed.Subsequently, the LSE tissue is placed on the test panel of not putting test media, at the CO that is adjusted to 37 ℃ of temperature and 15 to 20%RH relative humiditys 2Cultivated 24 hours in the incubator.Then, from CO 2Shift out LSE tissue in the incubator, and according to the main points of the appended workbook of LSE-003 test kit, 1.2 milliliters of mixed solutions that will contain the test media of 0.333 grams per milliliter tetrazolium salts (MTT) reagent join in the test panel.Subsequently, the LSE in the test panel is organized in the CO that is adjusted to 37 ℃ of temperature and relative humidity 15 to 20%RH 2Cultivated 3 hours in the incubator.
After the MTT processing, use the biopsy of 8mm φ to drill through device (biopsy punch), the central part that includes the LSE tissue of polycarbonate film is drilled through out, obtain a LSE tissue, it is gone in the small test pipe then, 0.04N hydrochloric acid-isopropyl alcohol to wherein adding 700 μ L in the dark extracted two hours.Extract after the termination, stir extract solution and mixing up hill and dale.Subsequently, at the 562nm place, measure the absorbance of the bluish violet first hairpin that is extracted.Be closely related by this method absorbance that obtains and the effect of improving pachylosis.Thus, this method can be effective to quantitative, the coarse improvement of simple and economical ground evaluating skin.
The preparation of embodiment 1:MEL
The Pseudozyma antarctica NBRC 10736 of 1 ring (loop) is seeded in the seed culture medium (20 milliliters/500 milliliters Sakaguchi flasks), carries out kind of bacterium and cultivate.Carry out incubated overnight at 30 ℃.Make the culture medium that obtains as kind of a bacterium.Seed culture medium is made up of following: 4% glucose, 0.3% NaNO 3, 0.02% MgSO 4H 2O, 0.02% KH 2PO 4With 0.1% yeast extract.Above-mentioned kind of bacterium (75 milliliters) is seeded in 1.5L (5L-jar) the production culture medium, under the condition of 30 ℃, 300rpm (stirring frequency) and 0.5L/min0 (air) (using the 5L-jar), cultivates.The production culture medium is by 3% soybean oil, 0.02% MgSO 4H 2O, 0.02% KH 2PO 4Form with 0.1% yeast extract.With culture medium (250 milliliters) centrifugal (6,500rpm, 30 minutes), remove supernatant, collecting precipitation (thalline).Ethyl acetate (50 milliliters) is joined in the precipitation, then it is stirred up hill and dale and centrifugal (8,500rpm, 30 minutes), with separation of supernatant from precipitation.Use the vaporizer concentrated supernatant.By using silica gel and using hexane: acetone=5: 1 and hexane: acetone=carry out eluting at 1: 2 obtains MEL fraction (MEL-A, MEL-B and MEL-C).
The preparation of embodiment 1A:MEL-B
In 500 milliliters of Sakaguchi flasks, the P.tsukubaensis (0.2 milliliter) of stored frozen is seeded in 20 milliliters of YM seed culture mediums, and under 26 ℃, 180rpm overnight incubation, with preparation seed kind bacterium.In 500 milliliters of Sakaguchi flasks, seed kind bacterium is seeded in 20 milliliters of YM seed culture mediums once more, and under 26 ℃, 180rpm overnight incubation, as kind of a bacterium.In the 5L jar, will plant bacterium (20 milliliters) and be seeded in the YM culture medium of 2L, and 26 ℃, (1/4VVM, 0.5L air/min) was cultivated 8 days at 300rpm.With culture medium 7,900rpm, 4 ℃ centrifugal 60 minutes, with separating thallus from supernatant (comprising MEL-B).Ethyl acetate (80 milliliters) is joined in the thalline fraction, then it is shaken to thorough suspension, then 7,900rpm, centrifugal 30 minutes at 4 ℃.The saline of equivalent is joined in the supernatant that obtains, stir the mixture, produce ethyl acetate layer.The anhydrous sodium sulfate of appropriate amount is joined in the ethyl acetate layer, it is left standstill 30 minutes then, evaporate, obtain the crude product of the MEL-B of purification.Use silicagel column (200 gram), the crude product (20 gram) of the purification MEL-B that obtains is further purified, and uses the hexane/acetone eluting, obtain purification MEL-B product.
Embodiment 2
Though be used as raw materials for production in the MEL preparation of soybean oil in embodiment 1, change in this example and use olive oil to separate and purification MEL-A, MEL-B and MEL-C as raw materials for production, and with cultivating with embodiment 1 the same method.The MEL fraction that obtain this moment is called MEL-A (OL), MEL-B (OL) and MEL-C (OL), so that the MEL that they and embodiment 1 are obtained distinguishes.
Embodiment 3
Though be used as raw materials for production in the MEL preparation of soybean oil in embodiment 1, change in this example and use methyl myristate to separate and purification MEL-A, MEL-B and MEL-C as raw materials for production, and with cultivating with embodiment 1 the same method.The MEL fraction that obtain this moment is called MEL-A (MY), MEL-B (MY) and MEL-C (MY), so that the MEL that they and embodiment 1 are obtained distinguishes.
Embodiment 4: estimate MEL-A in the pachylosis model
Use the pachylosis model of three-dimensional skin model by following making.By using 1%SDS Processing Test skin (LSE-002 or 003; Toyobo Co. Ltd.) comes except that the lipid components in the destratum corneum, thereby makes the pachylosis model.Following check pachylosis preventive effect: the olive oil that will dissolve MEL-A is added on the cell, and its placement is spent the night, and uses subsequently and can calculate the cells survival rate by the commercial MTT test kit of buying.As shown in Figure 1, improved the cells survival rate, proved that MEL-A has played the effect of the substitute of ceramide in the concentration dependent mode of MEL-A.Simultaneously, independent olive oil does not demonstrate such effect.
Embodiment 5: estimate MEL-B in the pachylosis model
Use the pachylosis model of three-dimensional skin model by following making.By using 1%SDS Processing Test skin (LSE-002 or 003; Toyobo Co. Ltd.) comes except that the lipid components in the destratum corneum, thereby makes the pachylosis model.Following check pachylosis preventive effect: the olive oil that will dissolve the MEL-B that embodiment 1A obtained is added on the cell, and its placement is spent the night, and uses subsequently and can calculate the cells survival rate by the commercial MTT test kit of buying.As shown in Figure 4, improved the cells survival rate, proved that MEL-B has played the effect of the substitute of ceramide in the concentration dependent mode of MEL-B.Simultaneously, independent olive oil does not demonstrate such effect.
Embodiment 6: estimate MEL-C in the pachylosis model
Use the pachylosis model of three-dimensional skin model by following making.Come except that the lipid components in the destratum corneum by usefulness 1%SDS Processing Test skin (Ltd. provides for LSE-002 or 003, Toyobo Co.), thereby make the pachylosis model.By following check pachylosis preventive effect: the olive oil that will dissolve the MEL-C that embodiment 1 obtained is added on the cell, and its placement is spent the night, and uses subsequently and can calculate the cells survival rate by the commercial MTT test kit of buying.As shown in Figure 4, improved the cells survival rate, proved that MEL-C has played the effect of the substitute of ceramide in the concentration dependent mode of MEL-C.Simultaneously, independent olive oil does not demonstrate such effect.
Embodiment 7: estimate MEL-A (OL) and MEL-A (MY) in the pachylosis model
Similar to embodiment 4, use the pachylosis model of three-dimensional skin model by following making.Come except that the lipid components in the destratum corneum by usefulness 1%SDS Processing Test skin (Ltd. provides for LSE-002 or 003, Toyobo Co.), thereby make the pachylosis model.Following check pachylosis preventive effect: the olive oil that will dissolve MEL-A (embodiment 1), MEL-A (OL) (embodiment 2) or MEL-A (MY) (embodiment 3) is added on the cell, its placement is spent the night, use subsequently and can calculate the cells survival rate by the commercial MTT test kit of buying.As shown in Figure 3, improved the cells survival rate, proved that MEL-A has played the effect of the substitute of ceramide in the concentration dependent mode of MEL-A.Simultaneously, independent olive oil does not demonstrate such effect.
Embodiment 8: in the application on human skin crude test, contain the effect of the emulsifiable paste of MEL-A
By people's upper arm inboard is contacted 10 minutes with 1%SDS solution, roughen the skin.Immediately apply the emulsifiable paste of the above-mentioned 5%MEL-A of containing, after 3 hours, use the warm water washed skin.Wipe oil content with the Kim towel, use Si Jikang (Skicon) to measure the water quantities of keratodermatitis.As shown in Figure 2, when applying the emulsifiable paste that contains MEL-A, observed the recovery of moisture.
Embodiment 9: in the application on human skin crude test, contain the effect of the emulsifiable paste of MEL-B
By people's upper arm inboard is contacted 10 minutes with 1%SDS solution, roughen the skin.Immediately apply the above-mentioned emulsifiable paste that contains 5%MEL, after 3 hours, use the warm water washed skin.Wipe oil content with the Kim towel, use Si Jikang (Skicon) to measure the water quantities of keratodermatitis.As shown in Figure 5, when applying the emulsifiable paste that contains MEL-B or C, observed the recovery of moisture.
The dispersion stabilization test of embodiment 10:MEL-B and MEL-C
MEL-B or MEL-C are added to the water with the concentration of 10 mg/ml, stir also and suspend.Measure absorbance at the 650nm place.The results are shown among Fig. 6.Find out clearly that by the result among Fig. 6 the dispersion stabilization of MEL-B and MEL-C is outstanding especially.
The preparation of embodiment 11:MEL-B liposome solutions
Following use alcohol injection, preparation MEL-B liposome solutions.10 milligrams of MEL-B are dissolved in 0.5 milliliter of ethanol, and add 1 milliliter and be warming up to about 70 ℃ distilled water in advance.Mixture is shaken slightly and mix, use rotary evaporator to distill out remaining ethanol.Use water-bath type ultrasonoscope (W-220R; Honda Electronics Co. Ltd.), applies about 5 minutes supersound process to it, then adds distilled water, and making cumulative volume is 1 milliliter.
Following use Bang Hamu (Bangham) method, preparation MEL-B liposome solutions.10 milligrams of MEL-B are dissolved in 1 milliliter of chloroform, and use the rotary evaporator distilling off solvent, with the preparation thin film.To wherein adding 1 ml distilled water, use water-bath type ultrasonoscope (W-220R; HondaElectronics Co. Ltd.), applies about 5 minutes supersound process to it.
Be prepared as follows the MEL-B suspension.1 ml distilled water is joined among 10 milligrams of MEL-B, use turbine mixer to stir, with supending.
Use is shown in the three-dimensional skin model among the embodiment 4, MEL-B liposome aqueous solution and the MEL-B suspension that utilizes alcohol injection, the preparation of Bang Hamu (Bangham) method is carried out the pachylosis test, and check their effect.The results are shown among Fig. 7.The result shows, utilizes the MEL-B liposome aqueous solution of any preparation in alcohol injection, Bang Hamu (Bangham) method to demonstrate all with suspension that (MEL-B concentration: 1%) identical pachylosis improves effect with the MEL-B olive oil solution.
Embodiment 12: the preparation beautifying liquid
Use the standard method preparation to have the beautifying liquid of composition as follows.Thing also uses the standard method preparation not contain the beautifying liquid of MEL in contrast.
(composition) (weight %)
Sorbitol 4.0
Dipropylene glycol 6.0
Polyethylene glycol 1500 5.0
POE (20) oleyl alcohol ether 0.5
Fatty acid cane sugar ester 0.2
Methylcellulose 0.2
MEL-B 5.0
Purify waste water to total amount 100%
Embodiment 13: the preparation emulsion
Use the standard method preparation to have the emulsion of composition as follows.Thing also uses the standard method preparation not contain the emulsion of MEL in contrast.
(composition) (weight %)
Glyceryl ether 1.5
Fatty acid cane sugar ester 1.5
Monostearate sorbitan ester 1.0
Squalane 7.5
Dipropylene glycol 5.0
MEL-B 5.0
Purify waste water to total amount 100%
Embodiment 14: the preparation emulsifiable paste
Use the standard method preparation to have the emulsifiable paste of composition as follows.Thing also uses the standard method preparation not contain the emulsifiable paste of MEL in contrast.
(composition) (weight %)
Propylene glycol 6.0
Dibutyl phthalate 19.0
Stearic acid 5.0
Monostearin 5.0
Monostearate sorbitan ester 12.0
Poly-ethylene sorbitan monostearate 38.0
Sodium ethylene diamine tetracetate 0.03
MEL-B 5.0
Purify waste water to total amount 100%
Embodiment 15: the preparation oil for cosmetic purpose
(composition) (weight %)
Olive oil 90
MEL-A 10
Embodiment 16: skin tonic oil
(composition) (weight %)
Olive oil 50
MEL-C 30
Squalane 10
Oleum sesami 10
Embodiment 17: skin tonic oil
(composition) (weight %)
Olive oil 39
MEL-C 59
Oleum sesami 1
Essential lavender oil 0.4
Oil of rosemary 0.4
Sage oil 0.1
Delta-Tocopherol 0.1
Embodiment 18: cleansing oil
(composition) (weight %)
Olive oil 40
MEL-B 28
Methyl phenyl silicone 2
Ethanol 0.3
Isostearic acid 0.1
2 ethyl hexanoic acid cetyl 20
Polyethylene Glycol diisopstearate 2
Palm oil fatty acid diglycollic amide 0.1
Polyethyleneglycol isostearate 2
Delta-Tocopherol 0.1
Purify waste water 1
Aromatic is an amount of
Embodiment 19: bathe oil
(composition) (weight %)
Olive oil 25
MEL-A 25
Liquid paraffin 25
Neopentyl glycol dicaprylate 10
Polyoxyethylene oleyl ether 10
Purify waste water 0.5
Delta-Tocopherol 0.1
Aromatic is an amount of
Industrial applicibility
According to the present invention, lose by replenishing with MEL-A of the present invention, MEL-B or MEL-C The ceramide that goes can prevent pachylosis, and described MEL-A, MEL-B or MEL-C are not Only as emulsifying agent but also can be as the substitute of ceramide, because they are than nerve Therefore the easier preparation of acid amides estimates that it has very big contribution to industry.

Claims (9)

1. a skin nursing is made up and is expected that it comprises at least a biosurfactant.
2. make up according to the skin nursing of claim 1 and expect that it is used to improve pachylosis.
3. make up according to the skin nursing of claim 1 and expect that it is used for the improved effect pachylosis by surfactant.
4. make up according to the skin nursing of claim 1 and expect that wherein said biosurfactant is mannose erythrose alcohol ester (MEL) and/or mannose mannose alcohol ester (MML).
5. according to the skin nursing of claim 1 material of making up, wherein said biosurfactant is to be selected from least a among mannose erythrose alcohol ester A (MEL-A), mannose erythrose alcohol ester B (MEL-B) and the mannose erythrose alcohol ester C (MEL-C).
6. make up according to the skin nursing of claim 1 and expect that wherein said biosurfactant is mannose erythrose alcohol ester B (MEL-B).
7. make up according to the skin nursing of claim 1 and expect that wherein said biosurfactant is mannose erythrose alcohol ester C (MEL-C).
8. make up according to the skin nursing of claim 1 and expect that wherein said biosurfactant is mannose erythrose alcohol ester A (MEL-A).
9. pachylosis improving agent, it is made up of at least a biosurfactant.
CNA200680044160XA 2005-11-25 2006-11-21 Skin care cosmetic and skin and agent for preventing skin roughness containing biosurfactants Pending CN101316574A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103589764A (en) * 2013-11-05 2014-02-19 浙江大学 Production method for mannosylerythritol lipids
CN104125821A (en) * 2011-12-28 2014-10-29 赢创工业集团股份有限公司 Aqueous hair and skin cleaning compositions comprising biotensides
CN110099689A (en) * 2016-12-27 2019-08-06 国立大学法人广岛大学 The purposes of biosurfactant

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104125821A (en) * 2011-12-28 2014-10-29 赢创工业集团股份有限公司 Aqueous hair and skin cleaning compositions comprising biotensides
US9271908B2 (en) 2011-12-28 2016-03-01 Evonik Industries Ag Aqueous hair and skin cleaning compositions comprising biotensides
CN104125821B (en) * 2011-12-28 2017-04-12 赢创德固赛有限公司 Aqueous hair and skin cleaning compositions comprising biotensides
CN103589764A (en) * 2013-11-05 2014-02-19 浙江大学 Production method for mannosylerythritol lipids
CN103589764B (en) * 2013-11-05 2015-06-17 浙江大学 Production method for mannosylerythritol lipids
CN110099689A (en) * 2016-12-27 2019-08-06 国立大学法人广岛大学 The purposes of biosurfactant

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Application publication date: 20081203