FR2470595A2 - Cationic surfactants for hair and skin compsns. - prepd. from alcohol(s) obtd. from lanolin, waxes or resin acids - Google Patents

Abstract

The cpds. have the formula R1O- C2H3(CH2OH)O -n CH2-CHOH-CH2-NR1R2 (I). In (I), R1 is a hydrocaryl radical derived from alcohols obtd. from lanolin, natural waxes or resin acids, pref. from lanolin or hydrogenated lanolin; n is 0.5-10; R1 and R2 are 1-4C alkyl or hydroxyalkyl or together are alkylene radicals linked to form a 5- or 6-membered heterocycle, pref. piperidine or morpholine. Also cpds. of formula R1O- C2H3(CH2OH)O -n CH2CHOH-CH2-circled positive NR1R2R3Y circled negative (II) and R1O- C2H3(CH2XO -NCH2CHOH-CH2-NR1R2 (III) are novel. In the formulae, R3 is 1-2C alkyl and Y is an anion such as Cl, Br, I, CH3SO4, C2H5SO4; X is hal, pref. Cl or Br. The cpds. are used in cosmetic compsns. for the hair and skin. They are stable over a large pH range, have improved emulsification properties and are esp. beneficial to the skin.

Description

dans laquelle R' désigne avantageusement un reste hydrocarboné dérivé d'alcools et/ou de stérols obtenus à partir de la lanoline, de cires naturelles telles que la cire d'abeilles, des acides résiniques ou d'acides gras cycliques et de préférence un reste hydrocarboné dérive des alcools et/ou stérols de la lanoline ou de la lanoline hydrogénée; n est un nombre compris entre 0,5 et 10;R1 et R2 désignent des radicaux alcoyles ou hydroxyalcoyles inférieurs séparés ayant de préfe- rence de 1 à 4 atomes de carbone ou des radicaux alcoylènes réunis entre eux en formant un hétérocycle; ainsi que leurs sels d'ammonium quaternaires de formule

dans laquelle R', R1 et R2 ont la signification précitée, R3 désigne un radical alcoyle inférieur de 1 à 2 atomes de car bone, Y# désigne un anion tel que Cl#, Br#, I#, CH@SO 4,
C2H5SO4@. This addition relates to main patent application no. 78 34 418 of December 6, 1978, in which cationic surfactants of the formula have been described.

in which R 'advantageously denotes a hydrocarbon residue derived from alcohols and / or sterols obtained from lanolin, natural waxes such as beeswax, resin acids or cyclic fatty acids and preferably a residue hydrocarbon derived from alcohols and / or sterols from lanolin or hydrogenated lanolin; n is a number between 0.5 and 10; R1 and R2 denote separate lower alkyl or hydroxyalkyl radicals preferably having from 1 to 4 carbon atoms or alkylene radicals joined together to form a heterocycle; as well as their quaternary ammonium salts of formula

in which R ', R1 and R2 have the abovementioned meaning, R3 denotes a lower alkyl radical of 1 to 2 carbon atoms, Y # denotes an anion such as Cl #, Br #, I #, CH @ SO 4,
C2H5SO4 @.

 Said main application also describes the use of surfactants of formula (A1) and (B1) in cosmetic compositions, in particular for the treatment of hair.

 The inventors have discovered that the cationic surfactants of formula (A1), their salts obtained with acids and their quaternary ammonium salts of formula can also be used in cosmetology for the skin and in dermatology, because they make it possible to prepare cosmetic compositions intended for the care and treatment of the skin, of weakly alkaline and even acid pH (pH 5 to 8).

Such use of cationic surfactants has so far been little developed because of the disadvantages attributed to them, in particular
- toxicity and aggressiveness,
- incompatibility with other constituents used in dermatological compositions;
- too much water solubility leading to poor emulsifying properties.

 The Applicant has discovered that the compounds of formulas (A1) and (B1) do not have these drawbacks and can therefore be used in dermatology, in particular in cosmetic compositions intended for the treatment and care of the skin.

 In addition, during the preparation of the compounds of formula (A1) and (B1), the hydrophilic-lipophilic character (H.L.B.) can be modified, according to the values of n and the nature of the substituents R1 and R2. The hydrophilic-lipophilic character can also be modified by salification or total or partial quaternization.

 The compounds of formula (A1) can also be used in the form of mineral or organic salts, for example in the form of salts obtained with hydrochloric, phosphoric, acetic, citric, lactic or tartaric acids.

 The compounds of formula (ale, their salts obtained with acids and their quaternary ammonium salts of formula (B1) make it possible to obtain cosmetic preparations which have a great affinity for the skin and in which one can introduce treatment agents such as bactericides, in particular quaternary ammonium salts or antiseborrheic agents.

 The subject of the invention is the use of surfactants of formula (A1), their salts obtained with acids and their quaternary ammonium salts of formula (B1) as a cationic emulsifier for the production of emulsions for skin care and treatment.

dans laquelle R' désigne un reste hydrocarboné dérivé d'alcool et/ou de stérols obtenus à partir de la lanoline, de cires naturelles telles que la cire d'abeilles ou des acides résiniques et de préférence un reste hydrocarboné- dérivé des alcools et/ou stérols de la lanoline ou de la lanoline hydro génée;; n est un nombre compris entre O,5 et 10 et
R1 et R2 désignent les radicaux alcoyles ou hydroxyalcoyles inférieurs séparés ou des radicaux alcoylènes réunis entre eux en formant un hétérocycle et de préférence un hétérocycle pipéridinique ou morpholinique ou (b) un sel du composé A1 obtenu avec un acide ou (c) un agent de surface sous forme de sel d'ammonium quaternaire de formule (B1)

dans laquelle R', R1 et R2 ont la signification précitée,
R3 désigne un radical alcoyle inférieur de r 2 atomes de carbone, désigne un anion tel que Cl0, B , , CH3SO4t C2H5SO4#
A titre d'exemple de compositions cosmétiques pour le traitement de la peau on peut citer les lotions démaquillantes pour les yeux, les laits et crèmes protecteurs pour le visage, les laits et crèmes démaquillants, les laits et crèmes contre l'acné, les laits, crèmes et gels adoucissants pour les mains, les laits et crèmes hydratants, les laits et crèmes corporels, les crèmes moussantes, les bases de maquillage, les compositions anti-solaires, les crèmes anti-transpirantes, les crèmes déodorantes.A subject of the invention is also a cosmetic composition for the care and treatment of the skin, characterized in that it contains at least (a) a cationic surfactant of formula

in which R 'denotes a hydrocarbon residue derived from alcohol and / or sterols obtained from lanolin, from natural waxes such as beeswax or resin acids and preferably a hydrocarbon residue derived from alcohols and / or lanolin or hydro gen lanolin sterols; n is a number between O, 5 and 10 and
R1 and R2 denote the separate alkyl or lower hydroxyalkyl radicals or alkylene radicals joined together to form a heterocycle and preferably a piperidinic or morpholinic heterocycle or (b) a salt of the compound A1 obtained with an acid or (c) an agent of surface in the form of a quaternary ammonium salt of formula (B1)

in which R ', R1 and R2 have the abovementioned meaning,
R3 denotes a lower alkyl radical of r 2 carbon atoms, denotes an anion such as Cl0, B,, CH3SO4t C2H5SO4 #
By way of example of cosmetic compositions for the treatment of the skin, mention may be made of make-up removing lotions for the eyes, protective milks and creams for the face, cleansing milks and creams, acne milks and creams, milks , softening hand creams and gels, moisturizing milks and creams, body milks and creams, foaming creams, makeup bases, sunscreen compositions, antiperspirant creams, deodorant creams.

 These compositions can be in the form of an aqueous or hydroalcoholic solution, cream, gel, oil-in-water emulsion, suspension, dispersion, compact product or packaged in the form of aerosol and pre ference in the form of an oil-in-water emulsion.

 These compositions generally contain from 0.1 to 30% by weight of one or more compounds of formula (A1) or (B1) or of salts of the compound (A1) obtained with an acid. The pH of these compositions is generally between 3 and 10 and advantageously from 5 to 8.

 According to an advantageous embodiment of the invention, the composition for caring for or treating the skin is in the form of an oil-in-water emulsion containing (1) from 0.1 to 30% by weight d '' one or more compounds of formula (A1) or (B1) or of salts of a compound (A1) obtained with an acid, (2) from 5 to 608 by weight of fatty substances or animal or vegetable oils or waxes , mineral or synthetic, (3) from 10 to 95% water.

 The compounds of formula (A1) and their salts obtained with an acid are the preferred compounds for producing oil-in-water emulsions.

 The cosmetic compositions for the skin may also contain one or more adjuvants usually used in cosmetics and advantageously chosen from polymers and preferably from cationic polymers, surfactants and preferably from cationic surfactants, oils or animal, vegetable, mineral or synthetic waxes, perfumes, preservatives, softeners, humectants, protective agents against ultraviolet radiation, antiseborrheic agents, antioxidants, gums and natural resins possibly modified, protein derivatives, natural substances which may have an action for the treatment or care of the skin, pH-modifying agents, solvents such as lower alcohols and preferably ethanol.

 The invention also relates to a method of treating the skin, characterized in that a sufficient quantity of a composition described above is applied to the skin.

 The invention will be better understood using examples of preparation which illustrate some compounds which can be used in the compositions according to the invention as well as examples of compositions for the treatment and care of the skin.

PREPARATION EXAMPLES
EXAMPLE 1
Preparation of the mixture of compounds of general formula

R 'denotes the remainder of lanolin alcohols n denotes a mean statistical value of 1.

300 g (720 meq) of lanolin alcohols, sold by the
Croda company under the trade name "Satulan", 1.73 ml of BF3 etherate are added, then 133.2 g (1.44 mole) of epichlorohydrin at 50 / 550C in 1 hour 30 minutes. about 30 minutes with stirring at the same temperature.

 The polyhalogenated derivatives are obtained in the form of a pasty product of light brown color, the hydroxyl index is 1.57 meq / g.

 To 140 g of polyhalogenated derivatives thus obtained, 25 g of 40% sodium hydroxide are added over 20 minutes at a temperature of 450C. After 1 hour of stirring at this temperature, 140 g of tert-butyl alcohol are added and then, within 10 minutes, 26.3 g (233 meq) of diethanolamine. The mixture is left under stirring at reflux of the alcohol for 2 hours 30 minutes.

 The reaction mass is taken up with 50 g of water and after 30 minutes with stirring at 800C the aqueous phase is separated by decantation.

 The organic phase is washed with twice 150 ml of boiling water, then dehydrated by heating under reduced pressure.

 To 132 g (200 meg. In chlorine) of the product obtained is added 132 g of dipropylene glycol, 20.6 g (210 meq.) Of potassium acetate and then heated with stirring and under a nitrogen atmosphere, at 1800C for 6 hours. The reaction mass is then washed with twice 400 ml of boiling water. The organic phase is then saponified by adding 21.2 g of sodium hydroxide at 9.9 meq / g in the presence of 70 ml of isopropanol and heating at reflux temperature for 1 hour.

 The reaction medium is washed with water in the presence of hydrochloric acid.

 To 40 g (56.8 meq.) Of cationic derivative prepared above, 13 g of methanol are added, then 7.11 g (56.4 meq.) Of dimethyl sulfate in 1 hour at 350C. The mixture is then left stirring for 1 hour 30 minutes at this temperature.

 After removal of the methanol, a product is obtained which is in the form of a soft paste of brown color soluble in water with a slight opalescence.

EXAMPLE II
Preparation of the mixture of compounds of general formula

R 'denotes the remainder of lanolin alcohols n denotes a mean statistical value of 1.

 To 278.5 g (442 meq in hydroxyl groups) of polyhalogenated derivatives obtained according to Example 1, 278 g of tert-butyl alcohol are added, then at 45 ° C., 70.23 g of sodium hydroxide at 9.9 meq / g in 10 minutes. The mixture is heated with stirring at 50 / 600C for 30 minutes and then the product is washed with twice 600 ml of water at 700C. After dehydration under reduced pressure, a light brown paste is obtained, the epoxy index of which is 2 meq / g.

 To 60 g (120 meq) of derivative prepared above is added in 30 minutes at 80 ° C., under a nitrogen atmosphere, 11.5 g (142 meq) of morpholine. After 3 hours of stirring at 80-850C the product is washed with three times 100 ml of boiling water, then dehydrated by heating under reduced pressure.

 A light brown paste is thus obtained, the basicity index of which is 1.39 meq / g, and the chlorine index is of 1.58 meq / g.

 To 58 g (86.63 meg in chlorine) of the preceding product, 58 g of dipropylene glycol, 8.8 g 191 meq) of potassium acetate are added then the mixture is heated with stirring and nitrogen atmosphere at 1800C for 6 hours.

 The product obtained is washed with three times 100 ml of boiling water in the optional presence of isopropanol to facilitate salting out. It is then saponified with 9.2 g of sodium hydroxide at 9.9 meq / g at 800C for 1 hour 30 minutes.

 The reaction mass is washed with three times 100 ml of boiling water and then dried by heating under reduced pressure.

 This gives a brown paste soluble in water in the presence of acid and whose basicity index is 1.43 meg / g.

 To 45 g (65 meq. In basicite) of the product obtained previously, 10 g of methanol are added and then at 35 ° C., within 1 hour, 8.1 g of dimethyl sulphate. Heating and stirring are continued for another 1 hour. A brown water-soluble paste is thus obtained after heating.

EXAMPLE III
Preparation of the mixture of compounds of general formula

R 'is the remainder of lanolin alcohols n denotes a mean statistical value of 2.

 To 300 g (720 meq3 of lanolin alcohols, sold under the trade name "SATULAN" by the company CRODA, 2 ml of BF3 etherate are added then at 50/55 C, in the space of 1 hour 30 minutes , 199.8 g (2.16 moles) of epichlorohydrin, followed by stirring for 1 hour 30 minutes at the same temperature.

 To 482 g (694 meq) of polyhalogenated derivatives obtained previously, 480 g of tert-butyl alcohol are added, then, in 10 minutes, at the temperature of 500 ° C., 129.6 g of sodium hydroxide at 9.9 meq / g. The mixture is then left stirring for 30 minutes at 600C, under a nitrogen atmosphere.

 The product is then washed with three times 900 ml of water at 60 / 700C, then dehydrated under reduced pressure.

 A light brown paste is thus obtained, the epoxy index of which is 1.48 meq / g.

 To 120 g (177.6 meq. In epoxy group) of derivative prepared above, there is added, over 15 minutes at 80 ° C., under a nitrogen atmosphere, 25.5 g (237 meq) of diethanolamine. After 2 hours of stirring at this temperature, the product is washed with three times 200 ml of boiling water, optionally in the presence of chloroform to facilitate decantation, then dried by heating under reduced pressure.

 A pasty product is thus obtained, the basicity index of which is 1.19 meq / g.

 To 127 g (332 meq. In chlorine) of the preceding product, 127 g of dipropylene glycol, 34.1 g of potassium acetate are added, then the mixture is heated with stirring and nitrogen atmosphere at 1800C for 6 hours. The product obtained is then washed with three times 200 mol of water in the presence, if necessary, of butanol to facilitate decantation, then saponified with 34.5 g of sodium hydroxide at 9.9 meq / g at 900C for 1 hour 15 minutes.

The reaction mass is then washed with three times 200 ml of boiling water, then dehydrated by heating under reduced pressure.

 The product thus obtained has a basicity index of 1.33 meq / g.

 To 30 g (40 meq. In basicity) of product obtained previously, 5 g (0.04 mole) of dimethyl sulfate at 30/350 ° C. are added in 1 hour, then the mixture is left stirring for 1 hour at this temperature.

 A light brown paste is thus obtained which has a slight cloudiness in water.

EXAMPLE IV
Preparation of the mixture of compounds of general formula

R '= residue of lanolin alcohols n denotes a mean statistical value of 6.

 To 100 g (240 meq) of lanolin alcohols, 1.02 ml of BF3 etherate is added, then 155.4 ml (1680 meq) of epichlorohydrin at 50 / 550C, in 3 hours, under a nitrogen atmosphere . The mixture is then left stirring for 30 minutes at the same temperature.

 To 248 g (233.4 meq) of polyhalogenated derivatives obtained previously, 240 g of tert-butyl alcohol are added, then, at 50 ° C., 45.4 g of sodium hydroxide at 9.9 meq / g in 10 minutes and left with stirring for 1 hour at 600C.

 The product is then washed with 2 times 300 ml of hot water, then dehydrated under reduced pressure. It is in the form of a very light brown paste with an epoxy index of 1.07 meq / g.

 To 100 g (107 meq) of the above derivative, 16.5 g of diethylamine are added under a nitrogen atmosphere at 65 / 700C in 15 minutes, then the mixture is left stirring at 600C for 3 hours.

 The product is then washed with 400 ml of hot water and then dehydrated by heating under reduced pressure.

 To 90 g (491 meq. In chlorine) of the preceding product, 90 g of dipropylene glycol, 50.6 g of potassium acetate are added, then the mixture is heated with stirring and nitrogen atmosphere at 1800C for 6 hours. The product obtained is washed with 2 times 150 ml of hot water and then dehydrated by heating under reduced pressure.

 80 ml of absolute ethanol and 0.8 g of sodium methoxide at 5.4 meq / g are added.

 After overnight at room temperature, the solvent is removed by heating under reduced pressure.

 A water-soluble brown paste is thus obtained with a slight haze which disappears by addition of a mineral or organic acid and the basicity index of which is 0.87 meq / g.

EXAMPLE V
Preparation of the mixture of compounds of general formula

R '= residue of lanolin alcohols n denotes a mean statistical value of 2.

 To 300 g of lanolin alcohols, 0.72 equivalents in hydroxyl groups, 2 ml of BF3 therate are added, then 200 g (2.16 moles) of epichlorohydrin at 50 / 550C, in 1 hour 30 minutes, under nitrogen atmosphere. Then left for 1 hour 30 minutes with stirring at the same temperature.

 To 482 g (0.69 mole) of polyhalogenated derivatives obtained previously, 480 g of tert-butyl alcohol are added, then at 500 ° C., 105 g of sodium hydroxide at 9.9 meq / g in 10 minutes and the mixture is left stirring for 1 hour at 600C.

 The product is then washed with 2 times 300 ml of hot water, then dehydrated under reduced pressure. It is in the form of a very light brown paste with an epoxy index of 1.48 meq / g.

 To 120 g (183 meq. In epoxy groups) of previous drift, 25.6 g (0.23 mole) of diethanolamine are added under nitrogen atmosphere at 65 / 700C over 15 minutes, then left to stir. at 800C for 2 hours.

 The product is then washed with three times 200 ml of hot water and then dehydrated by heating under reduced pressure.

 To 127 g (332 meq. In chlorine) of the preceding product, 127 g of dipropylene glycol, 34.1 g of potassium acetate are added, then the mixture is heated with stirring and nitrogen atmosphere at 1800C for 6 hours. The product obtained is saponified at 900C with 34.5 g of sodium hydroxide at 10 meq / g, washed three times with 200 ml of boiling water, then dehydrated by heating under reduced pressure.

 The product thus obtained is in the form of a soft paste with a basicity index of 1.33 meq / g.

vendu sous la marque "Hyamine 1622" par Rohm & Haas - Trans thiolane 3,4-diol S-dioxyde utilisé comme agent anti-séborrhéique .................................................0,3 g - Parfum ................................................................0,5 g - Conservateur ..........................................................0,4 g - Eau déminéralisée stérile q.s.p 100 g
EXEMPLE 6
Gel adoucissant pour les mains - Composé de l'exemple III................................................4,5 g - Gomme de guar quaternisée, vendue sous la marque "Guar HP 13" par Meyhall Chemicals 0,4 g - Dérivé quaternaire d'éthers de cellulose, vendu sous la marque nJR 400" par Union Carbide .0,5 g - Parfum ................................................................0,3 g - Conservateur ..........................................................0,3 g - Eau déminéralisée q.s.p 100 g APPLICATION EXAMPLES
EXAMPLE 1
Protective face cream - Vaseline oil Codex ........................................ .... 20 g - Cetyl Laurate sold under the brand name "Cetiol LC" by Henkel .............................. ................... 15 g - Composed of example V ...................... ......................... 8 g - Quaternary polyvinylpyrrolidone copolymer with a molecular weight of approximately 1,000,000, sold under the brand "Gafquat 755" by General Aniline ............................. 0.3 g - Preservative ............. ............................................ 0.2 g - Perfume .................................................. ............. 0.3 g - Sterile demineralized water qs ............................ .100 g
EXAMPLE 2
Acne Cream - Codex Vaseline Oil ........................................ ...... 15 g - Isopropyl myristate ..................................... .......... 5 g - Carboxymethyl cysteine used as an antiseborrheic agent ............................... ....................... 0.5 g - Trimethyl cetyl ammonium bromide sold under the brand name "Cetavlon" by the company ICI ..... 0 , 2 g - Compound of example V ........................................ ........ 5.6 g - Perfume .................................... ........................... 0.3 g - Preservative ................. ......................................... 0.3 g - Sterile demineralized water qs ....................................... 100 g
EXAMPLE 3 Oil in Water Emulsion Cream - Cetyl Laurate, oil sold under the brand name "Cetiol LC" by Henkel ......................... .......................... 40 g - Compound of example V ............... ................................. 10 g - Perfume ............. .................................................. .0.3 g - Preservative ........................................... ............... 0.3 g - Sterile demineralized water qs ......................... 100 g
EXAMPLE 4
Eye make-up removing lotion - Composed of example IV ...................................... ....... 3 g - Lactic acid ...................................... ................ 0.1 g - Trimethyl cetyl ammonium bromide, sold under the brand name "Cetavlon" by the company ICI O, 1 g - Perfume ...... .................................................. ... 0.3 g - Preservative s 0.3 g - Sterile demineralized water qs 100 g
EXAMPLE 5
Make-up removing lotion for oily skin - Composed of Example II ...................................... 4 4 g - Ethyl alcohol ............................ 4 4 g - Cationic surfactant of formula

sold under the brand "Hyamine 1622" by Rohm & Haas - Trans thiolane 3,4-diol S-dioxide used as an anti-seborrheic agent ..................... ............................ 0.3 g - Perfume ................ ................................................ 0, 5 g - Preservative .............................................. ............ 0.4 g - Sterile demineralized water qs 100 g
EXAMPLE 6
Softening Hand Gel - Composed of Example III ...................................... .......... 4.5 g - Quaternized guar gum, sold under the brand "Guar HP 13" by Meyhall Chemicals 0.4 g - Quaternary derivative of cellulose ethers, sold under the brand nJR 400 "by Union Carbide .0.5 g - Perfume ...................................... .......................... 0.3 g - Preservative .................. ........................................ 0.3 g - Demineralized water qs 100 g

Claims (6)

 1. Cosmetic composition for the care and treatment of the skin, characterized in that it contains at least one cationic surfactant of formula (A1) below, according to claim 1 of main patent application No. 78 34 418,

 in which R 'denotes a hydrocarbon residue derived from alcohols and / or sterols obtained from lanolin, from natural waxes such as beeswax, resin acids and preferably a hydrocarbon residue derived from alcohols and / or lanolin or hydrogenated lanolin sterols; n is a number between 0.5 and 10 and R1 and R2 denote separate lower alkyl or hydroxyalkyl radicals or alkyl radicals joined together to form a heterocycle; or a salt of compound A1 obtained with an acid or a surfactant in the form of a quaternary ammonium salt of formula (B1) below, according to claim 3 of main patent application No. 78 34 418

 in which R ', R1 and R2 have the abovementioned meaning, R3 denotes a lower alkyl radical of 1 to 2 carbon atoms, y denotes an anion such as Cl0, BP,, CH2SO4 #, C2H5S04  2. Composition according to Claim 1, characterized in that it contains from 0.1 to 30% by weight of one or more compounds of formula A1 or B1 or a salt of the compound A1 obtained with an acid.  3. Composition according to claims 1 or 2, characterized in that it is in the form of an oil-in-water emulsion, an aqueous or hydroalcoholic solution, gel, suspension or dispersion  4. Composition according to any one of claims 1 to 3, characterized in that it also contains one or more adjuvants chosen from polymers and preferably from cationic polymers, surfactants and preferably from agents cationic surface, animal, vegetable, mineral or synthetic oils or waxes, perfumes, preservatives, softeners, humectants, agents protecting against ultraviolet radiation, antiseborrhoeic agents, antioxidants, natural gums and resins optionally modified, protein derivatives, natural substances which may have an action for the treatment or care of the skin, pH-modifying agents, solvents such as ethanol.  5. Composition according to any one of claims 1, 2 or 4 characterized in that it is in the form of an oil-in-water emulsion containing (1) from 0.1 to 30% by weight d one or more compounds of formula (A1) or (B1) or of salt of compound (Al) obtained with an acid, (2) from 5 to 60% by weight of fatty substances or of animal or vegetable oils or waxes, mineral or synthetic, (3) from 10 to 95% water.  6. A method of treating the skin, characterized in that a sufficient amount of a composition according to any one of claims 1 to 5 is applied to the skin.