AU2155599A - Cosmetic agents - Google Patents

Abstract

The invention relates to cosmetic agents containing 0.1-10 wt. % carophyllene. Carophyllenes are terpenes which can be isolated out of ethereal oils and exhibit a caring effect on both skin as well as on hair when used in the required concentrations.

Description

1 Cosmetic Agents The invention relates to cosmetic agents comprising caryophyllene, and to the use of caryophyllene for the preparation of skincare and haircare agents. The cosmetic treatment of skin and hair is an important part of human bodycare. The 5 importance of care products is growing, not least as a result of severe stressing of the skin and hair by environmental impact. Both the cleansing of the hair using shampoos and the decorative arrangement of the hairstyle, for example by colouring or permanent waving, are interventions which can influence the natural structure and the properties of the hair also in an undesired manner. For example, following such 10 treatment, the wet and dry combability of the hair, the hold and volume of the hair can be unsatisfactory, or the hair can have an increased number of split ends. For some time, it has therefore been recommended to subject the hair in this case to a special after-treatment. For this, the hair is usually treated, in the form of a rinse, with special active ingredients, for example quaternary ammonium salts or special polymers. Depending on the 15 formulation, this treatment improves combability, hold and volume of the hair, and reduces the proportion of split ends. Agents of this type are - mostly containing relatively low active ingredient concentrations - also supplied as preparations which remain in the hair. Furthermore, so-called combination preparations have recently been developed in order to reduce the time and effort of said multistage procedures, in particular in the case of direct application 20 by consumers. As well as the customary components, for example for the cleansing of the hair, these preparations additionally comprise active ingredients which had earlier been reserved for hair after treatment agents. The consumer thus saves an application step; at the same time, the expenditure on packaging is reduced since one product uses less. 25 However, the active ingredients which are available both for separate after-treatment agents and for combination preparations are still unable to satisfy all of the wishes of the consumer. Thus, for example, the biodegradability of the quaternary ammonium compounds is not entirely satisfactory, and their often inadequate compatibility with anionic surfactants severely restricts the formulation possibilities. The same disadvantages also apply to the cationic polymers. Furthermore, in 30 the case of certain polymers, undesired accumulation on the hair can occur. Although alkyl phosphonates and alkyl phosphates are compatible with anionic surfactants, they have only limited care properties. Cosmetic skincare has also recently become more important since many people regard their skin as sensitive, and others stress their skin by frequent exposure to solar radiation or to skin 35 irritative agents, or suffer from allergic and inflammatory skin conditions. There has therefore been no lack of attempts to prevent such skin conditions or to remedy them using cosmetic and dermatological skin treatment agents. In this connection, the use of panthenol or mink oil in skin treatment agents, for example, is known.

2 There therefore continues to be a need for active ingredients or active ingredient combinations for cosmetic agents having good care properties and good biodegradability which can be incorporated into existing formulations without problems. The invention provides cosmetic agents comprising 0.1 to I Owt% of caryophyllene. 5 The invention further provides for the use of caryophyllene in skincare and haircare products. Surprisingly, we have found that the cosmetic agents according to the invention, comprising 0.1 to lOwt%, in particular 0.6 to 5wt%, of caryophyllene are notable for good skin and hair compatibility, and care action and, particularly in the case of use in hair cosmetics, lead to improved wet combability and to the hair feeling softer. It was particularly surprising that in the case of the use of caryophyllene 10 in skincare and haircare products, it was possible to achieve very good effects with regard to long term action, in particular improved wet combability, and care action. Caryophyllene Caryophyllenes are sesquiterpenes which can be isolated from essential oils, for example clove oil, and have a characteristic odour. They are also found in many other essential oils, for example as 15 a constituent of copaiva balsam or cinnamon tree oil. In the meantime, it has been found that of the substances originally referred to as a-, P- and y-caryophyllene, only a- and @-caryophyllene are compounds of the same empirical formula. Nowadays, s-caryophyllene is usually referred to as caryophyllene, while a-caryophyllene is also known as humulene. p-caryophyllene has already been used for a long time as fragrances. For the purposes of the present application, the term 20 "caryophyllene" means both a-, and also, preferably, p-caryophyllene. For the purposes of the present invention, caryophyllene is preferably used in concentrated form. Within the scope of the teaching of the invention, this means caryophyllene having an active substance content of at least 60wt%, preferably at least 90wt%. It is, however, also possible, as is already known from the prior art, to use essential oils containing caryophyllene. Hitherto, these oils 25 have primarily been used for the aromatisation of the corresponding agents. The present invention is, however, based on the finding that high-concentration caryophyllene in particular has care properties for skin and hair. In an alternative embodiment, fatty alcohols are also preferably used. Fatty alcohols 30 The term "fatty alcohols" means primary aliphatic alcohols of the formula (I)

R

1 OH (1) in which R 1 is a linear or branched hydrocarbon radical having 6 to 22 carbon atoms which is saturated or olefinically unsaturated with up to 3 double bonds. Typical examples are caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl 35 alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and the technical-grade mixtures thereof which are produced, for example, during the high pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from the 40 Roelen oxosynthesis, and as a monomer fraction during the dimerisation of unsaturated fatty alcohols.

3 Preference is given to long-chain fatty alcohols, such as cetyl alcohol and stearyl alcohol, and to technical-grade fatty alcohol mixtures having 12 to 18 carbon atoms, such as, for example, coconut, palm, palm kernel or tallow fatty alcohol. The agents according to the invention preferably comprise the fatty alcohols in amounts of from 5 0.1 to 20wt%, in particular 1 to 1Owt%. Surfactants In a particularly preferred embodiment, the agents according to the invention also comprise surfactants in addition to caryophyllene and fatty alcohols. These can either be nonionic, anionic, cationic, zwitterionic or amphoteric surfactants; preference is, however, given to nonionic and/or 10 anionic surfactants, particular preference to compounds having one or more carboxyl groups. Typical examples of anionic surfactants are alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, a-methyl ester sulfonates, sulfo fatty acids, fatty alcohol sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl 15 sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, acyl lactylates, acyl tartrates, acyl glutamates, acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (in particular vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these can have a conventional, 20 but preferably a narrowed, homologue distribution. For the purposes of the present invention, particular preference is given to using carboxyl-group-containing anionic surfactants, preferably soaps, and ether sulfates. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol 25 ethers, alkoxylated triglycerides, mixed ethers and mixed formals, alk(en)yl oligoglycosides, fatty acid N-alkylglucamides, polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. For the purposes of the present invention, the nonionogenic surfactants which may be used are preferably the following compounds: 30 - addition products of from 2 to 30mol of ethylene oxide and/or 0 to 5mol of propylene oxide with linear fatty alcohols having 8 to 22 carbon atoms, with fatty acids having 12 to 22 carbon atoms and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, - C12-C22-fatty acid mono- and diesters of addition products of from 1 to 30mol of ethylene oxide with glycerol, 35 - C8-C22-alkyl mono- and oligoglycosides and the ethoxylated analogues thereof, and - addition products of from 5 to 16mol of ethylene oxide with castor oil and hydrogenated castor oil. These compounds containing alkyl groups can in each case be uniform substances. It is, however, usually preferred in the case of the preparation of these substances to start from native vegetable or animal raw materials, thus giving mixtures of substances having varying alkyl chain 40 lengths depending on the raw material in each case.

4 In the case of the nonionogenic surfactants, which are addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products, it is possible to use either products having a "normal" homologue distribution or those having a narrowed homologue distribution. "Normal" homologue distribution means here mixtures of homologues obtained during the 5 reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alkoxides as catalysts. By contrast, narrowed homologue distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products having a narrowed homologue distribution may be preferred. 10 Alkyl polyglycosides according to the formula RO-(Z)x in which R is an alkyl radical having 8 to 22 carbon atoms, Z is a mono- or oligosaccharide and x is a number from 1.1 to 5 are particularly preferred nonionogenic surfactants. These compounds are characterised by the following parameters. The alkyl radical R contains 8 to 22 carbon atoms and can either be linear or branched. Preference is given to primary linear radicals and aliphatic radicals methyl-branched in the 2-position. 15 Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particular preference is given to 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. If so-called "oxo alcohols" are used as starting materials, compounds having an uneven number of carbon atoms in the alkyl chain predominate. The alkyl glycosides which can be used according to the invention can only contain a certain 20 alkyl radical R. However, these compounds are usually prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R present are mixtures corresponding to the starting compounds or corresponding to the respective work-up of these compounds. Particular preference is given to those alkyl polyglycosides in which R consists - essentially of C 8 - and Cia-alkyl groups, 25 - essentially of C12- and C14-alkyl groups, - essentially of C 8 - to C16-alkyl groups, or - essentially of C12- to C1e-alkyl groups. As the sugar building block Z, it is possible to use any mono- or oligosaccharides. Sugars having 5 or 6 carbon atoms, and the corresponding oligosaccharides, are usually used. Such sugars 30 are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; glucose is particularly preferred. The alkyl polyglycosides which can be used according to the invention contain, on average, 1.1 to 5 sugar units. Alkyl glycosides having x values of from 1.3 to 2 are preferred. Very particular 35 preference is given to alkyl glycosides in which x is from 1.4 to 1.6. Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternised fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazoliniumbetaines and sulfobetaines.

5 Said surfactants are exclusively known compounds. With regard to the structure and preparation of these substances, reference may be made to relevant review papers, for example J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.), "Katalysatoren, Tenside und Mineral6ladditive" [Catalysts, Surfactants and Mineral Oil 5 Additives], Thieme Verlag, Stuttgart, 1978, pp. 123-217. In a preferred embodiment, the agents according to the invention comprise 0.1 to 40wt%, in particular 1 to 30wt%, of surfactant. These amounts are, in particular, dependent on the cosmetic agent, for example shower preparations usually have a higher surfactant content than, for example, hair rinses. 10 In a further preferred embodiment, the agents to be used according to the invention also comprise dicarboxylic acids chosen from the group formed by compounds of the general formula (II), 0 R2 OH X Y(II) in which R 2 is a linear or branched alkyl or alkenyl group having 4 to 12 carbon atoms, n is a number from 4 to 12, and one of the two groups X and Y is a COOH group and the other is hydrogen or a 15 methyl or ethyl radical, dicarboxylic acids of the general formula (II) which additionally also carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring, dicarboxylic acids produced formally from the dicarboxylic acids according to formula (11) by addition of one molecule of water to the double bond in the cyclohexene ring, and alkyl- and alkenylsuccinic acids having 1 to 18 carbon atoms in the alkyl chain, or a physiologically compatible salt of one of these acids. 20 The dicarboxylic acid (mixture) which forms by reacting linoleic acid with acrylic acid has proven particularly effective according to the invention. This is a mixture of 5- and 6-carboxy-4-hexyl 2-cyclohexen-1-octanoic acid. Such compounds are commercially available under the names Westvaco Diacid@ 1550 and Diacid@ H 240 (Manufacturer: Westvaco). As well as the ingredients according to the invention, other components can also be present. 25 The choice of these other components is essentially determined by the nature of the cosmetic agent. Particular preference is given to additionally using water-soluble polymers. Within the meaning of the present invention, these can either be nonionic, cationic, anionic and/or amphoteric polymers. Preferred polymers are the nonionogenic polymers, such as, for example, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers and cellulose ethers, starch and/or cyclodextrins, and 30 anionic polymers, such as, for example, the acrylates obtainable under the trade names Carbopol@, Acrysol@ and POC@ (DEGUSSA). In addition, yet further fats and oils can also be present, for example natural fats and oils, mono-, di- and triglycerides of saturated and unsaturated fatty acids, ethylene glycol esters of fatty acids, fatty acids, fatty acids with a low degree of ethoxylation, fatty alcohols with a low degree of 35 ethoxylation, cholesterol and cholesterols with a low degree of ethoxylation, but also synthetic products, such as, for example, silicone oils and mixtures thereof.

6 The nature of the cosmetic agents according to the invention is not subject to any limitation. The agents according to the invention can either remain on the skin and/or hair (leave-on), or, in particular in the case of hair treatment agents, can be rinsed out again after a contact time of a few seconds to minutes (rinse-off). Examples of agents used according to the invention are shower 5 lotions, shower preparations, body lotion, hand cream, shampoos, rinses, treatments, conditioning agents, tinting agents, colorants, permanent wave agents, fixatives, hair sprays and blow-waving agents. Further components of these compositions can then be, for example: - stucturants, such as glucose and maleic acid, 10 - protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soybean protein and wheat protein hydrolysates, the condensation products thereof with fatty acids, and quaternised protein hydrolysates, - perfume oils and dimethyl isosorbide, - solubilisers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and 15 diethylene glycol, - dyes, - further substances for adjusting the pH, - active ingredients, such as panthenol, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extracts and vitamins, 20 - light protection agents, - bodying agents, such as sugar esters, polyol esters or polyol alkyl ethers, - waxes, such as beeswax and montan wax, - fatty acid alkanolamides, - complexing agents, such as EDTA, NTA and phosphonic acids, 25 - swelling and penetration substances, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogencarbonates, guanidines, ureas, and primary, secondary and tertiary phosphates, - opacifiers, such as latex, - pearlising agents, such as ethylene glycol mono- and distearate, 30 - propellants, such as propane/butane mixtures, N 2 0, dimethyl ether, CO 2 and air, and - antioxidants, - reducing agents, such as, for example, thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid and a-mercaptoethanesulfonic acid, The agents according to the invention can be formulated, for example, as aqueous, alcoholic or 35 aqueous-alcoholic solutions, creams, gels or emulsions. Examples A. Investigation procedure A.1 Deliberate damage to hair swatches Dry hair swatches weighing about 2g (Fischbach and Miller type 6923) were bleached using 8g 40 of bleaching mixture (commercial product Poly Blond Medium lightener) per swatch for half an hour.

7 After the bleaching mixture had been washed out, the hair swatches were subjected immediately, without interim drying, to a permanent-wave treatment using the commercial product Poly Lock Normal, using 7g of waving gel and fixative per swatch. The contact times for the waving component and fixing component were 30 and 15 minutes respectively. After the fixing component had been 5 rinsed out, the swatches were dried and conditioned for at least two days under ambient conditions. A.2 Testing the wet combability Prior to the test, the rinsed hair swatch was vigorously shampooed with in each case 0.2mL of a 50% strength solution of Texapon@ N25 (28% strength solution of sodium lauryl ether sulfate in water) and then rinsed. Then, 0.5mL of the formulation to be tested was massaged uniformly into the 10 hair, left in the hair for one minute and then carefully rinsed out. The hair was then combed using a fine-toothed comb and the combing resistance was assessed subjectively. A standard formulation was then tested on the same swatch in the same manner as a comparison. The assessment was made in accordance with an assessment system from 1 (= very good) to 5 (= unsatisfactory). B. Formulation examples 15 1. Cream shampoolshower preparation Tab. 1: Cream shampoo (formulations 1,2)Ishower preparation (formulations 3,4) Raw material Formulation number Data in wt% 1 2 3 4 Coconut fatty alcohol 4.0 3.0 5.0 3.0 Texapon@ N 28' 25.0 25.0 30.0 30.0 Na stearate - - 3.0 3.0 Caryophyllene 86% strength by wt. - 1.0 - 2.0 Water 71.0 71.0 62.0 62.0 1 lauryl ether sulfate, sodium salt, 30wt% of active substance For the formulations I and 2, the wet combability was assessed as already described, while for formulations 3 and 4 the care effect on the hair was assessed (likewise subjectively). 20 Tab. 2: Wet combabilityIcare effect Formulation Assessment 1 4to5 2 3 3 after showering, no care effect, dry skin 4 supple, soothed skin following showering 2. Hair rinses Tab. 3: Hair rinses Raw material Formulation number Data in wt% 5 6 7 8 9 10 11 12 13 14 15 Coconut fatty alcohol 2.0 1.0 2.0 2.0 - - - - - - Cetearyl alcohol - - - - - 1 1 1 1 1 Texapon@N 28 1.6 1.6 - - - - - - - - Copaiva balsam oil - 1.0 - 2.0 - - - - - - Cremophor@ RH 402 - - - - - - - - 1 1 Saponin - - 0.4 0.4 - - - - - - Guar seed flour - - 1.0 1.0 1.0 1.0 - - - - Soybean lecithin - - - - 2.0 2.0 - - - - Candelilla wax - - - - 3.0 2.0 - - - - Caryophyllene 86% - - - - - 1.0 - 0.5 - 0.5 0.5 strength by wt.

8 Raw material Formulation number Data in wt% 5 6 7 8 9 10 11 12 13 14 15 Westvaco Diacid@ H - - - - - - 7.5 7.5 - - 7.5 2403, 41% strength by wt. Citric acid - - - - 2.0 2.0 - - - - Water 96.4 96.4 96.6 94.6 92 91 91.5 91.0 98.0 97.5 92.0 2 Hydrogenated castor oil containing 45 EO (BASF) 3 Potassium salt of 4-hexyl-5(6)-carboxy-2-cyclohexene-l-octanoic acid (about 41% of active substance in water) (WESTVACO) Tab.: 4 Wet combability Formulation Assessment 5 4 to 5 6 3 7 4 to 5 8 3 9 3 10 2 11 2 12 1to 2 13 4 to 5 14 3 to 4 15 3 to 4 5 3. Colouring cream Tab. 5: Colouring cream Raw material Formulation number Data in % by wt. 16 17 Coconut fatty alcohol 10.0 9.0 Texapon@ N 25 20.0 20.0 Dehyton@ K 4 10.0 10.0 Polymer JR 5 0.4 0.4 Sodium sulfite 0.5 0.5 Ammonium chloride 0.4 0.4 Ammonia solution 25% strength by wt. 6.0 6.0 EDTA di-Na salt 0.2 0.2 p-Aminophenol hydrochloride 0.07 0.07 p-toluylenediamine sulfate 0.2 0.2 Resorcinol 0.09 0.09 Caryophyllene 86% strength by wt. - 1.0 Water 52.14 52.14 4 N,N-Diethyl-N(C8/C18-cocamidopropyl)ammoniumacetobetaine (30wt% of active substance) 5 Hydroxyethylcellulose trimethylammoniumpropyl ether (Union Carbide) The formulations according to Table 5 were mixed in a 1:1 ratio with a 6% strength by weight 10 hydrogen peroxide solution. On light-blonde hair, a mid-blonde coloration was achieved. In the wet combability test, after a contact time for the colour mixture of 30 minutes and after rinsing, formulation 16 was graded 3, and formulation 17 was given the subjective grade 2.

9 4. Care lotion which remains in the hair Tab. 6: Care lotion Raw material Formulation number Data in wt% 18 19 Ethanol (cosmetic) 50.0 50.0 Caryophyllene - 1.0 Water 50.0 49.0 0.5g of each of the care lotions according to formulations 18 and 19 were massaged into a damp hair swatch (2g) pretreated as already described. The wet combability was then determined. 5 Formulation 18 was graded 5, while formulation 19 was graded 1. After shampooing once or twice with a commercially available shampoo, the wet combability of the two hair swatches was determined again. The swatch pretreated with formulation 19 was given the grade 2 to 3 after shampooing once, and 3 to 4 after shampooing twice.

Claims (13)

1. A cosmetic agent comprising 0.1 to 1 Owt% of caryophyllene.

2. The cosmetic agent as claimed in claim 1, comprising 0.6 to 5wt% of caryophyllene.

3. The cosmetic agent as claimed in either of claims 1 or 2, comprising a fatty alcohol. 5

4. The cosmetic agent as claimed in claim 3, comprising 1 to 10wt% of a fatty alcohol.

5. The cosmetic agent [lacuna] claim 3 or 4, comprising a fatty alcohol having 12 to 18 carbon atoms.

6. The cosmetic agent as claimed in any of claims 1 to 5, comprising anionic surfactants.

7. The cosmetic agent as claimed in claim 6, comprising 1 to 30wt% of an anionic and/or a 10 nonionic surfactant.

8. The cosmetic agent as claimed in claim 7, comprising a surfactant containing one or more carboxyl groups.

9. The use of caryophyllene in cosmetic agents for the care of skin and/or hair.

10. The use as claimed in claim 9, wherein 0.1 to lOwt%, in particular 0.6 to 5wt%, of 15 caryophyllene are used.

11. The use as claimed in claim 9 or 10, wherein caryophyllene is used in haircare agents for improving wet combability.

12. The use as claimed in claim 9 or 10, wherein the agent is a hair treatment agent which remains in the hair. 20

13. The use as claimed in claim 9 or 10, wherein caryophyllene is used in cosmetic agents for skincare.