AU2007294011A1 - Bioquinones for stimulating keratin synthesis - Google Patents

Description

PCT/EP2007/058481 H 07094 BIOQUINONES FOR STIMULATING KERATIN SYNTHESIS [0002] The present invention relates to the cosmetic use of one or more bioquinones to combat age-related changes in hair follicles, to promote keratin synthesis in hair, and to positively influence hair structure. The invention further relates to a cosmetic method for combating age-related changes in hair follicles, and to a method for stimulating keratin synthesis in hair. [0003] The quantity of a hair-active substance that can penetrate to the hair bulb, usually transdermally and especially in transfollicular fashion, is extremely small, and depends substantially on the physical and chemical properties of the substance itself (e.g. size, charge, liphophilicity) and on the formulation selected. [0004] Hair follicle cells are subject to a genetically defined cycle of growth, regression, and rest phase. The hair follicle is thus the only organ that continually renews itself and thus exhibits a unique metabolism as a function of the particular growth phase. The synthesis of structure-providing keratins is also linked to this cycle. This cycle is controlled by a small, highly specialized cell population in the hair bulb (the dermal papilla cells), that control hair growth by way of a unique and complex system of molecular signals that is specific for each phase of the hair cycle (Botchkarev V.A. et al., (2003) J Invest Dermatol Symp Proc 8:46-55). If the invention is then to modulate the metabolism of these highly specialized cells by application of a test formulation, it is essential to act in targeted fashion on the corresponding mechanisms. [0005] Hepatocyte Growth Factor (HGF) and Keratinocyte Growth Factor (KGF) are important growth factors that are excreted by the dermal papillae in order to control proliferation of the hair keratinocytes that are responsible for the synthesis of hair keratins. They are also characteristic markers for the anagen phase, in which keratin synthesis is also maximal. It must furthermore be noted that as the hair ages, the proliferation capability of the hair follicle H 07094 cells decreases. In the context of a potentially keratin-activating substance that counteracts hair aging, it is advantageous if HGF and/or KGF is additionally induced. TGF-p2 and IGFBP-3 act in growth-inhibiting fashion, and are characteristic markers for the catagen phase, in which keratin synthesis in the follicle is shut off. In a substance that promotes keratin synthesis, these markers should advantageously be repressed. [0006] The ability to maintain the youthfulness of hair, or to rejuvenate it, by way of suitable active-substance formulations represents a challenge for cosmetic research. [0007] Topical applications for the treatment of disruptions in hair structure, e.g. split or broken hair, usually involve physical methods in which, for example, polymers or structural proteins are applied onto the hair. The duration of these methods is limited, and the risk also exists of "overloading" the hair by repeated application of care-providing substances. In addition, the only possibility for improving hair from the root in terms of its structure is by the oral application of specific active substances. [0008] There has hitherto been insufficient research regarding changes in age-affected hair. The fact that hair density and hair diameter are reduced is known (Birch et al. (2001), Br. J. Dermatol. 144: 297-304; Courtois et al. (1995), Br. J. Dermatol. 132: 86-93), as is the decrease in the cell division rate in hair follicle cells (Van Neste (2004), Eur. J. Dermatol. 14: 28-32). The existing data are based for the most part, however, on empirical observations. [0009] There have been very few investigations of the molecular and cell physiology-related reasons for these phenotypic changes during the aging process, or analyses of age- and gender-specific differences. Our own investigations have indicated that, among other things, synthesis of the structure-providing hair keratins decreases with age. The concentration of ubiquinone (coenzyme Q10) in human tissue also decreases with age (Crane, F. (2001): J. Am. Coll. Nutr. 20: pp. 591-596). 2 H 07094 [0010] Ubiquinone has hitherto been used principally as an antioxidant in skin cosmetics. There are furthermore a number of Applications that claim the use of ubiquinone in skin-care products. Application WO 2004/01095, for example, describes the use of a formulation that can contain, inter alia, ubiquinone as an antioxidant in order to improve the surface quality of hair. [0011] Application EP-A-1 059 081 claims the use of ubiquinone to decrease oxidative damage to hair. Applications EP-A-1 059 077 and EP-A-1 059 080 use ubiquinone to improve hair structure, but here this is a purely superficial, physical effect based on an improvement in combability. [0012] None of these Applications, however, claims the prevention of age dependent changes in the hair, or the stimulation of keratin synthesis by way of which the internal structure of the hair is improved. [0013] In Application EP-A-1 493 431, Buchholz and Wirth describe the use of an antioxidatively active Bauhinia extract to prevent the aging process in the skin and hair. The formulation can optionally also contain other antioxidants such as, for example, ubiquinone. [0014] Application WO 2004 089326 claims the use of an active-substance combination made up of creatinine, creatine, and bioquinones. This formulation is intended to be used in particular in inflammatory skin conditions and/or for skin protection. This Application, however, also does not discuss the effect of ubiquinone on keratin synthesis, and thus on the prevention of hair aging. [0015] There has hitherto been insufficient examination of changes in age affected hair. The market therefore offers almost no cosmetic preparations that are adapted particularly to the demands of older consumers' hair, or that counteract hair aging. [0016] Our own investigations have shown that keratin synthesis significantly decreases in hair follicles with age. The hair keratins hHal, hHa3 3 H 07094 1, hHa4, and various cytokeratins (c.g CK1) are particularly affected by these age-related changes. [0017] Hair keratins represent the most important structure-providing components of hair. The importance of hair keratins for healthy fibers is shown from the fact that genetic mutations in the hHb6 and hHb1 hair keratins result in serious changes such as, for example, deformation and breakage of the hair fibers (monilethix). In addition, mice having a point mutation of the Ha3 gene exhibit a naked phenotype with no fur covering (nude mice). [0018] At present, almost no cosmetic preparations exist on the market that reinforce the synthesis of hair-specific keratins in a biological and therefore long-lasting manner. [0019] The goal of the present invention was therefore to discover active substances suitable for the manufacture of cosmetic preparations that are applied topically onto the scalp and there activate keratin synthesis and therefore counteract hair aging. [0020] This goal was reached to a large degree by the use of one of more bioquinones for the manufacture of cosmetic preparations for hair treatment. [0021] The subject matter of the present invention is therefore the use of one or more bioquinones for the manufacture of cosmetic preparations for hair treatment, in particular for the manufacture of cosmetic preparations to combat age-related changes in hair follicles. [0022] The use of bioquinones enables, in particular, the development of new product and action concepts for biologically active hair care products that counteract or reverse the decline in keratin synthesis, decrease in cell division activity, and lowering of cell vitality. The use according to the present invention of bioquinones in cosmetic hair treatment agents furthermore counteracts or reverses increased microinflammation and apoptosis. 4 H 07094 [0023] The use of ubiquinone(s) and/or plastoquinone(s) is preferred according to the present invention. [0024] Ubiquinones represent the most common and therefore the best studied bioquinones. Ubiquinones are referred to as Q-1, Q-2, Q-3, etc. depending on the number of isoprene units linked in the side chain, or as U-5, U-10, U-15, etc. depending on the number of carbon atoms. They occur preferably with specific chain lengths, e.g. with n = 6 in certain microorganisms and yeasts. Q-10 predominates in most mammals (including humans). Ubiquinones serve organisms as electron transfer agents in the respiration chain. They are found in mitochondria, where they enable cyclic oxidation and reduction of the substrates of the citric acid cycle. [0025] The ubiquinones preferred according to the present invention have the following formula: 0 CH30 CH3 I | CH30 H O CH3 n1 where n = 6, 7, 8, 9, or 10. [0026] The ubiquinone of the formula where n = 10, also known as coenzyme Q10, is particularly preferred. [0027] Plastoquinones have the general structural formula 5 H 07094 O CH H 33 CH 3"CH O CH3 nl They can be isolated from chloroplasts, and play a role as redox substrates in photosynthesis in the context of cyclic and non-cyclic electron transport, transitioning reversibly into the corresponding hydroquinones (plastoquinol). Plastoquinones differ in terms of the number n of isoprene radicals and are designated accordingly, e.g. PQ-9 (n = 9). Other plastiquonones having different substituents on the quinone ring also exist. [0028] The use of 0.0000005 to 1% of one or more bioquinones is particularly preferred according to the present invention. The use of coenzyme Q10 is particularly preferred. [0029] A second subject of the invention is a method for manufacturing a cosmetic or pharmaceutical preparation to combat age-related changes in hair follicles, in which method a cosmetic agent based on one or more bioquinones is applied onto the hair or onto hairy skin. A method in which 0.0000005 to 1% of one or more bioquinones, in particular coenzyme Q10, in a cosmetically suitable preparation, is used, is preferred according to the present invention. [0030] A third subject of the invention is the use of one or more bioquinones for the manufacture of cosmetic preparations for hair treatment, in particular for the manufacture of cosmetic preparations to promote keratin synthesis in hair. [0031] It is preferred to use one or more bioquinones to stimulate. [0032] Also preferred is the use of one or more bioquinones to increase cytokeratin synthesis in hair follicles. 6 H 07094 [0033] The use of one or more bioquinones to stimulate cell vitality, cell proliferation, and the excretion of growth factors, and to repress catagen associated parameters, is likewise preferred according to the present invention. [0034] The use of a bioquinone, selected from the group of the ubiquinones and/or the plastoquinones, at a concentration from 0.0000005 to 1% has also proven particularly advantageous for the promotion of keratin synthesis in hair. Coenzyme Q10 is particularly preferred. [0035] A fourth subject of the invention is a method for manufacturing a cosmetic or pharmaceutical preparation to stimulate keratin synthesis in hair, in which method a cosmetic agent based on one or more bioquinones is applied onto the hair or onto hairy skin. A method in which 0.0000005 to 1% of one or more bioquinones, in particular coenzyme Q10, in a cosmetically suitable preparation, is used, is preferred according to the present invention. [0036] A fifth subject of the invention is the use of one or more bioquinones for the manufacture of cosmetic preparations for hair treatment, in particular for the manufacture of cosmetic preparations for positively influencing internal hair structure. [0037] It is preferred according to the present invention to use a bioquinone, selected from the group of the ubiquinones and/or plastoquinones, at a concentration from 0.0000005 to 1%. Coenzyme Q10 is particularly preferred. [0038] It has been shown that the treatment of cultured fibroblasts with ubiquinone(s) results in a cell-activating effect and thus in an increase in cell vitality. [0039] It has furthermore been found that the use of ubiquinone(s) in cosmetic hair treatment agents positively influences the hair in terms of its 7 H 07094 growth and its metabolism. Gene expression of the hair genes important for this has been significantly regulated by the use according to the present invention. It has been shown, for example, that the growth-inhibiting markers IGFBP3 and TGFp-2 are repressed. [0040] A further advantage of the invention is that the use of ubiquinone(s) in cosmetic hair treatment agents leads to a stimulation of hair growth and a strengthening of vital hair. An increase in the excretion of hepatocyte growth factor (HGF) has been demonstrated as a result of the treatment of organotypical hair follicle cell cultures with ubiquinone. [0041] It has furthermore been found that the use according to the present invention of bioquinones in cosmetic agents results in a positive influence on hair structure, by the fact that special hair-specific structural proteins (the hair keratins) are stimulated. For example, it has been shown, surprisingly, that the hair keratin expression of the hHa3-l, hHa4, hHb6, and hHa2 hair keratins is significantly elevated. The hair structure, and thus the hair, is thereby reinforced and strengthened. Because the hair structure is already influenced at the hair root, the hair can continue to grow in strong and healthy fashion with no occurrence of age-dependent phenomena such as hair thinning, fragility, or stiffness. [0042] The use of bioquinones in hair cosmetic agents furthermore yields positive results in terms of biological hair thickening. Stimulation of the keratinocytes of the outer root sheath, which are partly responsible for formation of the hair shaft, is accomplished via the growth factors HGF and KGF. Biologically based hair thickening avoids effects such as "over-care" of the hair. The hair grows out from the root strongly and with a larger diameter, so that this effect is particularly long-lasting. [0043] There are no limitations in principle with regard to the kinds of cosmetic preparations in which the bioquinones can be used. Presentations suitable for these preparations are, for example, creams, lotions, solutions, tonics, emulsions such as water-in-oil, oil-in-water, or phase inversion 8 H 07094 temperature (PIT) emulsions, microemulsions, and multiple emulsions, coarse, unstable, single- or multiphase bulk mixtures, gels, sprays, aerosols, and foam aerosols. These are usually formulated on an aqueous or aqueous-alcoholic basis. The alcohol components used in this context are lower alkanols as well as polyols such as propylene glycol and glycerol. Ethanol and isopropanol are preferred alcohols. Water and alcohol can be present in the aqueous alcoholic base at a weight ratio from 1:10 to 10:1. Water, as well as aqueous-alcoholic mixtures that contain up to 50 wt%, in particular up to 25 wt%, alcohol based on the alcohol/water mixture, can be substrates preferred according to the present invention. The pH of these preparations can range, in principle, from values of 2 to 11. It is preferably between 2 and 7, values from 3 to 5 being particularly preferred. Practically any acid or base usable for cosmetic purposes can be utilized to establish this pH value. Edible acids are usually used as acids. "Edible acids" are understood as those acids that are ingested in the context of usual nutrient intake, and have positive effects on the human body. Edible acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid, and gluconic acid. The use of citric acid and lactic acid is particularly preferred in the context of the invention. Preferred bases are ammonia, alkali hydroxides, monoethanolamine, triethanolamine, and N,N,N',N'-tetrakis-(2-hydroxypropyl)ethylenediamine. [0044] The use of bioquinones in preparations that remain on the skin and the hair has proven particularly effective, and can therefore represent a preferred embodiment of the teaching of the present invention. The term "remaining on the skin and the hair" is understood according to the present invention to mean those preparations that are not, in the context of the treatment, rinsed off again from the skin or out of the hair after a period from a few seconds to an hour, using water or an aqueous solution. Instead, the preparations remain on the skin or the hair until it is next washed. [0045] According to a preferred embodiment of the invention, the bioquinones are used in hair therapies or hair conditioners. These preparations can be rinsed out, after a contact time has elapsed, with water or with an at 9 H 07094 least predominantly water-containing agent; preferably, however, they are left on the hair as stated above. [0046] According to further embodiments, however, the bioquinones can also be used in cleaning agents for the skin and hair such as shampoos, makeup removers, face cleaners, care-providing agents for the skin and hair such as rinses, day creams, night creams, face masks, or in setting agents for the hair such as hair-setting agents, foam setting agents, styling gels, and blow-dry waves, in permanent deformation agents such as permanent-wave and immobilization agents, and in hair coloring agents. [0047] In a particular embodiment, the bioquinones are used in agents that are present as a microemulsion. For purposes of the invention, "microemulsions" are also understood as so-called PIT emulsions. These emulsions are, in principle, systems having the three components water, oil, and emulsifier, which exist at room temperature as an oil-in-water (o/w) emulsion. As these systems are heated, in a specific temperature range (usually referred to as the phase inversion temperature or PIT) microemulsions form; upon further heating, these convert into water-in-oil (w/o) emulsions. Subsequent cooling then causes o/w emulsions to form again, but these are present even at room temperature as microemulsions having an average particle diameter less than 400 nm, in particular having a particle diameter of approximately 100 to 300 nm. [0048] The bioquinones can also be used according to the present invention in cosmetic agents that are suitable for treating the skin. "Skin" is to be understood in accordance with the present invention as, in particular, human skin and mucous membrane. [0049] The use of bioquinones in these agents likewise produces thickening of epithelial cells and cell layers, in particular on the skin; an improvement in skin strength; strengthening of the epidermis; a decrease in thinning of the skin, in particular as a result of skin aging phenomena; a reduction in transepidermal water loss from the skin; an improvement in skin moisture; and 10 H 07094 protection of the skin from infections, from exogenous factors such as smog and cigarette smoke, and from stress caused by damaging and/or irritating substances, in particular surfactants, and/or by frequent water contact. [0050] In addition to the use according to the present invention of bioquinones in cosmetic hair treatment agents, the use of further components known to the skilled artisan for such agents may be preferred according to the present invention. [0051] For example, the use of a hair-growth-stimulating active substance may be preferred. It is particularly preferred to use as hair-growth-stimulating active substances those compounds that are selected from 5-a-reductase inhibitors, minoxidil (6-piperidino-2,4-pyrimidinediamine-3 oxide), and aminexil (diaminopyrimidine oxide). [0052] As 5-a-reductase inhibitors are, in particular, functional C2 to C12 carboxylic acids and physiologically acceptable metal salts thereof, in particular 10-hydroxydecanoic acid, 10-hydroxydecenoic acid and derivatives thereof, derivatives of C 3 to C9 polyols, phenol derivatives, plant extracts, odorants, flavonoids, isoflavonoids, 6,7-disubstituted 2,2-dialkylchromanes or chromenes, aluminum chlorohydrate, 2-phenylethanol, etidronic acid, 7-acetyl 1,1,3,4,4,6-hexamethyltetraline, tropolone derivatives, esters of sulfuric acid with alkoxylated C8 to C1a fatty alcohols and physiologically acceptable metal salts thereof, esters of phosphoric acid and triphosphoric acid with monovalent to hexavalent hydroxy compounds, silicic acid esters, mycosporin-like amino acids (MAAs) isolatable from marine organisms, and quaternary silicone compounds. "Derivatives" are to be understood in particular as salts, esters, and amides thereof. Very particularly preferred in this context are 10-hydroxydecanoic acid, 10 hydroxydecenoic acid, and finasteride (N-tert.-butyl-3-oxo-4-aza-5a-androst-1 ene-17p-carboxamide) and derivatives thereof. 11 H 07094 [0053] The use of the hair-growth-stimulating active substances minoxidil and Finasteride is very particularly preferred. [0054] Also preferred is the use of polymers in addition to the bioquinones. "Polymers" are to be understood as both natural and synthetic polymers, which can be anionically, cationically, or amphoterically charged, or nonionic. [0055] "Cationic polymers" are to be understood as polymers that comprise in the main chain and/or side chain a group that can be "temporarily" or "permanently" cationic. According to the present invention, those polymers that possess a cationic group regardless of the pH of the agent are referred to as "permanently cationic." These are, as a rule, polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bound via a C1.4 hydrocarbon group to a main polymer chain made up of acrylic acid, methacrylic acid, or derivatives thereof, have proven to be particularly suitable. [0056] Homopolymers of the general formula (PI) R 18 -[CH2-C-]n X~ (PI)

CO-O-(CH

2 )m-NR 1R 20R in which R1 8 = -H or -CH 3 , R", R 20 and R 21 are selected, mutually independently, from C1.4 alkyl, alkenyl, or hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number, and X~ is a physiologically acceptable organic or inorganic anion, as well as copolymers made up substantially of the monomer units presented in formula (PI) as well as nonionogenic monomer units, are particularly preferred cationic polymers. In the context of these polymers, those for which at least one of the following conditions apply are preferred according to the present invention: 12 H 07094 - R 18 denotes a methyl group - R", R" and R" denote methyl groups - m has the value of 2. [0057] Possibilities as physiologically acceptable counterions X~ are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions, and organic ions such as lactate, citrate, tartrate, and acetate ions. Halide ions, in particular chloride, are preferred. [0058] A particularly suitable homopolymer is the poly(methacryloyloxyethyltrimethylammonium chloride) (crosslinked, if desired) having the INCI name Polyquaternium-37. The crosslinking can be accomplished, if desired, with the aid of polyolefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylene bisacrylamide, diallyl ether, polyallylpolyglyceryl ether, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose, or glucose. Methylene bisacrylamide is a preferred cross linking agent. [0059] The homopolymer is preferably used in the form of a nonaqueous polymer dispersion that should comprise a polymer proportion not less than 30 wt%. Such polymer dispersions are obtainable commercially under the designations Salcare* SC 95 (approx. 50 % polymer proportion, further components: mineral oil (INCI name: Mineral Oil) and tridecylpolyoxypro pylenepolyoxyethylene ether (INCI name: PPG-1-Trideceth-6)), and Salcare* SC 96 (approx. 50 % polymer proportion, further components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: Propylene Glycol Dicaprylate/Dicaprate) and tridecylpolyoxypropylenepolyoxyethylene ether (INCl name: PPG-1-Trideceth 6)). [0060] Copolymers having monomer units according to formula (PI) preferably contain acrylamide, methacrylamide, acrylic acid C 1 4 alkyl esters, and methacrylic acid C 1 4 alkyl esters as nonionogenic monomer units,. Of 13 H 07094 these nonionogenic monomers, acrylamide is particularly preferred. These copolymers as well, as in the case of the homopolymers described above, can be crosslinked. A copolymer preferred according to the present invention is the crosslinked copolymer of acrylamide and methacryloyloxyethyltrimethylammonium chloride. Such copolymers, in which the monomers are present at a weight ratio of approximately 20:80, are commercially obtainable, as an approx. 50% nonaqueous polymer dispersion, under the designation Salcare* SC 92. [0061] Additional preferred cationic polymers are, for example: - quaternized cellulose derivatives such as those obtainable commercially under the designations Celquat* and Polymer JR®. The compounds Celquat* H 100, Celquat* L 200, and Polymer JR* 400 are preferred quaternized cellulose derivatives; - cationic alkyl polyglycosides; - cationized honey, for example the commercial product Honeyquat* 50; - cationic guar derivatives such as, in particular, the products marketed under the trade names Cosmedia* Guar and Jaguar; - polysiloxanes having quaternary groups, such as, for example, the commercially obtainable products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 Emulsion (containing a hydroxylamino-modified silicone that is also referred to as Amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker), and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80); - polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products available commercially under the designations Merquat* 100 (poly(dimethyldiallylammonium chloride)) and Merquat® 550 (dimethyldiallylammonium chloride / acrylamide copolymer) are examples of such cationic polymers; - copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as, for example, 14 H 07094 vinylpyrrolidone / dimethylaminoethylmethacrylate copolymers quaternized with diethyl sulfate. Such compounds are obtainable commercially under the designations Gafquat 734 and Gafquat* 755; - vinylpyrrolidone / vinylimidazolium methochloride copolymers, such as those offered under the designations Luviquat* FC 370, FC 550, FC 905, and HM 552; - quaternized poly(vinylalcohol); and the polymers known under the designations - Polyquaternium-2, - Polyquaternium-17, - Polyquaternium-18, and - Polyquaternium-27, having quaternary nitrogen atoms in the main polymer chain. [0062] The polymers known under the designations Polyquaternium-24 (commercial product e.g. Quatrisoft* LM 200) can similarly be used as cationic polymers. Likewise usable according to the present invention are the copolymers of vinylpyrrolidone such as those available as the commercial products Copolymer 845 (manufacturer: ISP), Gaffix* VC 713 (manufacturer: ISP), Gafquat* ASCP 1011, Gafquat* HS 110, Luviquat* 8155, and Luviquat* MS 370. [0063] Additional cationic polymers according to the present invention are the so-called "temporarily cationic" polymers. These polymers usually contain an amino group that is present at certain pH values as a quaternary ammonium group and therefore cationically. Chitosan and its derivatives, such as those readily available commercially, for example, under the commercial designations Hydagen* CMF, Hydagen* HCMF, Kytamer* PC, and Chitolam* NB/101, are, for example, preferred. Chitosans are deacetylated chitins that are available commercially at various degrees of deacetylation and various degrees of decomposition (molecular weights). Their manufacture is described, for example, in DE 44 40 625 Al and DE 1 95 03 465 Al. 15 H 07094 [0064] Chitosans that are particularly suitable have a degree of deacetylation of at least 80%, and a molecular weight from 5 - 10 5 to 5 - 106 (g/mol). [0065] For the manufacture of preparations according to the present invention, the chitosan must be converted into salt form. This can be accomplished by dissolution in dilute aqueous acids. Suitable acids are both mineral acids such as, for example, hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as low-molecular-weight carboxylic acids, polycarboxylic acids, and hydroxycarboxylic acids. Higher-molecular weight alkylsulfonic acids or alkylsulfuric acids or organophosphoric acids can also be used, provided they exhibit the necessary physiological acceptability. Suitable acids for converting chitosan into the salt form are, for example, acetic acid, glycolic acid, tartaric acid, malic acid, citric acid, lactic acid, 2 pyrrolidinone-5-carboxylic acid, benzoic acid, or salicylic acid. Low-molecular weight hydroxycarboxylic acids such as, for example, glycolic acid or lactic acid are preferably used. [0066] The anionic polymers that can reinforce the effect of the bioquinone(s) used according to the present invention are anionic polymers that comprise carboxylate and/or sulfonate groups. Examples of anionic monomers of which such polymers can be made up are acrylic acid, methacrylic acid, crotonic acid, maleic acid anhydride, and 2-acrylamido-2 methylpropanesulfonic acid. The acid groups can be present entirely or partially as a sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid. [0067] Anionic polymers that contain 2-acrylamido-2-methylpropanesulfonic acid as a sole monomer or co-monomer have proven to be very particularly effective, in which context the sulfonic acid group can be present entirely or partially as a sodium, potassium, ammonium, mono- or triethanolammonium salt. 16 H 07094 [0068] The homopolymer of 2-acrylamido-2-methylpropanesulfonic acid that is available commercially, for example, under the designation Rheothik' 11-80, is particularly preferred. [0069] Within this embodiment, it may be preferred to use copolymers of at least one anionic monomer and at least one nonionogenic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionogenic monomers are acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, vinylpyrrolidone, vinyl ether, and vinyl ester. [0070] Preferred anionic copolymers are acrylic acid/acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid group-containing monomers. A particularly preferred anionic copolymer is made up of 70 to 55 mol% acrylamide and 30 to 45 mol% 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being present entirely or partially as a sodium, potassium, ammonium, mono-, or triethanolammonium salt. This copolymer can also be present in crosslinked form, polyolefinically unsaturated compounds such as tetraallyoxyethane, allylsucrose, allylpentaerythritol, and methylene bisacrylamide preferably being used as crosslinking agents. One such polymer is contained in the commercial product Sepigel* 305 of the SEPPIC company. The utilization of this compound, which in addition to the polymer component contains a hydrocarbon mixture (C13 to C14 isoparaffin) and a nonionogenic emulsifier (Laureth-7), has proven particularly advantageous in the context of the teaching according to the present invention. [0071] The sodium acryloyl dimethyl taurate copolymers marketed, under the designation Simulgel" 600, as a compound with isohexadecane and polysorbate-80 have also proven particularly effective according to the present invention. [0072] Similarly preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, of sucrose, and of 17 H 07094 propylene can be preferred crosslinking agents. Such compounds are obtainable commercially, for example, under the trademark Carbopol*. [0073] Copolymers of maleic acid anhydride and methylvinyl ether, in particular those having crosslinks, are also color-preserving polymers. A maleic acid/methylvinyl ether copolymer crosslinked with 1,9-decadiene is obtainable commercially under the designation Stabileze* QM. [0074] Amphoteric polymers can also be used as a constituent as polymers to enhance the effect of the bioquinone(s) used according to the present invention. The term "amphoteric polymers" encompasses both those polymers that contain in the molecule both free amino groups and free -COOH or SO 3 H groups and are capable of forming internal salts, and zwitterionic polymers, which contain quaternary ammonium groups and -COO- or -SO3 groups in the molecule, and those polymers that contain -COOH or SO 3 H groups and quaternary ammonium groups. [0075] One example of an amphopolymer usable according to the present invention is the acrylic resin obtainable under the name Amphomer*, which represents a copolymer of tert.-butylaminoethyl methacrylate, N-(1,1,3,3 tetramethylbutyl)acrylamide, and two or more monomers from the group of acrylic acid, methacrylic acid, and simple esters thereof. [0076] Amphoteric polymers that are preferred for use are those polymerizates that are made up substantially of (a) monomers having quaternary ammonium groups of the general formula (P11),

R

22

-CH=CR

23 CZ(CnH 2 n)-N(+)R24R2R2 A( (Pll) in which R 22 and R 2 3 , mutually independently, denote hydrogen or a 24 25 26 methyl group and R , R , and R , mutually independently, denote alkyl groups having 1 to 4 carbon atoms, Z denotes an NH group or an 18 H 07094 oxygen atom, n is a whole number from 2 to 5, and A" is the anion of an organic or inorganic acid; and (b) monomeric carboxylic acids of the general formula (Pill) R 27-CH=CR 2 8 -COOH (Pill) in which R 2 and R 2 , mutually independently, are hydrogen or methyl groups. [0077] These compounds can be used according to the present invention both directly and in a salt form obtained by neutralization of the polymerizates, for example using an alkali hydroxide. With regard to details of the manufacture of these polymerizates, reference is made explicitly to the content of German Application 39 29 973. Those polymerizates in which monomers of type (a) are used in which R , R , and R are methyl groups, Z is an NH group, and A" is a halide, methoxysulfate, or ethoxysulfate ion, are very particularly preferred; acrylamidopropyltrimethylammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably utilized as monomer (b) for the aforesaid polymerizates. [0078] The additional use of nonionogenic polymers may likewise be preferred according to the present invention. [0079] Suitable nonionogenic polymers are, for example: - Vinylpyrrolidone/vinyl ester copolymers such as those marketed, for example, under the trademark Luviskol* (BASF). Luviskol* VA 64 and Luviskol* VA 73, which are each vinylpyrrolidone/vinyl acetate copolymers, are likewise preferred nonionic polymers. - Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose, and methylhydroxypropyl cellulose, such as those marketed, for example, under the trademarks Culminal* and Benecel* (AQUALON). - Shellac 19 H 07094 - Polyvinylpyrrolidones such as those marketed, for example, under the designation Luviskol* (BASF). - Siloxanes. These siloxanes can be both water-soluble and water insoluble. Both volatile and nonvolatile siloxanes are suitable, "nonvolatile siloxanes" being understood as those compounds whose boiling point is above 200*C at standard pressure. Preferred siloxanes are polydialkylsiloxanes such as, for example, polydimethylsiloxane, polyalklyarylsiloxanes such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes, and polydialkylsiloxanes that contain amine and/or hydroxy groups. - Glycosidically substituted silicones. [0080] It is also possible according to the present invention to use several, in particular two, different polymers of the same charge and/or respectively one ionic and one amphoteric and/or nonionic polymer simultaneously. [0081] The term "polymer" is likewise to be understood, according to the present invention, to mean special preparations of polymers such as spherical polymer powders. A number of methods are known for manufacturing such microspheres from a variety of monomers, e.g. by way of special polymerization methods or by dissolving the polymer in a solvent and spraying it into a medium in which the solvent can evaporate or can diffuse out of the particles. One such method is known, for example, from EP 466 986 B1. Suitable polymerizates are, for example, polycarbonates, polyurethanes, polyacrylates, polyolefins, polyesters, or polyamides. Those spherical polymer powders whose primary particle diameter is less than 1 pm are particularly suitable. Products of this kind based on a polymethacrylate copolymer are on the market, for example, under the trademark Polytrap* Q5-6603 (Dow Corning). Other polymer powders, for example based on polyamides (nylon-6, nylon-12), having a particle size from 2 to 10 pm (90 %) and a specific surface of approx. 10 m 2 /g, are obtainable under the commercial designation Orgasol* 2002 DU Nat Cos (Atochem S.A., Paris). Further spherical polymer powders that are suitable for the purpose of the present invention are, for example the polymethacrylates (Micropearl M) of SEPPIC or (Plastic Powder A) of NIKKOL, 20 H 07094 the styrene/divinylbenzene copolymers (Plastic Powder FP) of NIKKOL, the polyethylene and polypropylene powders (ACCUREL EP 400) of AKZO, or also silicone polymers (Silicone Powder X2-1605) of Dow Corning or also spherical cellulose powders. [0082] Use of the polymers in quantities from 0.01 to 10 wt%, based on the entire agent, is preferred according to the present invention. Quantities from 0.1 to 5, in particular from 0.1 to 3 wt%, are particularly preferred. [0083] In a further embodiment of the invention, protein hydrolysates and/or derivatives thereof can be used to enhance the effect of the bioquinone(s) utilized according to the present invention. Protein hydrolysates are product mixtures obtained by the acid-, base-, or enzyme-catalyzed breakdown of proteins. [0084] According to the present invention, protein hydrolysates of both vegetable and animal origin can be used. [0085] Animal protein hydrolysates are, for example, hydrolysates of elastin, collagen, keratin, silk, and milk protein, which can also be present in the form of salts. Such products are marketed, for example, under the trademarks Dehylan* (Cognis), Promois* (Interorgana), Collapuron* (Cognis), Nutrilan* (Cognis), Gelita-Sol® (Deutsche Gelatine Fabriken Stoess & Co), Lexein* (Inolex), Sericin (Pentapharm), and Kerasol* (Croda). [0086] The use of protein hydrolysates of vegetable origin, e.g. soy, almond, rice, bean, potato, and wheat protein hydrolysates, is preferred according to the present invention. Such products are obtainable, for example, under the trademarks Gluadin" (Cognis), DiaMin® (Diamalt), Lexein® (Inolex), and Crotein* (Croda). [0087] Although the use of protein hydrolysates per se is preferred, it is also optionally possible to use instead of them, if applicable, amino-acid mixtures 21 H 07094 obtained in different fashion, or individual amino acids such as, for example, arginine, lysine, histidine, or pyrroglutamic acid. It is likewise possible to use derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are marketed, for example, under the designations Lamepon* (Cognis), Lexein* (Inolex), Crolastin* (Croda), Crosilk* (Croda), or Crotein" (Croda). [0088] Also usable according to the present invention are cationized protein hydrolysates, in which context the underlying protein hydrolysate can derive from animals, for example from collagen, milk, or keratin, from plants, for example from wheat, corn, rice, potatoes, soy, or almonds, from marine life forms, for example from fish collagen or algae, or from biotechnologically obtained protein hydrolysates. The protein hydrolysates serving as the basis for the cationic derivatives according to the present invention can be obtained from the corresponding proteins by way of a chemical, in particular alkaline or acid, hydrolysis, by an enzymatic hydrolysis, and/or by a combination of both types of hydrolysis. The hydrolysis of proteins results, as a rule, in a protein hydrolysate having a molecular weight distribution from approximately 100 dalton up to several thousand dalton. Those cationic protein hydrolysates whose underlying protein component has a molecular weight from 100 to 25,000 dalton, preferably 250 to 5,000 dalton, are preferred. Also to be understood as cationic protein hydrolysates are quaternized amino acids and mixtures thereof. Quaternization of the protein hydrolysates or amino acids is often carried out by means of quaternary ammonium salts such as, for example, N,N-dimethyl-N-(n-alkyl)-N-(2-hydroxy-3-chloro-n-propyl)ammonium halides. The cationic protein hydrolysates can furthermore also be further derivatized. Typical examples that may be mentioned of cationic protein hydrolysates and derivatives according to the present invention are the following products listed under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association, 1101 17 th Street, N.W., Suite 300, Washington, DC 20036-4702), and available commercially: Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium 22 H 07094 Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Silk, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl Silk Amino Acids, Hydroxypropyl Arginine Lauryl/Myristyl Ether HCI, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Silk, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein/Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein/Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Silk, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein. The vegetable-based cationic protein hydrolysates and derivatives are very particularly preferred. 23 H 07094 [0089] The protein hydrolysates and derivatives thereof are used preferably in quantities from 0.01 to 10 wt%, based on the entire agent. Quantities from 0.1 to 5 wt%, in particular 0.1 to 3 wt%, are very particularly preferred. [0090] In a further preferred embodiment of the invention, surfactants can additionally be utilized to enhance the effect of the bioquinone(s) used according to the present invention. [0091] The term "surfactants" is understood as surface-active substances that carry an anionic or cationic charge in the molecule. Likewise, both an anionic and a cationic charge can be present in the molecule. These zwitterionic or amphoteric surface-active substances can likewise be used according to the present invention. The surface-active substances can also be nonionic. [0092] All anionic surface-active substances suitable for utilization on the human body are suitable in principle as anionic surfactants in preparations according to the present invention. These substances are characterized by a water-solubility-creating anionic group such as, for example, a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group having approximately 8 to 30 carbon atoms. Glycol or polyglycol ether groups, ester, ether, and amide groups, and hydroxyl groups can additionally be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium, and ammonium as well as mono-, di-, and trialkanolammonium salts having 2 to 4 carbon atoms in the alkanol group: - linear fatty acids having 8 to 30 carbon atoms (soaps); - ethercarboxylic acids of the formula R-O-(CH 2

-CH

2 0)x-CH 2 -COOH, in which R is a linear alkyl group having 8 to 30 carbon atoms and x = 0 or is 1 to 16; - acylsarcosides having 8 to 24 carbon atoms in the acyl group; - acyltaurides having 8 to 24 carbon atoms in the acyl group; - acylisethionates having 8 to 24 carbon atoms in the acyl group; - sulfosuccinic acid mono- and -dialkyl esters having 8 to 24 carbon atoms in the alkyl group, and sulfosuccinic acid monoalkylpolyoxyethyl esters 24 H 07094 having 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups; linear alkanesulfonates having 8 to 24 carbon atoms; alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms; alkyl sulfates and alkylpolyglycol ether sulfates of the formula R-O(CH 2 CH 2 0)r,-OSO 3 H, in which R is a preferably linear alkyl group having 8 to 30 carbon atoms and x = 0 or is 1 to 12; mixtures of surface-active hydroxysulfonates according to DE A 37 25 030; sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds, according to DE-A-39 26 344; esters of tartaric acid and citric acid with alcohols that represent addition products of approximately 2 to 15 molecules ethylene oxide and/or propylene oxide with fatty alcohols having 8 to 22 carbon atoms. alkyl and/or alkenyl ether phosphates of the formula (TI) 0

R

2 (OCH 2CH 2)- O -P - OR 3 (TI) ox in which R 2 preferably denotes an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R3 denotes hydrogen, a (CH 2

CH

2 0)nR2 radical, or X, n denotes numbers from 1 to 10, and X denotes hydrogen, an alkali or alkaline-earth metal, or NR3 R 32R33R34, where R3 to R34, mutually independently, denote hydrogen or a C1 to C 4 hydrocarbon radical; sulfated fatty acid alkylene glycol esters of the formula (Til) RasCO(AlkO)nSO 3 M (TiI) in which R aCO- denotes a linear or branched, aliphatic, saturated and/or unsaturated acyl radical having 6 to 22 carbon atoms, Alk denotes

CH

2

CH

2 , CHCH 3

CH

2 , and/or CH 2

CHCH

3 , n denotes numbers from 0.5 to 25 H 07094 5, and M denotes a cation, as described in German Application 197 36 906.5; - monoglyceride sulfates and monoglyceride ether sulfates of the formula (Till)

CH

2 0(CH 2

CH

2 O),-COR36

CHO(CH

2

CH

2 O)y-H (TIll)

CH

2 0(CH 2

CH

2 0)-SO 3 X in which R 3Co denotes a linear or branched acyl radical having 6 to 22 carbon atoms, x, y, and z in total denote 0 or numbers from 1 to 30, preferably 2 to 10, and X denotes an alkali or alkaline-earth metal. Typical examples of monoglyceride (ether) sulfates suitable for purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride, and tallow fatty acid monoglyceride, and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. [0093] It is preferable to use monoglyceride sulfates of formula (Till) in which R 36 CO denotes a linear acyl radical having 8 to 18 carbon atoms. [0094] Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates, and ethercarboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group, and sulfosuccinic acid monoalkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups. [0095] "Zwitterionic surfactants" refers to those surface-active compounds that contain in the molecule at least one quaternary ammonium group and at least one -COO) or -SO3 group. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example cocalkyldimethylammonium glycinate, N 26 H 07094 acylaminopropyl-N,N-dimethylammonium glycinates, for example cocacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl 3-hydroxyethylimidazolines, having in each case 8 to 18 carbon atoms in the alkyl or acyl group, as well as cocacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine. [0096] "Ampholytic surfactants" are understood to be those surface-active compounds that contain in the molecule, in addition to a C8 to 1024 alkyl or acyl group, at least one free amino group and at least one -COOH or -SO 3 H group, and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2 alkylaminopropionic acids, and alkylaminoacetic acids, having in each case 8 to 24 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocalkylaminopropionate, cocacylaminoethyl aminopropionate, and C12 - C18 -acylsarcosine. [0097] Nonionic surfactants contain as a hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group, or a combination of a polyol and polyglycol ether group. Such compounds are, for example: - addition products of 2 to 50 mol ethylene oxide and/or 0 to 5 mol propylene oxide with linear and branched fatty alcohols having 8 to 30 carbon atoms, with fatty acids having 8 to 30 carbon atoms, and with alkylphenols having 8 to 15 carbon atoms in the alkyl group; - addition products, end-capped with a methyl or C2 to C6 alkyl group, of 2 to 50 mol ethylene oxide and/or 0 to 5 mol propylene oxide with linear and branched fatty alcohols having 8 to 30 carbon atoms, with fatty acids having 8 to 30 carbon atoms, and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as, for example, the grades obtainable under the marketing designations Dehydol" LS, Dehydol* LT (Cognis); - C12 to C30 fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide with glycerol; 27 H 07094 - addition products of 5 to 60 mol ethylene oxide with castor oil and hardened castor oil; - polyol fatty acid esters such as, for example, the commercial product Hydagen* HSP (Cognis), or Sovermol grades (Cognis); - alkoxylated triglycerides; - alkoxylated fatty acid alkyl esters of the formula R 37

CO

(OCH

2

CHR

3

).OR

3 9 (TIV), in which R 37 CO denotes a linear or branched, saturated and/or unsaturated acyl radical having 6 to 22 carbon atoms, R denotes hydrogen or methyl, R 3 9 denotes linear or branched alkyl radicals having 1 to 4 carbon atoms, and w denotes numbers from 1 to 20; - amine oxides - hydroxy mixed ethers, such as those described e.g. in German Application 197 38 866; - sorbitan fatty acid esters and addition products of ethylene oxide with sorbitan fatty acid esters, for example the polysorbates; - sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters; - addition products of ethylene oxide with fatty acid alkanolamides and fatty amines; - fatty acid N-alkyl glucamides; - alkyl polyglycosides corresponding to the general formula RO-(Z)x, where R denotes alkyl, Z sugar, and x the number of sugar units. The alkyl polyglycosides usable according to the present invention can contain only one specific alkyl radical R. Usually, however, these compounds are manufactured from natural fats and oils or mineral oils. In this case what is present as alkyl radicals R are mixtures corresponding to the initial compounds or corresponding to the particular processing of those compounds. [0098] Particularly preferred are those alkyl polyglycosides in which R comprises - substantially

C

8 and C1o alkyl groups; 28 H 07094 - substantially C 12 and C 14 alkyl groups; - substantially C 8 to C 16 alkyl groups; or - substantially C 12 to C 16 alkyl groups; or - substantially C 16 to C 18 alkyl groups. [0099] Any mono- or oligosaccharides can be used as the sugar module Z. Sugars having 5 or 6 carbon atoms, as well as the corresponding oligosaccharides, are usually used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose, and sucrose. Preferred sugar modules are glucose, fructose, galactose, arabinose, and sucrose; glucose is particularly preferred. [0100] The alkyl polyglycosides usable according to the present invention contain on average 1.1 to 5 sugar units, Alkyl polyglycosides having values of x from 1.1 to 2.0 are preferred. Alkyl polyglycosides in which x equals 1.1 to 1.8 are very particularly preferred. [0101] The alkoxylated homologs of the aforesaid alkyl polyglycosides can also be used according to the present invention. These homologs can contain, on average, up to 10 ethylene oxide and/or propylene oxide units per alkyl glycoside unit. [0102] The alkylene oxide addition products with saturated linear fatty alcohols and fatty acids, having respectively 2 to 30 mol ethylene oxide per mol fatty alcohol or fatty acid, have proven to be preferred nonionic surfactants. Preparations having outstanding properties are likewise obtained if they contain, as nonionic surfactants, fatty acid esters of ethoxylated glycerol. [0103] These compounds are characterized by the following parameters: The alkyl radical R contains 6 to 22 carbon atoms and can be both linear and branched. Primary linear aliphatic radicals, and those methyl-branched in the 2- position, are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl, and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, and 1 myristyl are particularly preferred. When so-called "oxo alcohols" are used as 29 H 07094 the starting materials, compounds having an odd number of carbon atoms in the alkyl chain predominate. [0104] The compounds having alkyl groups used as surfactants can in each case be uniform substances. It is generally preferred, however, to proceed from natural vegetable or animal raw materials when producing these substances, so that substance mixtures having different alkyl chain lengths, dependent on the particular material, are obtained. [0105] In the surfactants that represent addition products of ethylene oxide and/or propylene oxide with fatty alcohols, or derivatives of such addition products, both products having a "normal" homolog distribution and those having a restricted homolog distribution can be used. A "normal" homolog distribution is understood to mean mixtures of homologs that are obtained when reacting fatty alcohol and alkylene oxide using alkali metals, alkali-metal hydroxides, or alkali-metal alcoholates as catalysts. Restricted homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline-earth metal salts of ethercarboxylic acids, or alkaline-earth metal oxides, hydroxides, or alcoholates are used as catalysts. The use of products having a restricted homolog distribution can be preferred. [0106] These surfactants are used in quantities from 0.1 to 45 wt%, preferably 1 to 30 wt%, and very particularly preferably 1 to 15 wt%, based on the entire agent. [0107] In a preferred embodiment, nonionic, zwitterionic, and/or amphoteric surfactants, as well as mixtures thereof, are preferred. [0108] Also usable according to the present invention are cationic surfactants of the following types: quaternary ammonium compounds, esterquats, and amidoamines. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyl trimethylammonium chlorides, dialkyl dimethylammonium chlorides, and trialkyl methylammonium chlorides, e.g. cetyl trimethylammonium chloride, stearyl 30 H 07094 trimethylammonium chloride, distearyl dimethylammonium chloride, lauryl dimethylammonium chloride, lauryl dimethylbenzylammonium chloride, and tricetyl methylammonium chloride, as well as the imidazolium compounds known by the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the aforementioned surfactants preferably have 10 to 18 carbon atoms. [0109] Esterquats are known substances that contain both at least one ester function and at least one quaternary ammonium group as structural elements. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines, and quaternized ester salts of fatty acids with 1,2 dihydroxypropyldialkylamines. Such products are marketed, for example, under the trademarks Stepantex*, Dehyquart*, and Armocare*. Examples of such esterquats are the products Armocare® VGH-70 - an N,N-bis(2 palmitoyloxyethyl)dimethylammonium chloride - and Dehyquarts F-75 and Dehyquart* AU-35. [0110] The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. One compound from this group of substances that is particularly suitable according to the present invention is the stearamidopropyldimethylamine available commercially under the designation Tegoamid* S 18. [0111] The cationic surfactants are used preferably in quantities from 0.05 to 10 wt%, based on the entire agent. Quantities from 0.1 to 5 wt% are particularly preferred. [0112] In a further preferred embodiment, the effect of the bioquinone(s) used can be enhanced by emulsifiers. Such emulsifiers are, for example: - addition products of 4 to 30 mol ethylene oxide and/or 0 to 5 mol 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; 31 H 07094 - C12 to C 22 fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide with polyols having 3 to 6 carbon atoms, in particular with glycerol; - ethylene oxide and polyglycerol addition products with methyl glucoside fatty acid esters, fatty acid alkanolamides, and fatty acid glucamides; - C8 to C22 alkyl mono- and oligoglycosides and their ethoxylated analogs, degrees of oligomerization of 1.1 to 5, in particular 1.2 to 2.0, and glucose as the sugar component, being preferred; - mixtures of alkyl (oligo)glucosides and fatty alcohols, for example the commercially available product Montanov* 68; - addition products of 5 to 60 mol ethylene oxide with castor oil and hardened castor oil; - partial esters of polyols having 3 to 6 carbon atoms with saturated fatty acids having 8 to 22 carbon atoms; - Sterols. "Sterols" are understood to mean a group of steroids that carry a hydroxyl group on the third carbon atom of the steroid structure and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol, and sitosterol. Sterols called "mycosterols" are also isolated from fungi and yeasts. - Phospholipids. These are understood to mean principally the glucose phospholipids, which are obtained e.g. as lecithins or phosphatidylcholines from, for example, egg yolk or plant seeds (e.g. soybeans). - Fatty acid esters of sugars and sugar alcohols, such as sorbitol, - Polyglycerols and polyglycerol derivatives such as, for example, polyglycerol poly-1 2-hyd roxystearate (commercial product Dehymuls* PGPH). - Linear and branched fatty acids having 8 to 30 carbon atoms, and their Na, K, ammonium, Ca, Mg, and Zn salts. [0113]The emulsifiers are used preferably in quantities from 0.1 to 25 wt%, in particular 0.5 to 15 wt%, based on the entire agent. 32 H 07094 [0114]In principle, nonionogenic emulsifiers having an HLB value from 8 to 18 can be used. Nonionogenic emulsifiers having an HLB value from 10 to 15 may be particularly preferred according to the present invention. [0115]Among the aforesaid emulsifier types, the emulsifiers that contain no ethylene oxide and/or propylene oxide in the molecule may be very particularly preferred. [0116]In a further preferred embodiment of the invention, the effect of the quinone(s) used can be enhanced by fatty substances. "Fatty substances" are to be understood as fatty acids, fatty alcohols, natural and synthetic waxes that can be present both in solid form and in liquid form in aqueous dispersion, and natural and synthetic cosmetic oil components. [0117]The fatty acids that can be used are linear and/or branched, saturated and/or unsaturated fatty acids having 6 to 30 carbon atoms. Fatty acids having 10 to 22 carbon atoms are preferred. Among those that might be mentioned are, for example, the isostearic acids, such as the commercial products Emersol* 871 and Emersol* 875, and isopalmitic acids such as the commercial product Edenoro IP 95, as well as all other fatty acids marketed under the Edenor* commercial designations (Cognis). Further typical examples of such fatty acids are hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and erucic acid, as well as industrial mixtures thereof that occur, for example, upon high-pressure cleavage of natural fats and oils, upon oxidation of aldehydes from Roelen oxosynthesis, or upon dimerization of unsaturated fatty acids. The fatty acid cuts that are obtainable from coconut oil or palm oil are usually particularly preferred; the use of stearic acid is, as a rule, particularly preferred. 33 H 07094 [0118]The quantity used is 0.1 to 15 wt% based on the entire agent. In a preferred embodiment, the quantity is 0.5 to 10 wt%, quantities from 1 to 5 wt% being very particularly advantageous. [0119]The following can be used as fatty alcohols: saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols having C 6 to C 30 , preferably C 10 to C 22 , and very particularly preferably C 1 2 to C 22 carbon atoms. Usable in the context of the invention are, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, erucic alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol, and behenyl alcohol, as well as Guerbet alcohols thereof, this listing being intended to be exemplary and not limiting in nature. The fatty alcohols preferably derive, however, from natural fatty acids; it is usually possible to proceed from an extraction from the esters of the fatty acids by reduction. Also usable according to the present invention are those fatty alcohol cuts that are generated by the reduction of naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, colza oil, cottonseed oil, soybean oil, sunflower oil, and linseed oil, or from fatty acid esters resulting from their transesterification products with corresponding alcohols, and that thus represent a mixture of different fatty alcohols. Such substances are, for example, available commercially under the designations Stenol*, e.g. Stenol* 1618, or Lanette®, e.g. Lanette* 0, or Lorol*, e.g. Lorol* C8, Lorol* C14, Lorol* C18, Lorol* C8-18, HD-Ocenol®, Crodacol*, e.g. Crodacol* CS, Novol*, Eutanol* G, Guerbitol* 16, Guerbitol* 18, Guerbitol* 20, Isofol* 12, Isofol® 16 Isofol® 24, Isofol* 36, Isocarb* 12, Isocarb* 16, or Isocarbe 24. It is of course also possible according to the present invention to use wool-wax alcohols such as those available commercially under the designations Coronae, White Swan*, Coronet®, or Fluilan*. The fatty alcohols are used in quantities from 0.1 to 20 wt%, based on the entire preparation, preferably in quantities from 0.1 to 10 wt%. [0120]Solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candelilla waxes, ozocerites, ceresin, spermaceti, sunflower wax, fruit waxes such as, for 34 H 07094 example, apple wax or citrus wax, or microcrystalline waxes made from PE or PP can be used according to the present invention as natural or synthetic waxes. Such waxes are obtainable, for example, via Kahl & Co., Trittau. [0121]Among the natural and synthetic cosmetic oily substances that can enhance the effect of the quinone(s) used according to the present invention may be listed, for example: - Vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach-kernel oil, and the liquid components of coconut oil. Also suitable, however, are other triglyceride oils such as the liquid components of beef tallow, as well as synthetic triglyceride oils. - Liquid paraffin oils, isoparaffin oils, and synthetic hydrocarbons, as well as di-n-alkyl ethers having a total of between 12 and 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether, and n-hexyl-n-undecyl ether, as well as ditert.-butyl ether, diisopentyl ether, di-3-ethyldecyl ether, tert.-butyl n-octyl ether, isopentyl-n-octyl ether, and 2-methylpentyl-n-octyl ether. The compounds 1,3-di-(2-ethylhexyl)cyclohexane (Cetiol* S) and di-n octyl ether (Cetiol* OE), available as commercial products, can be preferred. - Ester oils. "Ester oils" are to be understood as the esters of Ce to C30 fatty acids with C2 to C30 fatty alcohols. The monoesters of fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid components used in the esters are hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and erucic acid, as well as industrial mixtures thereof that occur, for example, upon high-pressure cleavage of natural fats and oils, upon oxidation of aldehydes from Roelen oxosynthesis, or upon dimerization 35 H 07094 of unsaturated fatty acids. Examples of the fatty alcohol components in the ester oils are isopropyl alcohol, hexanol, octanol, 2-ethylhexyl alcohol, decanol, lauryl 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, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and brassidyl alcohol, as well as industrial mixtures thereof that occur, for example, upon high-pressure hydrogenation of industrial methyl esters based on fats and oils or aldehydes from Roelen oxosynthesis, and as a monomer fraction upon dimerization of unsaturated fatty alcohols. Particularly preferred according to the present invention are isopropyl myristate (Rilanit* IPM), isononanoic acid C16-18 alkyl ester (Cetiol* SN), 2-ethylhexyl palmitate (Cegesoft* 24), stearic acid 2-ethylhexyl ester (Cetiol* 868), cetyl oleate, glycerol tricaprylate, coconut fatty alcohol caprinate/caprylate (Cetiol* LC), n-butyl stearate, oleyl erucate (Cetiol* J 600), isopropyl palmitate (Rilanit* IPP), Oleyl Oleate (Cetiol*), lauric acid hexyl ester (Cetiol* A), di-n-butyl adipate (Cetiol* B), myristyl myristate (Cetiol* MM), Cetearyl Isononanoate (Cetiol* SN), oleic acid decyl ester (Cetiol* V). - Dicarboxylic acid esters such as di-n-butyl adipate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) succinate, and diisotridecyl acelaate, as well as diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethyl hexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate, neopentyl glycol dicaprylate. - Symmetrical, asymmetrical, or cyclic esters of carbonic acid with fatty alcohols, described for example in German Application DE 197 56 454, glycerol carbonate, or dicaprylyl carbonate (Cetiol* CC). - Mono-, di-, and trifatty acid esters of saturated and/or unsaturated linear and/or branched fatty acids with glycerol, for example Monomuls* 90-018, Monomuls' 90-L12, or Cutina* MD. 36 H 07094 [0122]The quantity used is 0.1 to 50 wt% based on the entire agent, preferably 0.1 to 20 wt%, and particularly preferably 0.1 to 15 wt% based on the entire agent. [0123]The total quantity of oily and fatty components usable according to the present invention is usually 6 to 45 wt%, based on the entire agent. Quantities from 10 to 35 wt% are preferred according to the present invention. [0124]It has furthermore been shown that the effect of the bioquinone(s) used according to the present invention can be enhanced when it/they is/are combined with hydroxycarboxylic acid esters. Preferred hydroxycarboxylic acid esters are full esters of glycolic acid, lactic acid, malic acid, tartaric acid, or citric acid. Further hydroxycarboxylic acid esters that are suitable in principle are esters of P-hydroxypropionic acid, tartronic acid, D-gluconic acid, saccharic acid, mucic acid, or glucuronic acid. Primary linear or branched aliphatic alcohols having 8 to 22 carbon atoms, i.e., for example, fatty alcohols or synthetic fatty alcohols, are suitable as alcohol components of these esters. The esters of C12 to C15 fatty alcohols are particularly preferred. Esters of this type are available commercially, e.g. under the trademark Cosmacol* of EniChem, Augusta Industriale. The quantity of hydroxycarboxylic acid esters used is 0.1 to 15 wt% based on the agent, preferably 0.1 to 10 wt%, and very particularly preferably 0.1 to 5 wt%. [0125]lt has likewise proven advantageous to combine the bioquinone(s) that is/are used with vitamins, provitamins, and vitamin precursors, and derivatives thereof. [0126]Those vitamins, provitamins, and vitamin precursors that are usually assigned to groups A, B, C, E, F, and H are preferred according to the present invention. [0127]The group of substances referred to as vitamin A includes retinol (vitamin A 1 ) as well as 3,4-didehydroretinol (vitamin A 2 ). p-Carotene is the 37 H 07094 provitamin of retinol. Vitamin A components that are suitable according to the present invention are, for example, vitamin A acid and its esters, vitamin A aldehyde, and vitamin A alcohol as well as its esters such as the palmitate and acetate. The preparations used according to the present invention contain the vitamin A component preferably in quantities from 0.05 to 1 wt% based on the entire preparation. [0128] The vitamin B group or the vitamin B complex includes, among others: e Vitamin B1 (thiamine). * Vitamin B2 (riboflavin). * Vitamin B 3 . The compounds nicotinic acid and nicotinic acid amide (niacinamide) are often listed under this designation. Nicotinic acid amide, which is used preferably in quantities from 0.05 to 1 wt% based on the entire agent, is preferred according to the present invention. * Vitamin B5 (pantothenic acid and panthenol). In the context of this group, panthenol is preferably used. Derivatives of panthenol that are usable according to the present invention are, in particular, the esters and ethers of panthenol as well as cationically derivatized panthenols. Individual representatives are, for example, panthenol triacetate, panthenol monoethyl ether and its monoacetate, and the cationic panthenol derivatives disclosed in WO 92/13829. The aforesaid compounds of the vitamin B5 type are used preferably in quantities from 0.05 to 10 wt% based on the entire agent. Quantities from 0.1 to 5 wt% are particularly preferred. * Vitamin B6 (pyridoxine, as well as pyridoxamine and pyridoxal). [0129]Vitamin C (ascorbic acid). The usual quantity of vitamin C used is 0.1 to 3 wt% based on the entire agent. Utilization in the form of the palmitic acid ester, the glucosides, or phosphates can be preferred. Utilization in combination with tocopherols can likewise be preferred. [0130]Vitamin E (tocopherols, in particular a-tocopherol). Tocopherol and its derivatives, which include in particular the esters such as the acetate, 38 H 07094 nicotinate, phosphate, and succinate, are used according to the present invention preferably in quantities from 0.05 to 1 wt% based on the entire agent. [0131]Vitamin F. The term "vitamin F" is usually understood to mean essential fatty acids, in particular linoleic acid, linolenic acid, and arachidonic acid. [0132]Vitamin H. What is referred to as "vitamin H" is the compound (3aS,4S,6aR)-2-oxohexahydrothienol[3,4-d]-imidazol-4-valeric acid, for which the trivial name "biotin" has nevertheless now become established. Biotin is used preferably in quantities from 0.0001 to 1.0 wt%, in particular in quantities from 0.001 to 0.01 wt%. [0133]The additional utilization of vitamins, provitamins, and vitamin precursors from groups A, B, E, and H is particularly preferred according to the present invention. [0134] Panthenol and its derivatives, as well as nicotinic acid amide and biotin, are particularly preferred. [0135]Lastly, the effect of the bioquinone(s) used according to the present invention can also be enhanced by combined utilization with plant extracts. [0136]These extracts are usually produced by extraction of the whole plants. In individual cases, however, it may also be preferred to produce the extracts exclusively from blossoms and/or leaves of the plants. [0137] Especially preferred according to the present invention are extracts from green tea, oak bark, nettle, hamamelis, hops, chamomile, burdock root, horsetail, hawthorn, linden blossoms, almond, aloe vera, pine needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lemon, wheat, kiwi fruit, melon, orange, grapefruit, salvia, rosemary, birch, mallow, lady's-smock, wild thyme, yarrow, thyme, lemon balm, restharrow, coltsfoot, hibiscus, ginseng, ginger root, Echinacea purpurea, Olea europea, Foeniculum vulgaris, and Apium graveolens. 39 H 07094 [0138]The extracts from green tea, oak bark, nettle, hamamelis, hops, chamomile, burdock root, horsetail, linden blossoms, almond, aloe vera, coconut, mango, apricot, lemon, wheat, kiwi fruit, melon, orange, grapefruit, salvia, rosemary, birch, lady's-smock, wild thyme, yarrow, restharrow, meristem, ginseng, and ginger root are particularly preferred. [0139]The extracts from green tea, almond, aloe vera, coconut, mango, apricot, lemon, wheat, kiwi fruit, and melon are very particularly suitable for the use according to the present invention. [0140]Water, alcohol, and mixtures thereof can be used as extraction media for producing the aforesaid plant extracts. Among the preferred alcohols are the lower alcohols such as ethanol and isopropanol, but in particular the polyvalent alcohols such as ethylene glycol and propylene glycol, both as the only extraction medium and mixed with water. Plant extracts based on water/propylene glycol at a ratio from 1:10 to 10:1 have proven particularly suitable. [0141]The plant extracts can, according to the present invention, be used both in pure and in diluted form. If they are used in diluted form, they usually contain approx. 2 to 80 wt% active substance and, as solvent, the extraction medium or extraction medium mixture used to obtain them. [0142] It may furthermore be preferred to use mixtures of several, in particular two, different plant extracts. [0143]lt has furthermore been found that the effect of the bioquinone(s) used according to the present invention can be further enhanced in combination with substances that contain primary or secondary amino groups. Examples that may be cited of such amino compounds are ammonia, monoethanolamine, 2 amino-2-methyl-1-propanol, 2-amino-2-methylpropanediol, and basic amino acids such as, for example, lysine, arginine, or histidine. These amines can, of course, also be used in the form of the corresponding salts with inorganic 40 H 07094 and/or organic acids, for example as ammonium carbonate, ammonium citrate, ammonium oxalate, ammonium tartrate, or lysine hydrochloride. The amines are used together with the active substance according to the present invention at ratios from 1:10 to 1:10, preferably 3:1 to 1:3, and very particularly preferably in stoichiometric quantities. [0144]ln addition to the bioquinone(s) mandatorily used according to the present invention, and the further preferred components cited above, these preparations can in principle contain all further components known to the skilled artisan for such cosmetic agents. [0145] Further active substances, adjuvants, and additives are, for example: - thickening agents such as gelatins or plant gums, for example agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin, and dextrins, clays and sheet silicates such as, for example, bentonite, or entirely synthetic hydrocolloids such as, for example, poly(vinyl alcohol), the Ca, Mg, or Zn soaps; - structuring agents such as maleic acid and lactic acid; - perfume oils; - dimethylisosorbide; - cyclodextrins; - solvents and solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, and diethylene glycol; - fiber-structure-improving active substances, in particular mono-, di-, and oligosaccharides such as, for example, glucose, galactose, fructose, fruit sugar, and lactose; - quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate; - defoamers such as silicones; - dyes for coloring the agent; - anti-dandruff active substances, such as piroctone olamine, zinc olamine, and climbazol; 41 H 07094 - light-protection agents, in particular derivatized benzophenones, cinnamic acid derivatives, and triazines; - further substances for adjusting the pH, for example a- and p hydroxycarboxylic acids; - active substances such as allantoin and bisabolol; - cholesterol; - complexing agents such as EDTA, NTA, -alaninediacetic acid, and phosphonic acids; - swelling and penetrating substances, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogencarbonates, guanidines, ureas, and primary, secondary, and tertiary phosphates; - Ceramides. "Ceramides" are understood as N-acylsphingosine (fatty acid amides of sphingosine) or synthetic analogs of such lipids (so-called pseudo-ceramides); - opacifiers such as latex, styrene/PVP copolymers, and styrene/acrylamide copolymers; - luster agents such as ethylene glycol mono- and distearate, as well as PEG-3 distearate; - pigments; - reducing agents such as, for example, thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid, and a mercatoethanesulfonic acid; - propellants such as propane/butane mixtures, N 2 0, dimethyl ether, C02, and air; - antioxidants; - deoxysugars; - plant glycosides; - polysaccharides such as fucose or rhamnose; - derivatives, and triazines; - further substances for adjusting the pH, for example a- and D hydroxycarboxylic acids; - active substances such as allantoin and bisabolol; - cholesterol; 42 H 07094 - consistency agents such as sugar esters, polyol esters, or polyolalkyl ethers; - fats and waxes such as spermaceti, beeswax, montan wax, and paraffins; - fatty acid alkanolamides; - complexing agents such as EDTA, NTA, P-alanine diacetic acid, and phosphonic acids; - swelling and penetrating substances, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogencarbonates, guanidines, ureas, and primary, secondary, and tertiary phosphates; - opacifiers such as latex, styrene/PVP copolymers, and styrene/acrylamide copolymers; - luster agents such as ethylene glycol mono- and distearate, as well as PEG-3 distearate; - pigments; - reducing agents such as, for example, thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid, and a mercatoethanesulfonic acid; - propellants such as propane/butane mixtures, N 2 0, dimethyl ether, C0 2 , and air; - antioxidants. [0146]The Examples that follow explain the invention without limiting it thereto. [0147]All indications are percentages by weight (wt%). EXAMPLE 1 [0148] Determining the cell vitality of cultured fibroblasts after treatment with ubiquinone [0149]A determination of the vitality of cultured cells provides information as to the cells' status. This analysis allows both a definition of cell-damaging substance concentration and a determination of cell-activating active substance effects. 43 H 07094 The vitality of cultured cells is determined using redox dyes. These dyes penetrate into the cell and are reduced by electron uptake at the outer mitochondrial membrane. This reduction causes a color change that is then determined photometrically. To quantify vitality, the solvent control is set to 100% and the measured values for the substance-treated samples are referred to it. The substance effects are referred to as "cell-damaging" at a relative vitality of less than 80%, and as "cell-activating" at a relative vitality greater than or equal to 120%. Test concentration 0.00000 0.0000 0.0000 0.000 0.000 0.00 ( 5 1 5 1 5 1 Relative vitality (%) 122 138 130 139 138 143 [0150]Over a wide range of concentrations, treatment with ubiquinone results in cell-activating effects in the fibroblasts that were investigated. EXAMPLE 2 [0151] Demonstration of differential expression of hair-relevant genes [0152]Hepatocyte growth factor (HGF) and keratinocyte growth factor (KGF) are important growth factors that are excreted by the dermal papillae in order to control the proliferation of the hair keratinocytes that are responsible for the synthesis of hair keratins. They are also characteristic markers for the anagen phase, in which keratin synthesis is also maximal. It must also be noted that as the hair ages, the proliferation capability of the hair follicle cells decreases. HGF and/or KGF should therefore be induced in the context of any substance that potentially activates keratin and counteracts hair aging. TGF-P2 and KGFBP-3 have a growth-inhibiting effect and are characteristic markers for the catagen phase, in which keratin synthesis in the follicle is shut off. These markers should be repressed in the context of a substance that promotes keratin synthesis. Differential gene expression was determined using quantitative RT-PCR. After cultivation of the dermal papilla cells, they were incubated for 24 hours with ubiquinone at concentrations of 0.00005% and 0.00001%. PCR was carried 44 H 07094 out by first isolating the RNA from the dermal papilla cells using the RNeasy Mini Kit of the Qiagen company, followed by reverse transcription into cDNA. In the subsequent polymerase chain reaction (PCR), which was carried out using gene-specific primers for the particular hair-relevant genes and served to amplify the gene segments of interest, formation of the PCR products was detected online via a fluorescence signal, which is proportional to the quantity of PCR product formed. The greater the expression of a specific gene, the larger the quantity of PCR product formed, and the higher the fluorescence signal. To quantify gene expression, the solvent control is set to 1 and expression of the genes being determined is referred thereto (X-times expression). Values that are greater than or equal to twice the expression, or less than or equal to 0.5 times the expression, of the untreated control are categorized as having a significantly differential expression. [0153]Tables 1 and 2: Influence of ubiquinone on the expression of hair relevant genes Conc. IGFBP3 HGF Mean SD Mean SD Control 1.00 1.00 Ubiquinone 0.00001% 0.08 0.07 1.92 0.59 0.00005% 0.11 0.03 1.56 0.11 Conc. TGFB-2 KGF Mean SD Mean SD Control 1.00 1.00 Ubiquinone 0.00001% 0.16 0.04 0.78 0.14 0.00005% 0.15 0.01 0.96 0.11 [0154]Ubiquinone results in concentration-dependent differential gene expression of the two catagen-associated marker genes that were investigated. EXAMPLE 3 45 H 07094 [0155] Demonstration of the release of growth factors [0156]Hepatocyte growth factor (HGF) and keratinocyte growth factor (KGF) are important growth factors that are excreted by the dermal papillae in order to control the proliferation of the hair keratinocytes that are responsible for the synthesis of hair keratins. They are also characteristic markers for the anagen phase, in which keratin synthesis is also maximal. It must also be noted that as the hair ages, the proliferation capability of the hair follicle cells decreases. HGF and/or KGF should therefore be induced in the context of any substance that potentially activates keratin and counteracts hair aging. The excretion of HGF and KGF can be quantified with the aid of commercially obtainable ELISA kits. This is done by incubating organotypical cell cultures for 72 hours with ubiquinone, and determining the concentration of the growth factors in the medium in the manner described. [0157]Table 3. Release of KGF and HGF after treatment of organotypical hair follicle cell cultures, as compared with solvent control. KGF HGF Mean SD Mean SD 0.00001% 92 15 124 18 0.00005% 98 17 181 2 [0158]In organotypical cell cultures, ubiquinone results in an increase in HGF excretion by a maximum of 81% as compared with the untreated control (Table 3). EXAMPLE 4 [0159] Demonstration of activation of keratin synthesis [0160]Hair thinning, and increased hair fragility, are age-related phenomena. Hair strength and hair structure depend substantially on the composition of special hair-specific structural proteins (hair keratins). Age-related changes in 46 H 07094 the composition of these specific protein influences hair structure on a biological level. The expression of various hair keratins in organotypical cell cultures can be investigated using the quantitative real-time PCR method described in Example 2. To quantify gene expression, the solvent control is set to 1 and expression of the genes being determined is referred thereto (X-times expression). Values that are greater than or equal to twice the expression, or less than or equal to 0.5 times the expression, of the untreated control are categorized as having a significantly differential expression. [0161]Table 4: Hair keratin expression after treatment of organotypical hair follicle cell cultures, as compared with solvent control. 6 hr after hHa3-l hHa4 hHb6 hHa2 application Mean SD Mean SD Mean SD Mean SD 0.00001% 1.1 0.17 1.2 0.17 2.1 0.13 1.2 0.73 0.00005% 2.9 0.69 5.5 2.35 4.7 1.73 2.9 1.17 24 hr after hHa3-l hHa4 hHb6 hHa2 application Mean SD Mean SD Mean SD Mean SD 0.00001% 1.0 0.37 1.3 0.45 1.5 0.69 1.5 0.6 0.00005% 6.2 4.13 8.7 0.9 4.5 0.66 4.5 2.29 [0162]ln organotypical cell cultures, ubiquinone results in an increase in keratin expression 6 hours and 24 hours after application (Table 4). EXAMPLE 5 [0163] Stimulation of keratinocyte proliferation [0164] The proliferation capability of hair follicle cells declines as the hair ages. In addition to excretion of the growth factors HGF and KGF, the activating 47 H 07094 effect of the test substance used can also be demonstrated from the layer thickness of the hair keratinocytes applied onto the model. In the context of a substance that potentially counteracts hair aging, the increased keratinocyte proliferation should also be demonstrable based on an increased keratinocyte layer in organotypical cell cultures. For this, three sections each of three organotypical cell cultures were prepared and were each measured at five locations. For better clarity, the histological sections were stained with eosin and hematoxylin. The layer thickness of the keratinocyte layer was then measured using a digital camera and image-processing software. [0165]Ubiquinone at a utilization concentration of 0.00001% raised the epithelial thickness by a maximum of 17% as compared with the solvent control. EXAMPLE 6 [0166] Demonstration of various hair-relevant markers using a DNA array [0167]ln order to characterize the overall effect of ubiquinone, organotypical cell cultures were treated for 6 hours and 24 hours with ubiquinone, the RNA was isolated, and the expression of 850 different markers was investigated with the aid of a cDNA microarray. Untreated cell cultures were included as a control. Differential gene regulation was demonstrated for various hair-relevant parameters after both 6 hours and 24 hours. [0168]To quantify gene expression, the solvent control is set to 1 and expression of the genes being determined is referred thereto (X-times expression). Values that are greater than or equal to 1.4 times the expression of the untreated control are categorized as statistically noteworthy; values greater than or equal to 1.9 times the expression of the untreated control are categorized as significant. [0169]The regulation of genes that counteract age-related changes in hair follicles is evident in particular after 6 hours. Our own investigations have shown, for example, that apoptosis-associated genes, among others, are more 48 H 07094 strongly expressed in the aging follicle, i.e. the more mature follicle is more likely to be affected by cell death. Treatment with ubiquinone results in a repression of apoptosis-associated genes. These genes are listed in Table 5. Ubiquinone 6 hours vs untreated Caspase -2.46 10 TNF-a -1.79 TNFSF6 -1.46 (Table 5) [0170]ln addition, a number of inflammation-associated genes are repressed. Increased expression of inflammation markers such as interleukin-6 or interleukin-la can also be demonstrated in older follicles. This inflammation reaction can be counteracted by the application of ubiquinone. Table 6 notes the genes involved. Ubiquinone 6 hours vs untreated Interleukin-6 -1.97 Interleukin-8 -1.49 Prostaglandin -1.49 synthase (Table 6) EXAMPLES 7 TO 13 [0171] Shampoo I Description Percentage Citric acid 0.5 Laureth sulfate 13 49 H 07094 Disodium Cocoamphodiacetate 6 Salicylic acid 0.2 D-panthenol 75% 0.2 Sodium benzoate 0.5 Euperlan*' PK 3000 AM 2.6 Cetiol*2 HE 0.5 Hydrogenated Castor Oil 0.1 Keratin hydrolysate 0.2 Ubiquinone 0.01 Ceteareth-259 0.5 Sodium chloride fine/medium 0.5 Water to make 100 [0172] Shampoo 2 Description Percentage Citric acid 0.5 Laureth sulfate 10 Disodium Cocoamphodiacetate 5 Salicylic acid 0.2 Panthenol 0.2 Sodium benzoate 0.5 Euperlan*' PK 3000 AM 2.6 Cetiol' HE 0.5 Hydrogenated Castor Oil 0.1 Tocopherol acetate 0.2 Ubiquinone 0.01 Ceteareth-2513 0.5 Sodium chloride fine/medium 0.5 Allantoin 0.1 Water to make 100 50 H 07094 [0173] Hair therapy I Description Percentage Paraffinum Liquidum 1.5 Dehyquart F 75 1.5 Isopropyl myristate 1 Varisoft" W 75 PG 1.5 Cetearyl Alcohol 4 Biotin 0.2 Ubiquinone 0.01 Ceteareth-9* 0.8 Stearamidopropyldimethylamine 0.8 Dehyquart' A CA 3 Citric acid 1560 0.4 Methylparaben 0.2 Phenoxyethanol 0.2 Panthenol 0.5 Salcarew SC 96 0.5 Water to make 100 [0174] Hair rinse 1 Description Percentage Stenol" 1618 7.00 Panthenol 0.2 Genamin"' KDM-P 1.20 Dehyquart F 75 1.20 Ubiquinone 0.01 Ceteareth-25*0 0.80 Cetyl ester 0.50 Methylparaben 0.20 Perfume 0.30 Phenoxyethanol 0.40 Water to make 100 51 H 07094 [0175]D Hair tonic 1 Description Percentage Panthenol 0.01 Allantoin 0.1 Benzophenone-4 0.03 Synthalen*" K 0.24 Neutrol*" TE 0.25 Ethanol 96% DEP denatured 40 Ubiquinone 0.01 Ceteareth-25** 0.1 Menthol, natural 0.03 Water to make 100 [0176]Hair tonic 2 Description Percentage Tocopherol acetate 0.1 Allantoin 0.1 Benzophenone-4 0.03 Synthalen"' K 0.24 Neutrolq" TE 0.25 Ethanol 96% DEP denatured 30 Ubiquinone 0.01 Ceteareth-25** 0.1 Water to make 100 [0177] Hair tonic 3 Description Percentage Panthenol 0.01 Allantoin 0.1 Benzophenone-4 0.03 Synthalen*" K 0.20 Neutrol*'2 TE 0.25 52 H 07094 Ethanol 96% DEP denatured 40 Ubiquinone 0.02 Ceteareth-25" 0.1 Biotin 0.01 Water to make 100 [0178]The following commercial products were used: 1 INCI name: Aqua, Glycol Distearate, Glycerin, Laureth-4, Cocamidopropyl Betaine, Formic Acid; active substance: 40% in water; Cognis. 2 INCI name: PEG-7 Glyceryl Cocoate; Cognis 3 C16 to C18 fatty alcohol, ethoxylated (25 EO) 4 INCI name: Distearoylethyl Hydroxyethylmonium methosulfate, Cetearyl Alcohol; active substance: 65 to 72%; Cognis 5 1-Methyl-2-nortallowalkyl-3-tallow fatty acid amidoethylimidazolinium methosulfate; INCI name: Quaternium-27, Propylene Glycol; active substance: 74 to 77%; Goldschmidt-Rewo 6 C16 to C18 fatty alcohol, ethoxylated (9 EO) Trimethylhexadecylammonium chloride; INCI name: Aqua, Cetrimonium Chloride; active substance: 24 to 26%; Cognis 8 INCI name: Polyquaternium-37, Propylene Glycol Dicaprylate/Dicaprate PPG-1 Trideceth-6; active substance: 50%; Ciba 9 Cetylstearyl alcohol; INCI name: Cetearyl Alcohol; Cognis N,N,N-Trimethyl-N-(C20-C22-alkyl)ammonium chloride; INCI name: Behentrimonium Chloride; active substance: 77 to 83%; Clariant 11 Polyacrylic acid; INCI name: Carbomer; 3V Sigma N,N,N,N-Tetrakis(2-hydroxypropyl)ethylenediamine edetol; INCl name: Tetrahydroxypropyl Ethylenediamine; BASF 53

Claims (15)

1. Use of one or more bioquinones for the manufacture of cosmetic preparations for hair treatment, in particular for the manufacture of cosmetic preparations to combat age-related changes in hair follicles.

2. The use according to Claim 1, wherein the preparations counteract or reverse the decline in keratin synthesis, decrease in cell division activity, and lowering of cell vitality.

3. The use according to Claim 1, wherein the preparations counteract or reverse increased microinflammation and apoptosis.

4. The use according to one of Claims 1 to 3, wherein the preparations contain 0.0000005 to 1% of one or more bioquinones.

5. The use according to one of Claims 1 to 3, wherein the bioquinone(s) is/are selected from ubiquinone(s) and/or plastoquinone(s).

6. A method for manufacturing a cosmetic or pharmaceutical preparation to combat age-related changes in hair follicles, in which method a cosmetic agent based on one or more bioquinones is applied onto the hair or onto hairy skin.

7. Use of one or more bioquinones for the manufacture of cosmetic preparations for hair treatment, in particular for the manufacture of cosmetic preparations to promote keratin synthesis in hair.

8. The use according to Claim 7, wherein in particular, synthesis of the hHa3-1, hHa4, hHa2, and hHb6 hair keratins that are affected by aging is stimulated. 54 H 07094

9. The use according to Claim 7, wherein cell vitality, cell proliferation, and the excretion of growth factors are stimulated, and the activation of catagen-associated parameters is repressed.

10. The use according to one of Claims 7 to 9, wherein the preparations contain 0.0000005 to 1% of one or more bioquinones.

11. The use according to one of Claims 7 to 9, wherein the bioquinone(s) is/are selected from ubiquinone(s) and/or plastoquinone(s).

12. A method for manufacturing a cosmetic or pharmaceutcal preparation to stimulate keratin synthesis in hair, in which method a cosmetic agent based on one or more bioquinones is applied onto the hair or onto hairy skin.

13. Use of one or more bioquinones for the manufacture of cosmetic preparations for hair treatment, in particular for the manufacture of cosmetic preparations for positively influencing internal hair structure.

14. The use according to Claim 13, wherein the preparations contain 0.0000005 to 1 % of one or more bioquinones.

15. The use according to Claim 13, wherein the bioquinone(s) is/are selected from ubiquinone(s) and/or plastoquinone(s). 55