DE10115840A1 - Retinyl carbonates in cosmetics and dermatics - Google Patents

Abstract

The invention relates to the use of retinyl carbonates of formula (I), wherein R represents an optionally substituted C1-C12 alkyl, C6-C12 aryl, C7-C13 aralkyl or a group of formula (II), for the cosmetic treatment of the skin or hair and for the dermatological treatment of skin diseases. The invention also relates to corresponding cosmetic and dermatological agents.

Description

The present invention relates to retinyl carbonate-containing Cosmetic and pharmaceutical preparations, in particular derma tological application and the use of Retinylcarbonaten for the cosmetic treatment of skin or hair and dermatologi treatment of skin diseases.

Skin changes altering aging processes and disorders of the skin have long been the cause of cosmetic or medical intervention fen. The underlying processes are complex, aging For example, intrinsic events and exogenous factors appear ren, z. As sunlight, to be involved. Acne, oily or dry skin, keratoses, rosaceae, photosensitive, inflammatory che, erythematous, allergic or autoimmune-reactive reactions like dermatoses, photodermatoses and other temporary or persistent skin disorders affect the well-being of Be concerned.

As a result of aging, the skin, epidermis and dermis dilute are weaker interlinked, and the number of cells and supplying blood vessels decreases. Increasingly, it comes to Ausbil fine lines and wrinkles, the skin becomes leathery, yellowish and hanging down, pigmentation disorders occur.

It is known that solar exposure to a variety uner Desirable effects in the skin: erythema, photosensitization tion and immunological changes are examples of such acute reactions during photoaging and carcinogenesis Represent long-term effects. It also seem in the Photoal oxidative processes play a role. Furthermore is known that after irradiation of the skin matrix degrading enzymes be induced and that this induction by low molecular weight Compounds, such. As retinoic acid can be reduced. On Another effect of UV radiation is the appearance of suns burn cells in the skin. This can necrotic processes on who induce an inflammatory reaction or ver strengthen.  

The same factors also affect hair, where it too damage can occur. The hair becomes brittle, less so elastic and lackluster; the surface texture of the hair becomes damaged.

Sometimes it tries to cosmetic or dermatological With radical scavenging, antioxidant, anti-inflammatory or to provide moisturizing effects.

So it is already known, antioxidant compounds in dermatological or cosmetic preparations not only as Preservative for stabilizing the formulation itself to use, but also to harmful or unwanted oxi dative processes in human or animal skin genzuwirken. Because the skin's own protective mechanisms are sufficient This purpose is usually not sufficient, so that these processes one significant contribution to skin aging, but also to general or pathological changes of the skin.

DE-A-197 39 349 proposes to support the endogenous Protective mechanisms of the skin have antioxidant ingredients too cosmetic and dermatological preparations. The However, the effect achieved is still in need of improvement.

Because of a high irritant effect is already often be described use of retinoic acid and retinoic acid derivatives for Protection against photoaging of disadvantage (inter alia in EP A-0 230 498, EP-A-0 379 367, EP-A-0 253 393 and US 4,603,146). With the The aim of a reduced irritation potential is described in WO 98/14167 special formulations of retinoic acid, retinol, reti and esters of retinoic acid on an emulsion or liposome basis.

Further, also retinyl acetate and retinyl palmitate become cosmeti proposed and formulated accordingly (US 4,826,828; EP 0 343 444; EP 0 330 496).

For protection against hair loss, WO 98/17273 proposes butyric acid and butyric acid derivatives, including esters of retin acid, in particular retinoyloxymethyl butyrate.

A structurally very heterogeneous group of fatty alcohol derivatives is described in WO 91/05754 as cytoprotective and cytotoxic ben. Among a variety of applications are also Hautalte called phenomena of growth.  

In view of those associated with retinoic acid and its derivatives Disadvantages of the present invention is the object of specify further active ingredients based on vitamin A, their use in the skin or hair cosmetic or dermatological area satisfies.

Surprisingly, this is possible with retinyl carbonates.

The invention therefore provides the use of at least ei nes Retinylcarbonats of formula I.

where R is optionally substituted C ₁ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₃ aralkyl or a radical of the formula

stands,
for the cosmetic treatment of the skin and / or the hair or for the dermatological treatment of skin diseases.

Alkyl which may be branched or unbranched C ₁ -C ₁₂ alkyl, be preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl , 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl , 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n -N-decyl, called n-dodecyl.

Particularly preferred alkyl are C ₁ -C ₆ -alkyl radicals, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1 Methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n -hexyl. Especially preferred are ethyl, 1-methylethyl, (iso-propyl) and 2-methylpropyl (isobutyl).

Aryl is preferably phenyl or naphthyl.

Substituents of these radicals are to be selected especially under Al kyl, alkoxy, halogen, hydroxy, alkylcarbonyl, alkylcarbonyloxy, Alkoxycarbonyl, amino, alkylamino and dialkylamino, wherein alkyl above embodiments can be configured accordingly.

In another aspect, R's are radicals preferably, which are physiologically compatible as alcohol ROH. The physiological compatibility should be especially for the amounts apply, which according to the invention Retinyl carbonates play a role. Physiological Compatible Above all, safety means being safe for your health acting individuals, but excludes efficacy, d. H. an off effect on the condition of individuals to be treated. Physiologically harmless z. For example, ethanol, isopropanol and α-tocopherol, in particular the latter is also effective.

The production of the retinyl carbonates according to the invention takes place in in a manner known per se, for example analogously to that in US Pat. No. 2,980,702 and in JP 42020050 for ascorbyl carbonates methods.

The preparation of retinyl-α-tocopheryl carbonate is carried out according to Farm. Zh. (1974), 29 (6), 36-38 in a manner known per se.

In principle, the novel retinyl carbonates are suitable both in the pharmaceutical and cosmetic field for those applications that are also considered for retinol become. Without being bound by theory, be Voted aspects of the invention that the present Retinylcar are pro-drugs that are in vivo at least partially in retinol, Carbon dioxide and the alcohol ROH, or metabolites thereof transferred become.

Retinyl carbonates of the formula I are suitable in an advantageous manner for the treatment of damage to keratinous surfaces, d. H. Skin and skin appendages, such. B. hair, nails and the same.  

Retinyl carbonates of the formula I provide effective protection oxidative processes, before by radiation, in particular UV radiation ment or reactive compounds Damage caused directly or indirectly by such processes be gentle. They are advantageous for the treatment of kos metabolic or dermatological changes on the skin and hair, such as As skin aging, the loss of skin moisture, the Loss of skin elasticity, the formation of wrinkles or wrinkles or pigmentation or age spots.

Furthermore, the present invention relates to the use of Retinylcarbonates of the formula I for the treatment of undesired Ver changes in the appearance of the skin, such as acne or oily skin, keratoses, Rosaceae and / or photosensitive, inflammatory, erythematous, allergic or autoimmune-reactive reactions, etc.

Retinyl carbonates of the formula I are also used to calm down emp sensitive and irritated skin, for the preventive regulation of Collagen, hyaluronic acid, elastin synthesis, stimulation of DNA Synthesis, especially in deficient or hypoactive skin conditions, regulation of transcription and translation matrixab building enzymes, especially the MMPs, increase the cell regeneration and regeneration of the skin, increasing the skin's own Protective and repair mechanisms for DNA, lipids and / or pro proteins.

Particular preference is given to retinyl carbonates of the formula I for Rejuvenation and / or revitalization of the skin. advantageously, As a rule, they can also observe energizing effects be. In particular, retinyl carbonates of the formula I have ei a positive effect on the function of the mitochondria. Überra Schenderweise so oxidative damage of the skin is not only bent, but already existing damage can, at least partially, be eliminated. This will be improvements in Moisture value and / or the elasticity of the skin recorded. Using retinyl carbonates of the formula I, the Increased new synthesis of collagen and / or elastin. this leads to in general to an, at least partial, smoothing of Fal the complexion looks brighter and fresher. Usually goes with the mentioned beneficial effects also a positive sub a subjective feeling of having overall "youthful" skin.

Surprisingly, in the application according to the invention effective treatment of premature aging of the skin (eg wrinkles, Age spots, telangiectasias, pigmentation disorders), Strahlenungsbe caused skin damage or radiation-related negative changes of the skin and / or skin appendages, environmental  (Ozone, Free Radicals, Singlet Oxygen, Reactive Oxygen or nitrogen compounds, cigarette smoke, toxins) Skin damage or environmental adverse skin changes and / or dermal appendages, photosensitive, inflammatory, ery thematösen, allergic or autoimmune-reactive changes the skin and / or the skin appendages (in particular acne, fet dry or dry skin, keratoses, rosaceae, dermatoses, atopi eczema, seborrhoic eczema, photodermatoses, polymorphic Photodermatosis), deficient, sensitive or hypoactive states the skin and / or the appendages, itching, dry Skin conditions and horny layer barrier disorders and / or hair loss case and reduced hair growth possible.

The use according to the invention of retinyl carbonates of the formula I also serves in a surprising and unpredictable way to Calming of sensitive and irritated skin, regulation of Collagen, hyaluronic acid, elastin synthesis, stimulation of DNA Synthesis, especially in deficient or hypoactive skin conditions, regulation of transcription and translation matrixab building enzymes, in particular matrix metalloproteinases, Stei cell regeneration and regeneration of the skin, increase the skin's own protective and repair mechanisms for DNA, lipids and / or proteins and for pre- and post-treatment in chirur gical interventions, in particular to counteract skin irritation ken and to promote the regeneration processes of the injured skin.

The invention further relates to the use of retinylcarbony of formula I for the stabilization of cosmetic and dermato logical preparations or to stabilize other active substances substances contained in such preparations, e.g. B. before harmful oxidation processes or microbial deterioration. From particular advantage is the fact that the retinyl carbonates even show a comparatively high stability, which made it possible light, according to stable means based on vitamin A available supply.

Particularly advantageous is the inventive use of Re tinyl carbonates with regard to the prophylactic treatment of Aging phenomena of human skin and human Hair, especially dry skin, wrinkling and / or pig ment disorders.

The treatment according to the invention can be applied to individual states or Disorders (abnormalities or pathological conditions) however, if desired, several may also be the cause  treated interconnected states or disorders become.

One aspect of a treatment according to the invention relates the treatment of acute or chronic disorders, conditions, at signs, symptoms and / or dysfunctions; a purpose of this Be Action is a correction of the disorders, regulation of access conditions, or alleviation of signs, symptoms and / or radio transmission tions. Another aspect concerns preventive treatment (Prophylaxis), in particular in the cosmetic sector; a purpose This preventative treatment is to prevent the occurrence of the disorder conditions, signs, symptoms and / or dysfunctions avoid, including a time delay of occurrence counts, especially in relation to skin aging. The treatment may be symptomatic, for example as symptom suppression be judged. It can take place for a short time, medium term be directed, or it may also be a long-term treatment, for example, as part of a maintenance therapy act.

The use according to the invention of retinyl carbonates includes in the context of treatment a procedure. This is to behan individual, preferably a mammal, especially one Human, animal or pet, an effective amount of Retinylcar Bonate component, usually the pharmaceutical, veterinary cosmetic, or food-technological practice speaking formulated, fed. Whether such a treatment is on shows and in what form it has to be made depends on the one zelfall and can both a professional medical (in the rule foreign diagnosis) as well as a non-specialist Beur division (usually self-diagnosis) are subject to the existing Signs, symptoms and / or dysfunctions, risks, specific Develop signs, symptoms and / or dysfunction, and may include other factors.

According to a preferred embodiment, the erfindungsge moderate application of Retinylcarbonaten of formula I advantageous through regular application over a period of time. These depends on the desired goal, d. H. the timespan may extend over the lifetime of the user, preferably over a period of up to three months, more preferably over one week to two months, if the goal is a depot build up in the skin. For an after-sun application is considered as duration of use in the context of the invention, the one-time application, but prefers a period of at least one day, FITS It prefers over three days to three months, especially before given over one to two weeks.  

It is recommended for the purposes of the invention, Retinylcarbonate of formula I in an amount of 0.1 ug / cm ² to 2 mg / cm ² , between once a week and 4 to 5 times a day, preferably 3 times a week to 3 times a day , particularly preferably once or twice a day, to be applied topically.

In addition to the retinyl carbonate component, the inventive Treatment include other agents. In these effects Substances may in particular be those of which we kung of the retinyl carbonate-mediated effect is similar or this complements. So it may be beneficial, in addition to inventions to the invention retinyl carbonate component, another active ingredient to administer, which is preferably selected under Antimyko tika, antiseptics, antibiotics, sulfonamides, disinfectants agents, corticoids, shale oil and tar sulphonates, astringents antihidrotic, acne, psoriasis, seborrhea and Itching, keratolytics, antioxidants, e.g. B. the other Place this description listed antioxidants, especially vitamins B, C and E, folic acid, lipoic acid, methylthioadeno sin, 5-adenosylmethionine and methyltetrahydrofolate, and Deri vates and salts thereof, etc. are preferred together with retinyl carbonates of the formula I administered.

The use can be both in cosmetic products such as Kör percolating, decorative cosmetics etc., which take place in the Usually not prescription, as well as in pharmazeu medicinal products, in particular dermatics, including medications for Therapy of diseases of the skin (dermatoses) understood who the. The invention therefore also relates to the production of mit using at least one Retinylcarbonats the For mel I.

The invention therefore also cosmetic products, ent holding

• a) at least one retinyl carbonate of the formula I,
• b) optionally at least one further cosmetic Active ingredient, and
• c) a cosmetically acceptable formulation base.

Another object of the invention are also dermatological agents containing

• a) at least one retinyl carbonate of the formula I,  
• b) optionally at least one further active ingredient, and
• c) a formulation basis.

Cosmetic compositions according to the invention can e.g. B. as a solution, what water-free preparation, emulsion or microemulsion of the water in-oil or oil-in-water type, multiple emulsion, for example water-in-oil-in-water, gel, gel spray, lotion, Cream, mousse, solid stick, ointment, spray (pump spray or Aero sol), suspensions, powders, or as an aqueous system or as a surfactant preparation for cleaning skin and / or hair, be formulated.

Examples of suitable dermatological formulations are ointments, Creams, hydrogels, pastes or patches, and liquid medications forms, such as solutions, emulsions, in particular oil-in-water emulsions ions, suspensions, for example lotions etc. desired if also liposomes or microspheres can be used.

It may also be advantageous to retinyl carbonates of the formula I ge optionally with further active ingredients in encapsulated form rich, z. As cellulose encapsulation, in gelatin, with poly amides, in niosomes, wax matrices, with cyclodextrins or lipo Somali encapsulated.

For example, the retinyl carbonates of the formula I are in kosme cleaning agents, such as bar soaps, toilet soap, core soaps, transparent soaps, luxury soaps, Cream soaps, baby soaps, skin protection soaps, abrasive soaps, syn dets, liquid soaps, pasty soaps, soft soaps, Waschpa , liquid washing, shower and bath preparations z. B. wash tions, shower baths, shower gels, bubble baths, creamed Oil baths, bath extracts, scrub preparations, in-situ products, Ra foam, shaving lotions, shaving creams used.

Furthermore, it is suitable for skin cosmetic preparations such as W / O or O / W skin and body creams, day and night creams, Au Gencremes, Sunscreen, After Sun Products, Hand Care Pro products, face creams, multiple emulsions, jellies, microemulsions liposome preparations, nosome preparations, anti-wrinkle creams, Facial oils, lipogels, sports gels, moisturizing creams, bleach mes, vitamin creams, skin lotions, body lotions, ampoules, after Shave lotions, pre-shaves, moisturizing lotions, tanning lotions cellulite creams, depigmenting agents, massage preparations, Body powder, toner, facial masks, deodorants, anti transpirants, nose strips, anti-acne, repellent, shaving,  Depilatory, personal care, footcare tel, baby care and others.

In addition, the Retinylcarbonate of formula I in cosmetic Hair care products such as hair conditioners, hair lotions, hairspun lungs, hair emulsions, top fluids, leveling agents for Perms, hot oil treatment preparations, conditioners, Festigerlo tations, shampoos, hair tinting and coloring agents, hair sprays, Hair dryer lotions, shine sprays, hair brillantine, hair styling products, hair lotions, alopecia skin care products and others become.

Retinyl carbonates of the formula I are also suitable for use in cosmetics for decorative cosmetics, for example as a make-up, powder, rouge, eye shadow, kohl pencils, eyeli ner, eyefoundation cream, lipsticks, eyebrow donor, account renstift, masking pens, theatrical make-up, mascara, eyelash tint, coloring, make-up removal products and others.

For After Sun applications provided dosage forms of Re tinyl carbonates of the formula I and, if appropriate, additional Active ingredients have advantageous penetration properties, the allow rapid penetration of the substance into the skin. because against is for applications with "preconditioning" character a quick penetration usually unimportant, but the ability It is advantageous to build up a depot in the skin.

For the application according to the invention, the cosmetic and the matological preparations in the usual way for cosmetics on the skin and / or hair in sufficient quantity introduced.

Preferably the agents contain from 0.001% to 30% by weight, in particular 0.01% by weight to 10% by weight, particularly preferably 0.05 to 5 wt .-%, most preferably 0.1 to 2 wt .-% of Kompo i), based on the total weight of the agent. The co composition is determined by z. B. after the penetration the active substance through the stratum corneum and its faeces ability to form a depot in the skin.

The agents may contain cosmetic adjuncts, as they are commonly used in such preparations, e.g. B. Preservatives, bactericides, perfumes, substances for ver foaming, dyes, pigments, thickeners, surface-active substances, emulsifiers, softening substances oils, lubricants, fats, oils, waxes or other common ingredients components of a cosmetic or dermatological formulation  such as alcohols, polyols, polymers, foam stabilizers, solutions mediators, electrolytes, organic acids, organic solvents medium or silicone derivatives.

The formulation base of inventive pharmaceutical, in particular dermatological agent preferably contains pharmazeu table or dermatologically acceptable excipients. pharmaceutical acceptable in the field of pharmacy, food technology and adjacent areas known to be usable Excipients, in particular those in relevant pharmacopoeias (eg. DAB Ph. Eur. BP NF) listed as well as other auxiliaries whose Properties of a physiological application does not oppose hen.

Suitable auxiliaries may be: lubricants, wetting agents, emul gelling and suspending agents, preservatives, anti oxidants, anti-irritants, chelating agents, emulsion stabilizers ren, film formers, gelling agents, odor masking agents, resins, Hydrocolloids, solvents, solubilizers, neutralizers medium, permeation enhancers, pigments, quaternary ammonium compounds, regreasing and superfatting agents, ointment, Cream or oil bases, silicone derivatives, stabilizers, Ste silanes, blowing agents, drying agents, opacifiers, Verdic curatives, waxes, plasticisers, white oils. A related Forms based on expert knowledge, as in For example, in Fiedler, H. P. Lexicon of excipients for pharmaceuticals zie, cosmetics and adjacent areas, 4th ed., Aulendorf: ECV- Editio-Kantor-Verlag, 1996, are shown.

The agents may be used in addition to the active substances mentioned Contain active ingredients that antioxidant, as radical scavengers, skin moisturizing or moisturizing, anti-erythematous, anti-inflammatory or antiallergic to supplement or to their effect strengthen. In particular, these compounds can be selected are from the group of vitamins, plant extracts, α- and β-Hy hydroxy acids, ceramides, anti-inflammatory, antimicrobial or UV-filtering substances, and their derivatives and Mischun from it.

Advantageously, the antioxidants are selected from amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and derivatives thereof, peptides such as D, L-carnosine, D-carnosine, L-carnosine and its derivatives (for example anserine), carotenoids, carotenes (for example α-carotene, β-calcin, lycopene, phytoene, phytofluene) and derivatives thereof, chloroformic acid and derivatives thereof, aurothioglucose, propylthiouracil and other thiols (e.g., thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-lino-leyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodiproic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), such as sulfoximine compounds (for example buthiosin sulfoximine, homocysteinesulfoximine , Buthione sulfones, penta-, hexa, heptathionine sulfoxime in) in very low tolerated dosings (eg. Pmol to μmol / kg), furthermore (metal) chelators (for example α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (for example citric acid, lactic acid, apple acid), humic acid, Bile acids, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamins C and Derivatives (eg, ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg, vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), as well as coniferyl benzoate of benzoin, rutinic acid, and their De hydrochloric acid, butylhydroxytoluene, butylhydroxyanisole, norihydroguaiacoic acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, sesamol, sesamolines, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and its derivatives (e.g. B. Selenium methionine), stilbenes and their derivatives (eg. B. stilbene oxide, trans-stilbene oxide) and the erfindungsge according to suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these drugs.

The antioxidants may be alone or in the form of mixtures be used. The amount of antioxidants in the Zu preparations, alone or in combination, is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 to 20 wt .-%, ins particular 1 to 10 wt .-%, based on the total weight of the Zu preparation.

If vitamin E and / or its derivatives, the anti or the represent oxidants, it is advantageous to their respective Concentrations from the range of 0.001-10 wt .-%, based on the total weight of the formulation to choose. If Vita min A or further vitamin A derivatives or carotenes or their Derivatives that are or the antixoidants, it is advantageous whose concentrations are in the range of 0.001% 10 wt .-%, based on the total weight of the formulation, too choose.  

In addition, the cosmetic compositions preferably contain substances absorb the UV radiation in the UV-B and / or UV-A range. Ge suitable UV filters are z. B. 2,4,6-triaryl-1,3,5-triazines, at where each of the aryl groups traits at least one substituent which is preferably selected from hydroxy, Al koxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl, and mixtures thereof. Suitable are still 4-aminobenzoic acid ester, wherein the amino group optionally al may be alkylated or alkoxylated. This includes z. N, N-Dime thyl-4-aminobenzoesäureisooctylester. Suitable are still 2-hydroxybenzoic acid esters, such as. B. the isooctyl ester. Further suitable UV filters are 2,4,6-trianiline (o-carbo-2'-ethylhexyl) 1'-oxy) -1,3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, menthyl-o-aminobenzoate, glyceryl-p-aminobenzoate, 2,2'-di hydroxy-4-methoxybenzophenone (dioxybenzone), 2-hydroxy-4-meth oxy-4-methylbenzophenone (Mexenon®), triethanolamine salicylate, di methoxyphenylglyoxalic acid, 3- (4'-sulfo) benzylidene-bornan-2-one and its salts, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-methylene bis [6 (2H-benzotriazol-2-yl-4- (1,1,3,3-tetramethylbutyl) phenol], 2,2 '- (1,4-phenylene) -bis-1H-benzimidazole-4,6-disulfonic acid and its Na salt, 2,4-bis [4- (2-ethylhexyloxy) -2-hydroxy] phenyl-6 (4-methoxyphenyl) - (1,3,5) -triazine, 3- (4-methylbenzylidene) -cam pher, 4-bis (polyethoxy) paraaminobenzoic acid polyethoxyethyl ester, 2,4-dihydroxybenzophenone and / or 2,2'-dihydroxy-4,4'-dimethoxy benzophenone-5,5'-disodium.

The list of mentioned UV filters, in combination with the he inventive drug combinations can be used Of course, this should not be limiting.

The total amount of the filter substances is usually 0.1% by weight. to 30 wt .-%, preferably 0.5 to 15 wt .-%, in particular Other 1 to 10 wt .-%, based on the total weight of the Zuberei tions to provide cosmetic preparations, the skin in front of the whole area of the ultraviolet ray protection.

If a lipid phase is used, it is preferably selected from among mineral oils, mineral waxes, branched and / or un branched hydrocarbons and waxes, triglycerides of saturated and / or unsaturated, branched and / or un-branched C ₈ -C ₂₄ -alkanecarboxylic acids; synthetic, semi-synthetic or natural oils such as olive oil, palm oil, almond oil or mixtures; Oils, fats or waxes; Esters of saturated and / or unsaturated, branched and / or unbranched C ₃ -C ₃₀ -alkanecarboxylic acids and saturated and / or unsaturated, branched and / or unbranched C ₃ -C ₃₀ -alcohols, esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched C ₃ -C ₃₀ -alcohols, for example isopropyl myristate, isopropyl stearate, hexyldecyl stearate, oleyl oleate; synthetic, semi-synthetic and natural mixtures of the aforementioned esters, such as jojoba oil, alkyl benzoates or Silikonö len such. As cyclomethicone, dimethylpolysiloxane, Diethylpolysilo xan, octamethylcyclotetrasiloxane and mixtures thereof or dialkyl ethers.

If an aqueous phase is used, it additionally contains optionally a water-miscible solvents such as C ₁ - to C ₁₀ -, preferably C ₁ - to C ₅ alcohols, diols or polyols, and ethers thereof, preferably ethanol, isopropanol, propylene glycol , Glycine, ethylene glycol monoethyl ether etc.

Emulsifiers are preferably known W / O and O / W Emulga such as polyglycerol esters, so- witer esters or partially esterified Glycerides into consideration.

Particularly suitable solubilizers are ethoxylated Sorbitan esters, ethoxylated lanolin alcohols and ethoxylated Ri to call zinusoil.

Usual native and synthetic thickeners or gel formers in the formulations are crosslinked polyacrylic acids and their Derivatives, polysaccharides such as xanthan gum or alginates, carboxy methylcellulose or hydroxycarboxymethylcellulose, hydrocolloids such as gum arabic or motmorillonite minerals such as bentonite or fatty alcohols, polyvinyl alcohol and polyvinylpyrrolidone.

As propellants for aerosols are the usual blowing agents in Question, by way of example propane, butane, pentane, dimethyl ether and an more complete.

The formulations are transdermally (topically) according to the invention administered.

To produce the erfindungegemäßen agent, the Wirk substances with a suitable excipient (excipient, carrier) ver mixed or diluted. These can be fixed, semi solid or be liquid materials acting as a vehicle, carrier or medium can serve for the drug or the. The admixture of others If desired, auxiliaries are known to those skilled in the art way.  

The invention will not be limited by the following the examples explained in more detail.

reference example Synthesis of retinyl isopropyl carbonate

206.25 g (0.18 mol, 1 eq) of retinoic solution (25% in heptane) submitted in a nitrogen atmosphere with exclusion of light. After addition of 21.36 g (0.27 mol, 1.5 eq) of pyridine, 270 ml (0.27 mol, 1.5 eq) of a 1 M solution of isopropyl chloroformate in Heptane added dropwise at room temperature within 4 hours. to closing the solution was stirred at 20, C for 2 hours, with Pyridinium hydrochloride precipitated. The batch was filtered and im Vacuum concentrated. After codistillation with heptane and washing with 500 ml of water were codistilled again with heptane. After Reini the obtained syrup on silica gel by MPLC (heptane / Vinegar: 15: 1) resulted in a yellowish syrup. Yield: 31.5 g (47%).

Further retinyl carbonates were prepared in an analogous manner, z. B. 67.8 g (68% yield) of retinyl isobutyl carbonate from 1.5 eq Retinoic solution, 1 eq isobutyl chloroformate and 1.2 eq pyridn.

Examples of cosmetic preparations

example 1 Soft Skin Fluid

Wt .-% Ceteareth-6 (reaction product of fatty alcohol and ethylene oxide) and stearyl alcohol 2.50 Ceteareth-25 (reaction product of fatty alcohol and ethylene oxide) 2.50 Hydrogenated coconut fat glycerides 1.50 Polyethylene glycol (40 EO units) -Dodecylglycolcopolymer 3.00 dimethicone 3.00 Phenethyldimethicon 2.00 cyclomethicone 1.00 cetearyl 5.00 avocado oil 1.00 sweet almond oil 2.00 Wheat germ oil 0.80 Retinylisopropylcarbonat 0.20 Panthenol USP 1.00 phytantriol 0.20 tocopheryl acetate 0.30 Propylene glycol 5.00 Perfume q. s. preservatives q. s. water 69.20

Example 2 Protective hand cream

Wt .-% cetearyl 1.00 glyceryl stearate 1.50 stearyl 1.50 cetyl palmitate 2.00 tocopheryl acetate 0.50 dimethicone 8.00 Ceteareth-6 (reaction product of fatty alcohol and ethylene oxide) and stearyl alcohol 3.00 octyl 5.00 propylene glycol 8.00 panthenol 1.00 Evening primrose oil 3.00 ethoxylated hydrogenated castor oil (7 EO) 6.00 glyceryl 1.00 Phenethyldimethicon 3.00 beeswax 1.50 Locust bean gum 0.80 Silkpowder 0.80 preservatives q. s. Perfume q. s. borax 0.10 Retinylthylcarbonat 0.10 water 52,30

Example 3 Sun Care Lotion

Wt .-% ethoxylated hydrogenated rininus oil (7 EO) 6.00 Ethoxylated Hydrogenated Rininus Oil (40 EO) 0.50 isopropyl palmitate 7.00 Polyethylene glycol (40 EO) -Dodecylglycolcopolymer 2.00 jojoba oil 3.00 magnesium stearate 0.60 octyl 8.00 C _12-15 alkyl benzoate 5.00 Titanium dioxide 4.00 propylene glycol 5.00 EDTA 0.20 preservatives q. s. water 57.20 sodium ascorbyl 1.00 tocopheryl acetate 0.50 Retinylisopropylcarbonat 0.20 Perfume q. s.

Example 4 Multiple emulsion

Wt .-% mineral oil 7.50 cetearyl 2.50 aluminum stearate 0.25 magnesium stearate 0.25 Microdrystalline Wax H 0.50 cetearyl 1.00 lanolin 1.50 Mineral alcohol and lanolin alcohol 1.50 ethoxylated hydrogenated rininus oil (7 EO) 0.75 Polyethylene glycol (40 EO) dodecyl glycol copolymer 2.00 Ceteareth-6 (reaction product of fatty alcohol and ethylene oxide) and stearyl alcohol 2.00 Ceteareth-25 (reaction product of fatty alcohol and ethylene oxide) 2.00 Trilauret-4 phosphate 1.00 hydroxyethyl 0.20 propylene glycol 7.50 magnesium sulfate 0.25 Retinylisopropylcarbonat 0.10 water 69.30

Example 5 microemulsion

Wt .-% Ceteareth-25 (reaction product of fatty alcohol and ethylene oxide) 13,00 Glyceryl cocoate (7 EO) 20.00 octyldodecanol 5.00 preservatives q. s. Retinylthylcarbonat 0.20 water 62,00

Example 6 liposome

Wt .-% ethoxylated hydrogenated castor oil (40 EO) 1.00 Bisabolol rac. 0.10 propylene glycol 8.00 panthenol 0.50 Water and tocopheryl acetate and polysorbate 80 and caprylic / capric triglyceride and lecithin 3.00 preservatives q. s. Perfume q. s. Carbomer 0.50 Retinylthylcarbonat 0.20 triethanolamine 0.70 water 86.30

Example 7 Blunted Oil Gel

Wt .-% silica 5.00 dimethicone 10.00 cetearyl 40,00 Caprylic / capric triglyceride 8.00 Phenethyldimethicon 2.00 mineral oil 28.50 sweet almond oil 5.00 phytantriol 0.30 Retinylethylcarbonat 0.10 tocopherol 0.50 Perfume 1.00

Example 8 Oil gel

Wt .-% silica 5.00 dimethicone 10.00 cetearyl 30.00 Caprylic / capric triglyceride 10.00 isopropyl 5.00 Phenethyldimethicon 5.00 mineral oil 28,20 jojoba oil 5.00 phytantriol 0.30 Retinylisopropylcarbonat 0.30 tocopherol 0.50 Perfume 1.00

Example 9 nourishing sunscreen

Wt .-% beeswax 12,00 Hydrogenated coconut fat glycerides 5.00 castor oil 40,00 isopropyl palmitate 10.00 mineral oil 10.00 candelilla 8.00 Phenethyldimethicon 5.00 Retinylethylcarbonat 0.20 petrolatum 5.00 3-Benzophenone 5.00

Example 10 Cooling Body Splash

Wt .-% Ethoxylated hydrogenated castor oil (40 EO) 2.00 menthyl 0.20 alcohol 5.00 Glyceryl cocoate (7 EO) 2.00 Witch Hazel 5.00 allantoin 0.10 Bisabolol rac. 0.20 propylene glycol 5.00 Panthenol USP 0.50 Lactic acid (80%) 0.20 Retinylethylcarbonat 0.20 Perfume q. s. water 79,80

Example 11 Make up

Wt .-% Ceteareth-6 (reaction product of fatty alcohol and ethylene oxide) and stearyl alcohol 9.00 dimethicone 5.00 cetearyl 8.00 macadamia nut oil 5.00 propylene glycol 5.00 water 53,00 Sicovit White E 171 8.00 Sicomet Brown 70 13E 3717 2.00 Retinylisopropylcarbonat 0.20 Perfume q. s. 3-Benzophenone 5.00

Example 12 Liquid make-up

Wt .-% Ceteareth-6 (reaction product of fatty alcohol and ethylene oxide) and stearyl alcohol 7.00 Ceteareth-25 5.00 dimethicone 5.00 cetearyl 8.00 macadamia nut oil 5.00 propylene glycol 5.00 water 53,00 Sicovit White E 171 8.00 Sicomet Braun 70 13E 3717 1.00 Retinylethylcarbonat 0.10 Perfume q. s. 3-Benzophenone 5.00

Example 13 Sun Care Oil

Wt .-% cetearyl 40,00 Caprylic / capric triglycerides 28.70 Evening primrose oil 3.00 macadamia nut oil 5.00 isopropyl palmitate 5.00 dimethicone 3.00 Octyl methoxycinnamate 8.00 octocrylene 5.00 3-Benzophenone 2.00 phytantriol 0.10 Retinylisopropylcarbonat 0.10 tocopheryl acetate 0.20 Perfume q. s.

Example 14 Facial deep cleaner

Wt .-% water 65.60 cocoamidopropyl 5.00 Sodium cocoate, hydrolyzed animal protein 8.00 Ethoxylated hydrogenated castor oil (40 EO) 2.00 Polyquaternium-44 7.70 Bisabolol rac. 0.20 panthenol 1.00 Perfume 0.50 hydroxyethyl 2.00 Retinylethylcarbonat 0.50 propylene glycol 5.00 jojoba 3.00

Example 15 hair conditioner

Wt .-% Ceteareth-6 and stearyl alcohol 2.00 Ceteareth-25 (reaction product of fatty alcohol and ethylene oxide) 1.00 cetearyl 6.00 Ceteareth-3 2.00 cetearyl 6.00 phytantriol 1.00 propylene glycol 5.00 Polyquaternium-11 5.00 panthenol 1.00 retinyl 0.50 Perfume q. s. Retinylethylcarbonat 0.50 preservatives q. s. water 70.50

Example 16 hair wax

Wt .-% Polyethylene glycol-6 30.00 Polyethylene glycol-75 45,00 liquid paraffin oil 0.50 Ethoxylated hydrogenated castor oil (40 EO) 1.00 glycerin 15.00 3-Benzophenone 2.00 phytantriol 0.10 Retinylisopropylcarbonat 0.30 Perfume q. s. water 6.40

Example 17 Anti-dandruff hair tonic

Wt .-% alcohol 45,00 Aloe Vera (10 times Conc.) 1.00 panthenol 1.00 tocopheryl acetate 0.50 Ethoxylated hydrogenated castor oil (40 EO) 0.50 allantoin 0.10 Hydrolyzed animal protein 1.50 1- (4-chlorophenoxy) -1- (1H-imidazolyl) -3,3-dimethyl-2-butanone 0.30 Perfume 0.10 Retinylethylcarbonat 0.40 water 50,00

Example 18 Foot Deodorant Spray

Wt .-% Ethoxylated hydrogenated castor oil (40 EO) 0.80 alcohol 20.00 farnesol 0.12 menthyl 0.08 1,2-propylene glycol 3.20 4-benzophenone 1.20 Glyceryl cocoate (7 EO) 0.80 Perfume q. s. Retinylethylcarbonat 0.40 water 13.80 butane 60,00

Example 19 hair spray

Wt .-% amino methyl propanol 0.40 dimethicone 0,030 alcohol 43.67 pentane 14,20 Acrylate / acrylamide copolymer 3.40 Perfume q. s. Retinylisopropylcarbonat 0.30 Butane 2.40 isobutane 35,90

Claims (9)

1. Use of at least one retinyl carbonate of the formula I.
where R is optionally substituted C ₁ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₃ aralkyl or a radical of the formula
stands,
for the cosmetic treatment of the skin and / or the hair. 2. Use of at least one retinyl carbonate of the formula I.
where R is optionally substituted C ₁ -C ₁₂ alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₃ aralkyl or a radical of the formula
stands,
for the dermatological treatment of skin diseases. 3. Use according to one of claims 1 or 2 for the prophylaxis against aging processes of human skin. 4. Use according to one of claims 1 to 3 for prophylaxis against dry skin, wrinkling and / or pigmentation disorders. 5. Use according to claim 1 for prophylaxis against aging Pro tessellated human hair. 6. Use according to one of the preceding claims, wherein R is C ₁ -C ₄ alkyl. 7. Cosmetic agent containing

• a) at least one retinyl carbonate of the formula I
• b) optionally at least one further cosmetic active substance, and
• c) a cosmetically acceptable formulation base.

8. Dermatological agent containing

• a) at least one retinyl carbonate of the formula I
• b) optionally at least one further active ingredient, and
• c) a formulation basis.

9. Composition according to claim 7 or 8, which the component i) in a Amount of 0.001 to 30 wt .-%, based on the total weight of the agent contains.