WO2002087533A1

WO2002087533A1 - Use of a clover extract for prophylaxis against and for treating degenerative skin conditions

Info

Publication number: WO2002087533A1
Application number: PCT/EP2002/004468
Authority: WO
Inventors: Stefan Gallinat; Helga Biergiesser; Ludger Kolbe; Kirsten Venzke; Thomas Döring; Franz STÄB
Original assignee: Beiersdorf Ag
Priority date: 2001-04-26
Filing date: 2002-04-24
Publication date: 2002-11-07
Also published as: WO2002087533A8; DE10120315A1

Abstract

The invention relates to the use of a clove extract in cosmetic or dermatological preparations for ensuring the treatment and prophylaxis of symptoms of negative skin alterations due to environmental conditions e.g. skin damage caused by ozone and/or smog and/or smoking and inflammatory, hyperactive and/or degenerative skin conditions.

Description

USE OF CLOVER EXTRACT FOR PROPHYLAXIS AGAINST AND TREATMENT OF DEGENERATIVE SKINNESS

The present invention relates to the use of clover extract in cosmetic or dermatological preparations for the treatment and prophylaxis of the symptoms of environmentally induced negative skin changes - for example skin damage induced by ozone and / or smog and / or smoking - as well as inflammatory and degenerative skin conditions

In particular, the present invention relates to cosmetic preparations with effective protection against harmful oxidation processes in the skin, but also for protecting cosmetic preparations themselves or for protecting the constituents of cosmetic preparations against harmful oxidation processes

Cosmetic skin care is understood primarily to mean that the natural function of the skin as a barrier against environmental influences (eg dirt, chemicals, microorganisms) and against the loss of the body's own substances (eg water, natural fats, electrolytes) is strengthened or is restored

If this function is disturbed, there may be an increased absorption of toxic or allergenic substances or an infestation of microorganisms and as a result toxic or allergic skin reactions

The aim of skin care is also to compensate for the loss of fat and water in the skin caused by daily washing. This is particularly important if the natural

T \ Dr abanus \ 201-075 clover extract docT \ Dr Rabanus \ 201-075 clover extract doc Before regeneration is not sufficient In addition, skin care products are intended to protect against environmental influences, in particular against the sun and wind, and to delay skin aging

Chronological skin aging is caused, for example, by endogenous, genetically determined factors. The following structural damage and functional disorders occur in the epidermis and dermis, for example, which can also fall under the term "senile xerosis"

a) dryness, roughness and the formation of wrinkles due to dryness, b) itching and c) reduced relubrication caused by sebum glands (e.g. after washing)

Exogenous factors, such as UV light and chemical noxae, can have a cumulative effect and, for example, accelerate or complement endogenous aging processes. In the epidermis and dermis, exogenous factors in particular lead to the following structural damage and functional disorders in the skin, which are excessive and quality of damage go beyond chronological aging

d) Visible vasodilation (telangiectasias, cuperosis), e) flaccidity and the formation of wrinkles, f) local hyper-, hypo- and incorrect pigmentation (e.g. age spots) and g) increased susceptibility to mechanical stress (e.g. cracking)

The present invention relates in particular to products for the care of skin stressed by environmental noxious substances, such as UV light, ozone, cigarette smoke, and for the treatment of the consequential damage caused by light aging, in particular the phenomena listed under a) to g)

Products for the care of aged skin are known per se. They contain, for example, retinoids (vitamin A acid and / or their derivatives) or vitamin A and / or their derivatives. However, their effect on structural damage is limited in scope Difficulty to sufficiently stabilize the active substances against oxidative decay The use of vitamin In addition, products containing A acid often cause severe erythematous skin irritation. Retinoids can therefore only be used in low concentrations

The damaging effect of the ultraviolet part of solar radiation on the skin is well known. While rays with a wavelength that is less than 290 nm (the so-called UVC range) are absorbed by the ozone layer in the earth's atmosphere, they cause rays in the range between 290 nm and 320 nm, the so-called UVB range, an erythema, a simple sunburn or even more or less severe burns

The narrower range around 308 nm is given as a maximum of the erythema effectiveness of sunlight

To protect against UVB radiation, numerous compounds are known which are derivatives of 3-benzyl camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and also 2-phenylbenzimidazole

Also for the range between about 320 nm and about 400 nm, the so-called UVA range, it is important to have filter substances available, since its rays can cause reactions in photosensitive skin. It has been proven that UVA radiation damages the elastic and collagen fibers of the connective tissue lead to what causes the skin to age prematurely and that it can be seen as the cause of numerous phototoxic and photoallergic reactions. The damaging influence of UVB radiation can be intensified by UVA radiation

To protect against the rays of the UVA range, certain derivatives of dibenzoylmethane are therefore used, the photostability (Int J Cosm Science 10, 53 (1988)) of which is insufficient

However, UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products intervene in the skin metabolism

Such photochemical reaction products are predominantly radical compounds, for example hydroxy radicals. Undefined radical see photo products, which are created in the skin itself, can show uncontrolled secondary reactions due to their high reactivity. But also singlet oxygen, a non-radical excited state of the oxygen molecule can occur with UV radiation, just as short-lived epoxies and many others. Singlet oxygen, for example, is characterized by increased reactivity compared to the triplet oxygen normally present (radical ground state). However, there are also excited, reactive (radical) triplet states of the oxygen molecule.

UV radiation also belongs to ionizing radiation. There is therefore a risk that ionic species also develop when exposed to UV rays, which in turn can oxidatively intervene in the biochemical processes.

In order to prevent these reactions, additional antioxidants and / or free radical scavengers can be incorporated into the cosmetic or dermatological formulations.

It has already been proposed to use vitamin E, a substance with a known antioxidant activity, in light protection formulations, but the effect achieved here also falls far short of the hoped-for effect.

The object of the invention was therefore also to create cosmetic, dermatological and pharmaceutical active substances and preparations and light protection formulations which are used for the prophylaxis and treatment of light-sensitive skin, in particular photodermatoses, preferably PLD.

Other names for polymorphic light dermatosis are PLD, PLE, Mallorca acne and a variety of other names, such as those in the literature (e.g. Voelckel et al., Zentralblatt Skin and Sexually transmitted Diseases (1989), 156, p.2) , are specified.

Antioxidants are mainly used as protective substances against the spoilage of the preparations containing them. Nevertheless, it is known that undesirable oxidation processes can also occur in human and animal skin.

In the article "Skin Diseases Associated with Oxidative Injury" in "Oxidative Stress in Der- matology ", S 323 ff (Marcel Decker Ine, New York, Basel, Hong Kong, publisher Jürgen Fuchs, Frankfurt, and Lester Packer, Berkeley / Cahfornien), oxidative damage to the skin and its closer causes are listed

Also for the reason of preventing such reactions, additional antioxidants and / or radical scavengers can be incorporated into cosmetic or dermatological formulations

Although some antioxidants and free radical scavengers are known, it has already been proposed in US Pat. Nos. 4,144,325 and 4,248,861 and numerous other documents to use vitamin E, a substance with a known antioxidant activity, in light protection formulations, but the effect achieved here still lags far behind the hoped back

The object of the present invention was therefore to avoid the disadvantages of the prior art and, in particular, to remedy or prevent the damage caused by environmental noxes permanently, sustainably and without the risk of side effects

It has surprisingly turned out that the

Use of clover extract in cosmetic or dermatological preparations for the treatment and prophylaxis of the symptoms of environmentally induced negative skin changes as well as inflammatory, hyperactive and / or degenerative skin conditions remedies the disadvantages of the prior art

Cosmetic or dermatological preparations according to the invention preferably contain 0.0001 to 50% by weight, particularly preferably 0.01 to 10% by weight, of clover extract, in each case based on the total weight of the preparation

When using the active ingredient used according to the invention or cosmetic or topical dermatological preparations with an effective content of the active ingredient used according to the invention is surprisingly an effective treatment, but also a prophylaxis • of certain degenerative symptoms of the skin (e.g. sagging skin, age spots, telangiectasias, disturbance of the osmolytic balance, natural skin pH and loss of epidermal and dermal cells, the components of the connective tissue, the reticles and capillary vessels of the skin) and / or skin appendages,

• from environmental (caused by smoking, smog, reactive oxygen species, free radicals and the like) negative changes in the skin and skin appendages,

• from deficient, sensitive or hypoactive skin conditions or deficient, sensitive or hypoactive conditions of skin appendages, with reduced skin thickness, with sagging and exfoliating skin, with disturbances of the normal skin pH value and the osmolyte balance, with pigmentation disorders, • from itching, from Horn stratified disorders, with changes in transepidermal water loss and normal

Moisture content of the skin, with changes in normal lipid peroxidations, • with changes in the ceramide, lipid and energy metabolism of healthy skin, hair loss and for improved hair growth, with deviations from normal cell-cell communication in the skin, with changes in normal Fibroblast and keratinocyte progression, • possible with changes in normal fibroblast and keratocyte differentiation, inflammatory skin conditions and atopic eczema, seborrheic eczema, polymorphic light dermatosis, psonasis and / or Vitihgo

The active ingredient according to the invention or cosmetic or topically dermatological preparations with an effective content of the active ingredient according to the invention also work in a surprising manner

• to calm sensitive or irritated skin, to maintain normal collagen, hyaluronic acid, elastin and glycosaminoglycan homeostasis, to stimulate estrogen synthetase, with increased activation of proteolytic enzymes in the skin, such as B. Metalloproteinases, to stimulate intracellular DNA synthesis, especially in deficient or hypoactive skin conditions, in wound healing disorders, to increase cell renewal and skin regeneration, • to reduce the production of sebum, to prevent the formation and removal of comedones and / or for the adjustment of a normal sebum homeostasis, for the prevention or elimination of seborrheic phenomena, especially for the prophylaxis and treatment of oily hair, but also for dandruff to increase the skin's own protective and repair mechanisms (e.g. for dysfunctional enzymes, DNA, lipids, proteins) , for pre-treatment and post-treatment with topical application of laser and abrasive treatments, e.g. B. serve the reduction of skin folds and scars to counteract the resulting skin irritation and to promote the regeneration processes in the injured skin.

It is particularly advantageous in the sense of the present invention to use the active ingredient or cosmetic or topical dermatological preparations used according to the invention with an effective content of active ingredient used according to the invention for cosmetic or dermatological treatment or prophylaxis of undesirable skin conditions.

Clover extract in the sense of the present invention is obtained from botanically known clover species (Trifolium spec, family Leguminosae) such as. B. Red clover (Trifolium pratense L.) obtained by extraction.

For this purpose, fresh and / or dried plants, in particular the flower heads, are extracted, for example by one of the following known methods: 1) fluid extract 1: 1 in 25% ethanol,

2) tincture 1:10 in 45% ethanol,

3) Mother tincture: Preparation of 1,000 mL mother tincture from 400 parts of moist plant matter (consisting of 100 g solid and 300 ml plant juice) and 730 ml ethanol

The list of the extraction processes mentioned should of course not be limiting. Clover extracts according to the invention are available in numerous ways known per se. In principle, new ways of producing the extracts are also conceivable. It is essential that the clover extracts show the properties according to the invention.

Typically, clover extract according to the invention contains some or all of the following ingredients:

Flavones (isopratol, luteolin, pectolinarigenin),

Flavonols (isorhamnetin, camphor oil, pratoletin),

Isoflavones (biochanin A, calicosin, formononetin, genistein, pratensin, pseudo-baptigenin),

Isoflavanes (arvensan, demethylvestitol, isosativan, isovestitol),

pterocarpans,

Phenylcoumarins with a condensed furan ring (cumestrol, reponsol),

Stilbene, especially resveratrol,

Condensed tannins,

coumaric,

Caffeic acid,

Essential oils

Red clover extracts from Trifolium pratense are particularly advantageous for the purposes of the present invention.

According to the invention, preparations containing the active substances used according to the invention, customary antioxidants can be used. The antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-camosin, D-carnosine, L-carnosine and its derivatives (e.g. Anseπn), carotenoids, carotenes (e.g. -carotene, ß-carotene, lycopene, phytoene) and their derivatives, lipoic acid and their derivatives (e.g. dihydrohonsoic acid), aurothioglucose, propylthiouracil and other thiols ( eg thioredoxm, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl -, Cholesteryl and glyceryl esters) as well as their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoninsulfoximine, butyl Hexa-, heptathioninsulfoximine) in very low contractual dosages (e.g. pmol to μmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactofernn), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), Tetrahydrocurcumm, humic acid, bile acid, bile extracts, bilirubin, bihverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-oleic acid, linoleic acid, oleic acid), folic acid and their derivatives, alanine diacetic acid, polyphenol, flavonoid, catechol C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, ferulic acid and its derivatives, butylated hydroxytoluene, nordoyl auric acid, nordylhydroxyanisethane, Nordylhydroxyanisole, butylated hydroxyanisole, Nordylauroyl aurate , Tπhydroxybutyrophenon, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ) selenium and its derivatives (eg Selenomethionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances

The amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 0.1 to 10% by weight, based on the total weight of the preparation

Prophylaxis or cosmetic or dermatological treatment with the invented The active ingredient used according to the invention or with the cosmetic or topical dermatological preparations with an effective content of the active ingredient used according to the invention is carried out in the usual way, in such a way that the active ingredient used according to the invention or the cosmetic or topical dermatological preparations with an effective content of the invention Active ingredient is applied to the affected skin

The active ingredient used according to the invention can advantageously be incorporated into customary cosmetic and dermatological preparations, which can be in various forms. For example, they can be a solution, an emulsion of the water-in-oil (W / O) type or of the type OI-in water (O / W), or a multiple emulsions, for example of the type water-in-OI-in-water (W / O / W) or oil-in-water-in-OI (O / W / O), a hydrodispersion or lipodispersion, a Pickering emulsion, a gel, a solid stick or an aerosol

Emulsions according to the invention in the sense of the present invention, for example in the form of a cream, a lotion, a cosmetic milk, are advantageous and contain, for example, fats, oils, waxes and / or other fatty substances, as well as water and one or more emulsifiers, such as them are usually used for such a type of formulation

It is also possible and advantageous for the purposes of the present invention to insert the active ingredient used according to the invention in aqueous systems or surfactant preparations for cleaning the skin and hair

It is of course known to the person skilled in the art that sophisticated cosmetic compositions are usually not conceivable without the customary auxiliaries and additives. These include, for example, consistency agents, fillers, perfume, dyes, emulsifiers, additional active ingredients such as vitamins or proteins, light stabilizers, stabilizers, Insect repellents, alcohol, water, salts, antimicrobial, proteolytic or keratolytically active substances, etc

It may also be advantageous to encapsulate the active compounds according to the invention, for example as so-called solid lipid nanoparts with the aid of melted waxes which ter other, but not exclusively, can be selected from the group of ester waxes, methylglycol waxes or hydrocarbon waxes. It may also be advantageous to encapsulate the active compounds according to the invention in polymers, for example in particles based on highly crosslinked polymethacrylates and / or cellulose acetates and / or as a core / Shell particles with a shell made of poly (oxymethylurea), nylon, polyamides, polyurethane, polyester, gelatin and polyolefins

Mutatis mutandis, corresponding requirements apply to the formulation of medical preparations

Medical topical compositions within the meaning of the present invention generally contain one or more medicaments in an effective concentration. For the sake of simplicity, reference is made to the legal provisions of the Federal Republic of Germany for a clear distinction between cosmetic and medical use and corresponding products (eg cosmetics regulation, food and Medicines Act)

It is also advantageous to add the active ingredient used according to the invention as an additive to preparations which already contain other active ingredients for other purposes

Accordingly, cosmetic or topical dermatological compositions in the sense of the present invention, depending on their structure, can be used, for example, as skin protection cream, cleansing milk, sunscreen lotion, nutritional cream, day or night cream, etc. It is possibly possible and advantageous to use the compositions according to the invention as a basis for to use pharmaceutical formulations

It is also advantageous for the purposes of the present invention to produce cosmetic and dermatological preparations, the main purpose of which is not protection against sunlight, but which nevertheless contain UV protection substances, for example in day creams or makeup products Usually UV-A or UV-B filter substances are incorporated. UV protection substances, as well as antioxidants and, if desired, preservatives, provide effective protection of the additives. Preparations even against spoilage Favorable are also cosmetic and dermatological preparations which are in the form of a sunscreen

Accordingly, the preparations within the meaning of the present invention preferably additionally contain, in addition to the clover extract according to the invention, at least one further UV-A and / or UV-B filter substance. The formulations can, although not necessary, optionally also one or more organic and / or inorganic Contain pigments as UV filter substances, which can be in the water and / or oil phase

Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (TιO ₂ ), zinc (ZnO), iron (e.g. Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (SιO ₂ ), Manganese (e.g. MnO), aluminum (Al ₂ O ₃ ), cerium (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides

For the purposes of the present invention, such pigments can advantageously be surface-treated (“coated”), with an amphiphilic or hydrophobic character being formed or retained, for example. This surface treatment can consist in the pigments having a thin hydrophobic layer by processes known per se be provided

For example, titanium dioxide pigments which are coated with octylsilanol are advantageous according to the invention. Suitable titanium dioxide particles are available from Degussa under the trade name T805. TιO ₂ particles coated with aluminum stearate, for example those available under the trade name MT 100 T from TAYCA, are also particularly advantageous

A further advantageous coating of the inorganic pigments consists of dimethyl polysiloxane (also dimethicone), a mixture of fully methylated, linear siloxane polymers, which are blocked with terminally methyl siloxane units. Zinc oxide pigments which are in this way particularly advantageous in the sense of the present invention be coated It is also advantageous to coat the inorganic pigments with a mixture of dimethylpolysiloxane, in particular dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane units, and Sihcagel, which is also referred to as simethicone. It is particularly advantageous if the inorganic pigments are additionally coated with aluminum hydroxide or aluminum oxide hydrate (also alumina, CAS No. 1333-84-2) are coated. Titanium dioxides coated with simethicone and alumina are particularly advantageous, the coating also being able to contain water. An example of this is that of the company under the trade name Eusolex T2000 Titanium dioxide available from Merck

An advantageous organic pigment for the purposes of the present invention is 2,2'-methylene-bιs- (6- (2H-benzotrιazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol) [INCI bisoctyl-tnazole], which is available under the trade name Tinosorb® M from CIBA-Chemika en GmbH

Preparations according to the invention advantageously contain substances which absorb UV radiation in the UV-A and / or UV-B range, the total amount of the filter substances, for example, 0.1% by weight to 30% by weight, preferably 0.5 to 20 % By weight, in particular 1.0 to 15.0% by weight, based on the total weight of the preparations, in order to provide cosmetic preparations which protect the hair or the skin from the entire range of ultraviolet radiation Sunscreen for hair or skin

Advantageous UV-A filter substances for the purposes of the present invention are dibenzoyl methandenvate, in particular 4- (tert-butyl) -4'-methoxydιbenzoylmethan (CAS No. 70356-09-1), marketed by Givaudan under the trade name Parsol ^® 1789 and is sold by Merck under the trade name Eusolex® 9020

Further advantageous UV-A filter substances are the phenylene-1,4-bιs- (2-benzιmιdazyl) - 3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts , in particular the phenylene-1,4-bιs- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bιs sodium salt with the INCI name bisimidazylate, which, for example, under the trade name Neo Hehopan AP Haarmann & Reimer is available Also advantageous are the 1,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt) , which is also known as benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid).

Advantageous UV filter substances in the sense of the present invention are also so-called broadband filters, i.e. Filter substances that absorb both UV-A and UV-B radiation.

Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyltriazine derivatives. Particularly preferred are 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (INCI: Aniso Triazin), which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH.

Particularly advantageous preparations in the sense of the present invention, which are distinguished by a high or very high UV-A protection, preferably contain a plurality of UV-A and / or broadband filters, in particular dibenzoylmethane derivatives [for example 4- (tert-butyl) -4'-methoxydibenzoylmethane], benzotriazole derivatives [for example the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol )], Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or its salts, the 1,4-di (2-oxo-10-sulfo-3 -bornylidenemethyl) -benzene and / or its salts and / or the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) - 1, 3,5-triazine, individually or in any combination with one another.

Also other UV filter substances, which the structural motif

are advantageous UV filter substances for the purposes of the present invention, for example the s-triazine derivatives described in European patent application EP 570 838 A1, the chemical structure of which is given by the generic formula

is reproduced, whereby

R represents a branched or unbranched dC ₁₈ alkyl radical, a C ₅ -C ₂ cycloalkyl radical, optionally substituted by one or more C _r C ₄ alkyl groups,

X represents an oxygen atom or an NH group,

Ri is a branched or unbranched CrCι ₈ alkyl radical, a C ₅ -C ₂ cycloalkyl radical, optionally substituted with one or more CC alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which

A represents a branched or unbranched C ₈ -C alkyl radical, a C ₅ -C ₁₂ cycloalkyl or aryl radical, optionally substituted with one or more CC ₄ alkyl groups, R _{3 represents} a hydrogen atom or a methyl group, n is a number of 1 to 10, R _{2 represents} a branched or unbranched d-Ciβ-alkyl radical, a C ₅ -Cι ₂ cycloalkyl radical, optionally substituted with one or more dC - alkyl groups, when X represents the NH group, and one branched or unbranched CC ₁₈ alkyl radical, a C ₅ -C ₂ cycloalkyl radical, optionally substituted with one or more C 1 -C 4 alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which

A represents a branched or unbranched Ci-Ciβ-alkyl radical, a Cs-C ₁₂ cycloalkyl or aryl radical, optionally substituted by one or more CC alkyl groups,

R _{3 represents} a hydrogen atom or a methyl group, n represents a number from 1 to 10 when X represents an oxygen atom.

A particularly preferred UV filter substance in the sense of the present invention is also an asymmetrically substituted s-triazine, the chemical structure of which is represented by the formula

is reproduced, which is also referred to below as dioctylbutylamidotriazon (INCI: dioctylbutamidotriazone) and is available under the trade name UVASORB HEB from Sigma 3V.

Advantageous for the purposes of the present invention is a symmetrically substituted s-triazine, 4,4 _'l 4' - (1, 3,5-triazine-2,4,6-triyltriimino) -THS-benzoic acid tris (2- ethylhexyl ester), synonym: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone), which is marketed by BASF Aktiengesellschaft under the trade name UVINUL® T 150.

European laid-open specification 775 698 also describes bis-resorcinyltriazine derivatives which are to be used with preference, the chemical structure of which is given by the generic formula

is reproduced, wherein Ri, R ₂ and Ai represent a wide variety of organic radicals.

Also advantageous in the sense of the present invention are the 2,4-bis - {[4- (3-sulfonato) - 2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-tazine sodium salt, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxy- phenyl) -1, 3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- [4- (2-methoxyethyl- carboxyl) phenylamino] -1, 3,5-triazine, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- [4- (2-ethylcarboxyl) phenylamino] -1, 3,5-thazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl } -6- (1-methyl-pyrrol-2-yl) -1, 3,5-triazine, the 2,4-bis - {[4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy] phenyl } -6- (4-methoxyphenyl) -1, 3,5-triazine, the 2,4-bis - {[4- (2 "-methylpropenyloxy) -2-hydroxy] phenyl} -6- (4th -methoxyphenyl) -1,3,5-triazine and the 2,4-bis - {[4- (1 \ 1 \ 1 \ 3 \ 5 \ 5 \ 5'-heptamethylsiloxy-2 "- methyl-propyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine.

An advantageous broadband filter in the sense of the present invention is 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol) , which is available under the trade name Tinosorb® M from CIBA-Chemicals GmbH.

Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1, 3,3,3-tetramethyl-1 - [( trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.

The UV-B and / or broadband filters can be oil-soluble or water-soluble. Advantageous oil-soluble UV-B and / or broadband filter substances are e.g. B .:

^■ 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;

^■ 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;

2,4,6-trianilino- (p-carbo-2'-ethyl-T-hexyloxy) -1,3,5-triazine;

■ esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester; ■ esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;

^■ Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone ^■ and UV filters bound to polymers.

Advantageous water-soluble UV-B and / or broadband filter substances are e.g. B .:

^■ salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself; ^■ sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene-methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene-methyl) sulfonic acid and salts thereof.

A further light protection filter substance according to the invention to be used advantageously is ethylhexyl-2-cyano-3,3-diphenylacrylate, obtainable (octocrylene) from BASF under the name Uvinul ^® N 539th

It can also be of considerable advantage to use polymer-bound or polymeric UV filter substances in preparations according to the present invention, in particular those as described in WO-A-92/20690.

It may also be advantageous, if appropriate, to incorporate further UV-A and / or UV-B filters into cosmetic or dermatological preparations, for example certain salicylic acid derivatives such as 4-isopropylbenzyl salicylate, 2-ethylhexyl salicylate (= octyl salicylate), homomenthyl salicylate.

The list of the UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.

The cosmetic and dermatological preparations according to the invention can contain cosmetic active ingredients, auxiliaries and / or additives, as are usually used in such preparations, e.g. B. antioxidants, preservatives, bactericides, perfumes, substances to prevent foaming, dyes, pigments elements that have a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moisturizing and / or moisturizing substances, fats, oils, waxes or other customary components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

If the cosmetic or dermatological preparation in the sense of the present invention is a solution or emulsion or dispersion, the following can be used as solvents: • Water or aqueous solutions

• oils, such as triglycerides of capric or caprylic acid, but preferably castor oil;

• Fats, waxes and other natural and synthetic fat bodies, preferably esters of fatty acids with alcohols of low C number, e.g. B. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with alkanoic acids lower C-

Number or with fatty acids;

• Alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerin, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol mononomethyl or monoethyl ether and analogues

Products.

Mixtures of the abovementioned solvents are used in particular. Water can also be a component of alcoholic solvents.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions for the purposes of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C-atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecylate, erylolate, erylolate, erylolate, erylolate, erylolate, erylolate, erylolate, erylolate, erylolate, erylylate, semi-synthetic and natural mixtures of such esters, e.g. B. Jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also the fatty acid triglycee de, especially the triglycerol esters, saturated and / or unsaturated , branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 - 18 carbon atoms. The fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, e.g. B. olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.

The oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, Cι ₂ .ι ₅ alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.

Particularly advantageous are mixtures of C _12- i ₅ -alkyl benzoate and 2-ethylhexyl isostearate, mixtures of _2- Cι i ₅ -alkyl benzoate and isotridecyl isononanoate and mixtures of _2- Cι ι ₅ -alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

Of the hydrocarbons, paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.

The oil phase can advantageously also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred, in addition to the silicone oil or the silicone oils, an additional content of other oil phases. to use lower components

Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention. However, other silicone cones can also be used advantageously in the context of the present invention, for example hexamethylcyclotπsiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

Mixtures of cyclomethicone and isotridecyl isononanoate, of cyclomethicone and 2-ethylhexyl isostearate are also particularly advantageous

The aqueous phase of the preparations according to the invention advantageously advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl - or -monoethyl ether and analog products, furthermore alcohols of low C number, for example ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners, which one or more can advantageously be selected from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of the polyacrylates, preferably a polyacrylate from the group of the so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, each individually or in combination

Gels used in accordance with the invention usually contain alcohols of low C number, for example ethanol, isopropanol, 1, 2-propanediol, glycerol and water or an oil mentioned above in the presence of a thickener which, in the case of oligo-alcoholic gels, preferably silicon dioxide or an aluminum silicate, with water alcoholic or alcoholic gels is preferably a polyacrylate

Solid sticks contain, for example, natural or synthetic waxes, fatty alcohols or fatty acid esters

Common raw materials which are suitable for use as cosmetic sticks for the purposes of the present invention are liquid oils (for example paraffinols, castor oil, iso- propyl myristate), semi-solid components (e.g. petroleum jelly, lanolin), solid components (e.g. beeswax, ceresin and microcrystalline waxes or ozokerite) as well as high-melting waxes (e.g. carnauba wax, candelilla wax)

Suitable blowing agents for cosmetic and / or dermatological preparations which can be sprayed from aerosol containers for the purposes of the present invention are the customarily known volatile, liquefied blowing agents, for example hydrocarbons (propane, butane, isobutane), which can be used alone or in a mixture with one another. Compressed air can also be used advantageously.

Of course, the person skilled in the art knows that there are non-toxic propellant gases per se which would fundamentally be suitable for realizing the present invention in the form of aerosol preparations, but which should nevertheless be dispensed with, in particular fluorocarbons and, because of their harmful effects on the environment or other accompanying circumstances Chlorofluorocarbons (CFCs).

Cosmetic preparations in the sense of the present invention can also be present as gels which, in addition to an effective content of the active ingredient according to the invention and solvents usually used for this purpose, preferably water, or organic thickeners, for. B. gum arabic, xanthan gum, sodium alginate, cellulose derivatives, preferably methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or inorganic thickeners, e.g. B. aluminum silicates such as bentonite, or a mixture of polyethylene glycol and polyethylene glycol stearate or distearate. The thickener is in the gel e.g. B. in an amount between 0.1 and 30 wt .-%, preferably between 0.5 and 15 wt .-%.

It is particularly advantageous in the sense of the present invention if the cosmetic or dermatological preparations according to the invention contain further active substances, in particular natural active substances and / or their derivatives, such as, for example, B. alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha glucosyl rutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, hop or hop malt extract, taurine and / or ß-alanine. The content of these active ingredients (one or more compounds) is advantageously chosen from the range from 0.0001 to 30% by weight, based on the total weight of the preparations.

The following examples are intended to illustrate the present invention.

Examples:

1. PIT emulsions

2. Examples of O / W creams

3. Examples of W / O emulsions

4. Examples of hydrodispersions

5th example (gel cream):

Mass content (%)

Acrylates / C 10-30 alkyl acrylates 0.40

Crosspolymer

Carbomer 0.20

Xanthan gum 0.10

Cetearyl alcohol 3.00

C ₁₂ . ₁₅ alkyl benzoates 4.00

Caprylic / Capric Triglyceride 3.00

Cyclometicone 5.00

Dimeticone 1, 00

Clover extract 0.20

Glycerin 3.00

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralized to 100.0 pH adjusted to 6.0

6. Example (W / O cream)

Lameform TGI 3.50

Glycerin 3.00

Dehymuls PGPH 3.50

Clover extract 0.50

Preservatives q.s.

Perfume q.s.

Water, demin. ad 100.0

Magnesium sulfate 0.6

Isopropyl stearate 2.0

Caprylyl ether 8.0

Cetearyl isononanoate 6.0 7. Example (W / O / W cream):

Mass content (%)

Glyceryl stearate 3.00

PEG-100 stearate 0.75 behenyl alcohol 2.00

Caprylic / Capric Triglyceride 8.0

Octyldodecanol 5.00

C-12-15 alkyl benzoates 3.00

Clover extract 1.00, magnesium sulfate (MgSO ₄ ) 0.80

EDTA 0.10

Conservation q.s.

Perfume q.s.

Water demineralized to 100.0 pH adjusted to 6.0

Claims

claims:

Use of clover extract in cosmetic or dermatological preparations for the treatment and prophylaxis of the symptoms of environmentally induced negative skin changes as well as inflammatory, hyperactive and / or degenerative skin conditions.

2. Use according to claim 1, wherein this use is a measure against

• Certain degenerative appearances of the skin (eg sagging skin, loss of elasticity, age spots, telangiectasias, disturbance of the osmolytic balance, the natural skin pH value as well as loss of the epidermal and dermal cell layers, the components of the connective tissue, the rete cones and capillary vessels the skin) and / or the skin appendages,

• environmental (caused by smoking, smog, reactive oxygen species, free radicals and the like) negative changes in skin and skin

Skin appendages,

Deficient, sensitive or hypoactive skin conditions or deficient, sensitive or hypoactive conditions of skin appendages (sebum and sweat glands), reduced skin thickness, • skin sagging and skin fatigue,

Disorders of normal skin pH and osmolytic balance,

pigmentation,

Itching,

Homolayer barrier disorders, • Changes in transepidermal water loss and normal

Moisture content of the skin,

Changes in normal lipid peroxidation,

Changes in the ceramide, lipid and energy metabolism of healthy skin,

Hair loss, for improved hair growth and / or for disorders in the structure of hair,

Deviations from normal cell-cell communication in the skin,

Changes in normal fibroblast and keratinocyte proliferation,

Changes in normal fibroblast and keratinocyte differentiation, • Inflammatory skin conditions as well as atopic eczema, seborrheic eczema, polymorphic light dermatosis, psohasis, vitiligo and / or to calm sensitive or irritated skin, to maintain normal collagen, hyaluronic acid, elastin and glycosaminoglycan homeostasis, to stimulate estrogen -Synthetase, for increased activation of proteolytic enzymes in the skin, such as B. Metalloproteinases, to stimulate intracellular DNA synthesis, especially in deficient or hypoactive skin conditions, in wound healing disorders, to increase cell regeneration and skin regeneration, to reduce the production of sebum, to prevent the formation and removal of comedones and / or for the adjustment of a normal sebum homeostasis, for the prevention or elimination of seborrheic phenomena, in particular for the prophylaxis and treatment of oily hair, but also for dandruff, to increase the skin's own protective and repair mechanisms (e.g. for dysfunctional enzymes, DNA, lipids, proteins) ), for pre- and post-treatment with topical application of laser and abrasive treatments, e.g. B. serve the reduction of skin folds and scars to counteract the resulting skin irritation and to promote the regeneration processes in the injured skin.

3. Use according to claim 1, characterized in that the clover extract content is selected from the range from 0.0005 to 50.0% by weight, in particular from 0.01 to 20.0% by weight, in each case based on the total weight of the composition.

4. Use according to claim 1, characterized in that the clover extract content from the range of 0.02 to 10.0 wt .-%, in particular from 0.5 up to 3.0% by weight is selected, in each case based on the total weight of the composition.

5. Use according to claim 1, wherein the cosmetic or dermatological preparations are characterized by an additional content of one or more of the following natural active ingredients and their derivatives: alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha glucosyl rutin, carnitine, carno - sin, natural and / or synthetic isoflavonoids, creatine, hop or hop malt extract, taurine and / or ß-alanine.