WO2014183973A1

WO2014183973A1 - Stabilized preparations containing ascorbic acid and phosphate ions

Info

Publication number: WO2014183973A1
Application number: PCT/EP2014/058486
Authority: WO
Inventors: Kerstin Heike; Juliane Schade; Julia Eckert; Jens Treu
Original assignee: Beiersdorf Ag
Priority date: 2013-05-14
Filing date: 2014-04-25
Publication date: 2014-11-20
Also published as: DE102013208865A1

Abstract

Disclosed are preparations, in particular cosmetic or dermatological preparations, containing a) at least 1% by weight, preferably at least 2% by weight, ascorbic acid and/or ascorbyl compounds relative to the total weight of the preparations, b) one or more water-soluble phosphates, in particular orthophosphates, c) 4-tert-butyl-4'-methoxydibenzoylmethane.

Description

description

The present invention relates to the use of phosphate ions for the protection of ascorbic acid and / or generally ascorbyl compounds against oxidation, in particular in cosmetic and dermatological preparations. Preferably, the present invention relates to cosmetic preparations with effective protection against harmful oxidation dationsprozessen in the skin, but also for the protection of cosmetic preparations themselves or to protect the components of cosmetic preparations from harmful oxidation processes.

The present invention further relates to antioxidant active substance combinations, preferably those which are used in skin-care cosmetic or dermatological preparations. In particular, the invention also relates to cosmetic and dermatological preparations containing such antioxidants.

In a preferred embodiment, the present invention relates to cosmetic and dermatological preparations for the prophylaxis and treatment of cosmetic or dermatological skin lesions, such as, for example, Skin aging, especially skin aging caused by oxidative processes.

The present invention particularly preferably relates to active ingredients and preparations containing such active ingredients for the recycling of oxidized vitamin E, protection against UV-related skin damage (erythema), stimulation of collagen synthesis, strengthening of dermo-epidermal junction zone (skin tightening), visible improvement of the skin condition premature aging of the skin (improvement of the complexion, anti-wrinkle effect), and stimulation of ceramide synthesis. The present invention further relates to active compound combinations and preparations which are used for the prophylaxis and treatment of the photosensitive skin, in particular photodermatoses. The damaging effect of the ultraviolet part of solar radiation on the skin is well known. While rays with a wavelength less than 290 nm (the so-called UVC range) are absorbed by the ozone layer in the earth's atmosphere, rays in the range between 290 nm and 320 nm, the so-called UVB range, cause erythema simple sunburn or even more or less severe burns.

As a maximum of the erythema efficiency of sunlight, the narrower range around 308 nm is given. For protection against UVB radiation, numerous compounds are known, which are derivatives of 3-Benzylidencamphers, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and also of 2-phenylbenzimidazole.

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

For protection against the rays of the UVA range, therefore, certain derivatives of dibenzoylmethane are used whose photostability (Int J. Cosm. Science 10, 53 (1988)) is not sufficiently given.

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

Predominantly such photochemical reaction products are radical compounds, for example hydroxy radicals. Also undefined radical Photoproducts that form in the skin itself may display uncontrolled sequelae due to their high reactivity. However, singlet oxygen, a non-radical excited state of the oxygen molecule, can also occur on UV irradiation, as can short-lived epoxides and many others. Singlet oxygen, for example, is distinguished from the normally present one

Triplet oxygen (radical ground state) due to increased reactivity. However, there are also excited, reactive (radical) triplet states of the oxygen molecule. Furthermore, UV radiation counts as ionizing radiation. Thus, there is a risk that ionic species may also be formed upon UV exposure, which in turn may oxidatively interfere with the biochemical processes.

As a result of all these influences, the cell is exposed to so-called oxidative stress, which is understood as stressing the living cell by accumulating cell-damaging oxidized compounds such as, for example, lipid hydroperoxides, hydrogen peroxide or reactive oxygen compounds such as singlet oxygen, hydroxyl, and peroxide anions. The oxidative stress can z. B. by radiation exposure, xenobiotics, heavy metal ions or other causes. He plays a role in the development of some diseases.

Although the body has limited defense mechanisms against oxidative stress. Thus, with the help of various enzyme activities [eg. As superoxide dismutase, peroxidases such as glutathione peroxidase (see glutathione), catalase, ceruloplasmin] the occurrence of reactive radicals can be prevented. However, this is often insufficient and must be supported, be it on a cosmetic or medical level.

In order to prevent oxidative stress, additional antioxidants and / or radical scavengers can be incorporated in the cosmetic or dermatological formulations.

Although some antioxidants and radical scavengers are known. For example, it has already been proposed in US Pat. Nos. 4,144,325 and 4,248,861, as well as numerous other documents, to use vitamin E, a substance with known antioxidant activity, in cosmetic formulations, but here too the effect achieved lags far behind the hoped-for effect. In itself excellent antioxidants are selected from the group of ascorbic acid and the ascorbyl compounds. L-ascorbic acid {(R) -5 - [(S) -1,2-dihydroxyethyl] -3,4-dihydroxy-5-H-furan-2-one, vitamin C} is characterized by the structural formula

out. It is readily soluble in water, readily soluble in alcohol, insoluble in ether, petroleum ether, chloroform, benzene and in fats u. fat oils. Ascorbic acid is an endiol and has a strong reducing effect as a reductone. Ascorbic acid is sensitive to heat and is decomposed in particular in the presence of heavy metal traces and in an alkaline medium by light and atmospheric oxygen, in pure, dry state, however, it is relatively resistant to light, air and heat. Ascorbyl compounds, preferably ascorbyl esters of fatty acids, more preferably ascorbyl palmitate, are often used in cosmetic and dermatological preparations, since the sensitivity of these compounds to oxidative influence on ascorbic acid is greatly reduced and these compounds are usually better oil-soluble, which can offer galenic advantages.

Ascorbyl compounds in the narrower sense are in particular the ascorbyl esters of the general structure

wherein R may represent a branched or unbranched alkyl radical having up to 25 carbon atoms. An object of the present invention was to eliminate the disadvantages of the prior art. In particular, active ingredients or preparations containing such active ingredients should be made available, in the use of which a stimulation of the collagen synthesis, a strengthening of the dermo-epidermal junction zone (skin tightening) and a visible improvement of the skin condition are achieved.

The aim was to solve galenic problems and to allow stabilization of vitamin C in the cosmetic formulations. However, it was surprising and unforeseeable for the skilled person that preparations, in particular cosmetic or dermatological preparations containing a) at least 1, preferably at least 2 wt .-% of ascorbic acid and / or

Ascorbyl compounds, based on the total weight of the preparations b) one or more water-soluble phosphates, in particular orthophosphates c) 4-tert-butyl-4'-methoxydibenzoylmethane

to remedy the disadvantages of the prior art. for the protection of at least one active ingredient selected from the group of ascorbic acid and the ascorbyl compounds, against oxidation, in particular for protection against oxidation in cosmetic or dermatological preparations, wherein the total content of ascorbic acid and ascorbyl compounds in the preparations at least 1, preferably at least 2 wt. -%, based on the total weight of the preparations. The phosphate or phosphates, in particular alkali metal phosphates, particularly preferably the potassium phosphate, are advantageously present in cosmetic or dermatological preparations, preferably at 0.001% by weight to 10% by weight, preferably from 0.05% by weight to 5% by weight. %, particularly preferably from 0.1 to 2.0% by weight, based on the total weight of the preparations. Hydrogen phosphates and dihydrogen phosphates also apply as "phosphate" in the context of the present invention.

The ascorbyl compound or the ascorbyl compounds, in particular vitamin C, is or are advantageously according to the invention in cosmetic or dermatological preparations to 1, preferably at least 2 wt .-% to 20 wt .-%, particularly preferably to 3 wt .-% to 5 wt .-%, based on the total weight of the preparations.

According to the invention, 4-tert-butyl-4'-methoxydibenzoylmethane is advantageously present in cosmetic or dermatological preparations, preferably up to 10% by weight, preferably from 0.05% by weight to 5% by weight, particularly preferably 0.1%. 2.0 wt .-%, based on the total weight of the preparations.

It was unforeseeable for the skilled person that the active substance combinations or cosmetic or dermatological preparations used according to the invention, containing such

act better as an antioxidant

better than radical scavengers

better prevent the binding of harmful photoproducts to lipids, DNA and proteins

better oxidized vitamin E recycler

better protect against UV-related skin damage

better to stimulate collagen synthesis

better tighten the dermo-epidermal junction (papillae)

as the active ingredients, drug combinations and preparations of the prior art.

Furthermore, it had not been foreseen that the active ingredient combinations used in cosmetic or dermatological preparations according to the invention have higher stability than the active ingredients used individually, which relates in particular to the ascorbyl compounds and more particularly the vitamin C.

According to the invention, therefore, the use of active compound combinations according to the invention as an antioxidant and its use for the control and / or prophylaxis of the skin aging caused by oxidative stress and inflammatory reactions onen.

As a particularly advantageous embodiment of the present invention is further considered the use of active compound combinations according to the invention for the control and / or prophylaxis of oxidative stress. The cosmetic or dermatological preparations according to the invention may be composed as usual and used for the treatment, care and cleansing of the skin and / or the hair and as a make-up product in decorative cosmetics. They preferably contain 0.001% by weight to 10% by weight, preferably 0.05% by weight to 5% by weight, in particular 0.1% to 2.0% by weight, based on the total weight of the preparations, on active compound combinations used according to the invention.

It is preferred according to the invention to add to the active ingredient combinations or cosmetic or dermatological preparations used according to the invention, such active substance combinations containing complexing agents.

Complexing agents are known auxiliaries of cosmetology or medical galenics. By complexing of interfering metals such as Mn, Fe, Cu and others, for example, unwanted chemical reactions in cosmetic or dermatological preparations can be prevented.

Complexing agents, in particular chelators, form complexes with metal atoms, which in the presence of one or more polybasic complexing agents, ie chelators, represent metallacycles. Chelates represent compounds in which a single ligand occupies more than one coordination site on a central atom. In this case, normally stretched compounds are closed by complex formation via a metal atom or ion into rings. The number of bound ligands depends on the coordination number of the central metal. The prerequisite for chelation is that the metal-reactive compound contain two or more atomic groups acting as electron donors.

The complexing agent (s) can advantageously be selected from the group of the customary compounds, preference being given to at least one substance selected from the group consisting of tartaric acid and its anions, citric acid and its anions, aminopolycarboxylic acids and their anions (such as, for example, ethylenediaminetetraacetic acid (EDTA) and theirs Anions, nitrilotriacetic acid (NTA) and their anions, hydroxyethylenediaminotriacetic acid (HOEDTA) and their anions,

Diethylenetaminopentaacetic acid (DPTA) and its anions, trans-1,2-diaminocyclohexanetetraacetic acid (CDTA) and their anions). The complexing agent (s) according to the invention are advantageously present in cosmetic or dermatological preparations, preferably at from 0.01% by weight to 10% by weight, preferably from 0.05% by weight to 5% by weight, particularly preferably 0.1 - 2.0 wt .-%, based on the total weight of the preparations.

For use, the cosmetic and dermatological preparations are applied according to the invention in the usual manner for cosmetics on the skin and / or hair in sufficient quantity. Cosmetic and dermatological preparations according to the invention can be present in various forms. So they can e.g. a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water type (O / W), a multiple emulsion, for example of the water-in-oil-in-water type. Water (W / O / W), a gel, a solid stick, an ointment or even an aerosol. It is also advantageous to present isoquercitrin in encapsulated form, e.g. in

Collagen matrices and other common encapsulating materials, e.g. as cellulase encapsulations, in gelatin, wax matrices or liposomally encapsulated. In particular wax matrices as described in DE-OS 43 08 282, have been found to be favorable.

It is also possible and advantageous for the purposes of the present invention to introduce active compound combinations used according to the invention into aqueous systems or surfactant preparations for cleaning the skin and hair. The cosmetic and dermatological preparations according to the invention may comprise cosmetic adjuvants conventionally used in such preparations, for example preservatives, bactericides, perfumes, foaming inhibitors, colorants, pigments having a coloring effect, thickeners, surface-active substances, emulsifiers, softening, moistening and / or moisturizing substances, fats, oils, waxes or other customary constituents of a cosmetic or dermatological formulation, such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives. In particular, compounds according to the invention may also contain further antioxidants and / or radical scavengers.

Such antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocaninic acid) and derivatives thereof, peptides such as D, L-carnosine, D-carnosine, L-carnosine. Carnosine and its derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg Thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl,

Cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteinesulfoximine, buthionine sulfones, penta, hexa, Heptathioninsulfoximin) in very low tolerated dosages (eg pmol to μηΊθΙ / kg), (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid , 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, tocopherols and derivatives (eg E-acetate), vitamin A and derivatives (vitamin A palmitate), as well as benzylic benzylic resin, rutinsea and their derivatives, butylhydroxytoluene, butylhydroxyanisole,

Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, uric acid and its derivatives, mannose and its derivatives, sesamol, sesamolin, zinc and its derivatives (eg ZnO, ZnS0 ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, Trans-stilbene oxide) and the inventively suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these drugs.

The amount of the aforementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 to 20 wt .-%, in particular 0.1 to 10 wt .-%, based on the Total weight of the preparation. If vitamin E and / or its derivatives represent the additional antioxidant (s), it is advantageous to choose their respective concentrations from the range of 0.001-10% by weight, based on the total weight of the formulation. If vitamin A or vitamin A derivatives, or carotenes or derivatives thereof, constitute the additional antioxidant (s), it is advantageous if their respective concentrations are in the range from 0.001 to 10% by weight, based on the total weight of the formulation , to choose. Emulsions according to the invention are advantageous and contain, for example, the said fats, oils, waxes and other fatty substances, as well as water and an emulsifier, as is customarily used for such a type of formulation.

The lipid phase can advantageously be selected from the following substance group:

- mineral oils, mineral waxes

Oils such as triglycerides of capric or caprylic acid, further natural oils such as e.g. Castor oil;

Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or lower esters of fatty alcohols with alkanoic acids

C number or with fatty acids;

benzoates;

Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols having 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 having a chain length of 3 to 30 C-atoms. Such ester oils can then advantageously be selected from the group consisting of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isobutyl stearate and isopropyl stearate. nonyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and also synthetic, semisynthetic and natural mixtures of such esters, for example jojoba oil. Furthermore, the oil phase can be advantageously 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 the fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12 to 18 carbon atoms. The fatty acid triglycerides can be selected, for example, advantageously from the group of synthetic, semi-synthetic and natural oils, such as 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 are also advantageous to use in the context of the present invention. It may also be advantageous, if appropriate, 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 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, _Ci2-i5-alkyl benzoate, caprylic-capric acid triglyceride, dicaprylyl ether.

Particularly advantageous are mixtures of _Ci2-i5-alkyl benzoate and 2-ethylhexyl isostearate, mixtures of _Ci2-i5-alkyl benzoate and isotridecyl isononanoate and mixtures of C _12- i5-alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

Of the hydrocarbons, paraffinol, squalane and squalene are to be used advantageously in the context of the present invention.

Advantageously, the oil phase may further comprise a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or silicone oils. Advantageously, cyclomethicone (octamethylcyclotetrasiloxane) is used as the silicone oil to be used according to the invention. However, other silicone oils are also advantageous for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

Also particularly advantageous are mixtures of cyclomethicone and isotridecyl isonanoate, of cyclomethicone and 2-ethylhexyl isostearate.

It has turned out to be particularly favorable according to the invention, if as

Emulsifier system mixtures of i) sodium stearoylglutamate and / or ii) cetylstearyl sulfate in combination with iii) glyceryl stearate.

According to the invention, it is particularly advantageous if the preparations

i) 0 to 10 wt .-% sodium stearoylglutamate

ii) 0 to 10 wt .-% Cetylstearylsulfat

iii) 0.05 to 10% by weight of glyceryl stearate

contain.

According to the invention, it is particularly advantageous if the preparations

i) 0.25 to 5% by weight sodium stearoylglutamate

ii) 0.25 to 5 wt .-% Cetylstearylsulfat

iii) 0.25 to 5% by weight of glyceryl stearate

contain. Preparations which are O / W emulsions and are distinguished by the following features are very particularly preferred according to the invention:

a) 2 to 20, in particular 3 to 5 wt .-% of ascorbic acid and / or ascorbyl compounds, based on the total weight of the preparations,

b) from 0.001% by weight to 10% by weight, preferably from 0.05% by weight to 5% by weight, in particular preferably from 0.1% to 2.0% by weight, of one or more water-soluble

Phosphates, especially orthophosphates,

c) from 0% by weight to 10% by weight, preferably from 0.05% by weight to 5% by weight, particularly preferably from 0.1 to 2.0% by weight, of 4-tert-butyl butyl-4'-methoxydibenzoylmethane, i) 0 to 10% by weight, preferably 0.25 to 5% by weight, of sodium stearoylglutamate ii) 0 to 10% by weight, preferably 0.25 to 5% by weight, of cetyl stearylsulfate iii) 0.05 to 10 wt .-%, preferably 0.25 to 5 wt .-% glyceryl stearate, each based on the total weight of the preparations.

If appropriate, the aqueous phase of the preparations according to the invention advantageously contains alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, di - ethylene glycol monomethyl or monoethyl ether and analogous products, furthermore low C-number alcohols, eg Ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called Carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.

In particular, mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another ingredient.

Emulsions of the invention are advantageous and contain e.g. the said fats, oils, waxes and other fatty substances, as well as water and an emulsifier, as commonly used for such a type of formulation. Gels according to the invention usually contain low C number alcohols, e.g. Ethanol, isopropanol, 1, 2-propanediol, glycerol and water or an above-mentioned oil in the presence of a thickener which is preferably silica or an aluminosilicate in oily-alcoholic gels, in aqueous-alcoholic or alcoholic gels, preferably a polyacrylate.

Suitable propellants for preparations which can be sprayed from aerosol containers according to the invention are the customary known highly volatile, liquefied propellants, for example hydrocarbons (propane, butane, isobutane), which can be used alone or mixed with one another. Also, compressed air is advantageous to use. Advantageously, preparations according to the invention may also contain other substances which absorb UV radiation in the UVA and / or UVB range, the total amount of filter substances being, for example, from 0.1% by weight to 30% by weight, preferably from 0.5 to 10 Wt .-%, in particular 1, 0 to 6.0 wt .-%, based on the total weight of the preparations, in order to provide cosmetic preparations that protect the hair or the skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for hair or skin.

If the preparations according to the invention contain UVB filter substances, these may be oil-soluble or water-soluble. Advantageously oil-soluble UVB filters according to the invention are, for example:

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

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

Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;

Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate,

Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;

Esters of benzalmalonic acid, preferably di (2-ethylhexyl) 4-methoxybenzalmalonate, - 2,4,6-trianilino (p-carbo-2'-ethyl-1 '-hexyloxy) -1, 3,5-triazine.

Advantageous water-soluble UVB filters are e.g.

Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself;

Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;

Sulfonic acid derivatives of the 3-benzylidene camphor, such as, for example, 4- (2-oxo-3-bomylidene-methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and its salts, and di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene and its salts (the debranching 10-sulfato compounds, for example the corresponding sodium, potassium or triethanolammonium salt), also referred to as benzene-1, 4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid

The list of said UVB filters which can be used in combination with the active compound combinations according to the invention should of course not be limiting.

The invention also provides the use of a combination of the active substance combinations used according to the invention with at least one UVB filter as antioxidant or the use of a combination of the active compound combinations used according to the invention with at least one UVB filter as antioxidant in a cosmetic or dermatological preparation.

It may also be advantageous to combine the combinations of active substances used according to the invention with UVA filters which have hitherto usually been present in cosmetic preparations.

Cosmetic and dermatological preparations with an effective content of active ingredient combinations used according to the invention may also contain inorganic pigments which are commonly used in cosmetics for the protection of the skin from UV rays. These are oxides of titanium, zinc, zirconium, silicon, manganese, cerium and mixtures thereof, as well as modifications in which the oxides are the active agents. Particular preference is given to pigments based on titanium dioxide.

On 22 September 2006, the EU Commission published a recommendation aimed at increasing the safety and transparency of sunscreen products. The EU recommendation provides for UVA protection of 1: 3 in relation to UVB protection. So far, only the protection of sunburn-causing UVB rays was regulated in the Cosmetics Regulation. With the new EU recommendation, each sunscreen should simultaneously protect against UVA radiation. The consumer should assume that UVA protection is guaranteed, which increases with increasing SPF value. For ethical reasons, an in vitro method is proposed. Beiersdorf AG developed an in-vitro method for UVA determination as a function of the sun protection factor: the UVA / UVB balance. In February 2005, the UVA / UVB balance was published as DIN 67502, making it the first official method for determining UVA protection in Europe.

A method for measuring the UVA protection performance is currently also being worked on in the COLI PA because the industry demands a uniform method. The COLIPA is the umbrella organization of the European cosmetics industry. a. Recommendations regarding the execution of the measurement method.

The UVA / UVB balance is the basis of the method discussed there. It is modified to include a pre-irradiation with UV light to include some special UV filter systems. So far, the products have been tested without pre-irradiation.

As a result, no information could be provided as to whether the protective effect of the product under real conditions is given by sun exposure. This advanced measurement method is called "COLIPA Ratio".

This means that UVA filters are used in relation of 1: 3 to UVB filters, and thus the UVA protection is increased with increasing light protection. Finally, according to the invention, the ratio of UV-A to UV-B protection, determined according to Colipa Guidlines Edition 2007a ("Method for the in vitro determination of UVA protection provided by sunscreen products"), is at least 1: 3, more preferably at least 2: 3. The cosmetic and dermatological substances contain active ingredients and auxiliaries customarily used for this type of preparations for hair care and hair treatment as adjuvants are preservatives, surface-active substances, substances for preventing foaming , Thickeners, emulsifiers, fats, oils, waxes, organic solvents, bactericides, perfumes, dyes or pigments. the purpose of which is to dye the hair or the cosmetic or dermatological preparation itself, electro- lytes, substances against the greasing of hair.

The following examples are intended to illustrate the present invention without limiting it. Unless indicated otherwise, all amounts, proportions and percentages are based on the weight and the total amount or on the total weight of the preparations.

Example 4: Lotion with Vitamin C% by weight

Paraffin Liquidum 10

Sodium stearoylglutamate 0.3

Glyceryl stearate 1, 5

Glycerol 10

Potassium hydrogen phosphate 0.5

Carbomer 0.2

Xanthan gum 1

Ascorbic acid 3.2

Alcohol Denat. 3

Q 10 0.04

Dimethicone 2

Cyclomethicone 3

Creatine 0.25

Perfume 0.2

Preservation q.s.

Water ad 100

Claims

claims

1. preparations, in particular cosmetic or dermatological preparations containing

a) at least 1, preferably at least 2 wt .-% of ascorbic acid and / or

Ascorbyl compounds, based on the total weight of the preparations b) one or more water-soluble phosphates, in particular orthophosphates c) 4-tert-butyl-4'-methoxydibenzoylmethane.

2. Use

b) one or more water-soluble phosphates, in particular orthophosphates c) 4-tert-butyl-4'-methoxydibenzoylmethane

for the protection of at least one active ingredient selected from the group of ascorbic acid and the ascorbyl compounds, against oxidation, in particular for protection against oxidation in cosmetic or dermatological preparations, wherein the total content of ascorbic acid and ascorbyl compounds in the preparations at least 1, preferably at least 2 wt. -%, based on the total weight of the preparations.

3. Preparations or use according to one of the preceding claims, characterized in that the one or more phosphates, in particular alkali metal phosphates, particularly preferably potassium phosphate, in the cosmetic or dermatological preparations to 0.001 wt .-% to 10 wt .-%, preferably to 0.05% by weight to 5% by weight, particularly preferably 0.1-2.0% by weight, based on the total weight of the preparations.

4. Preparations or use according to one of the preceding claims, characterized in that the ascorbyl compound or the ascorbyl compounds, in particular vitamin C, in the cosmetic or dermatological preparations to 2 wt .-% to 20 wt .-%, particularly preferably 3 wt. -% to 5 wt .-%, based on the total weight of the preparations, are included

5. Preparations or use according to one of the preceding claims, characterized in that the 4-tert-butyl-4'-methoxydibenzoylmethane in the cosmetic or dermatological preparations preferably to 10 wt .-%, preferably to 0.05 wt. % to 5 wt .-%, particularly preferably to 0.1 to 2.0 wt .-%, based on the total weight of the preparations contained.

6. Preparations or use according to one of the preceding claims, characterized in that in the cosmetic or dermatological preparations i) 0 to 10 wt .-% Natriumstearoylglutamat

ii) 0 to 10 wt .-% Cetylstearylsulfat

iii) 0.05 to 10% by weight of glyceryl stearate

are included.

7. Preparations or use according to one of the preceding claims, characterized in that in the cosmetic or dermatological preparations i) 0.25 to 5 wt .-% Natriumstearoylglutamat

ii) 0.25 to 5 wt .-% Cetylstearylsulfat

iii) 0.25 to 5% by weight of glyceryl stearate

are included.

8. Preparations according to one of the preceding claims, which are O / W emulsions and are distinguished by the following features:

b) from 0.001% by weight to 10% by weight, preferably from 0.05% by weight to 5% by weight, particularly preferably from 0.1% to 2.0% by weight, of one or more water-soluble phosphates, especially orthophosphates,

c) up to 10% by weight, preferably from 0.05% by weight to 5% by weight, particularly preferably from 0.1 to 2.0% by weight, of 4-tert-butyl-4'- methoxydibenzoylmethane

i) 0 to 10% by weight, preferably 0.25 to 5% by weight, of sodium stearoylglutamate ii) 0 to 10% by weight, preferably 0.25 to 5% by weight, of cetylstearylsulfate

iii) 0 to 10% by weight, preferably 0.25 to 5% by weight, of glyceryl stearate,

in each case based on the total weight of the preparations.

9. Preparations according to one of the preceding claims, in which the ratio of UV-A to UV-B protection, determined according to the Colipa Guidlines Edition 2007a ("Method for the in vitro determination of UVA protection provided by sunscreen products"), min at least 1: 3, more preferably at least 2: 3.