DE102004045482A1 - Formulation, for cosmetic preparation, comprises 2-phenylbenzimidazol-5-sulfonic acid, phenylene-1,4-bis (2-benzimidazyl)-3,3', 5,5'-tetrasulfonic acid, base, viscosity improver and water - Google Patents

Abstract

Formulation (I) comprises: 0.05-30 wt.% of 2-phenylbenzimidazol-5-sulfonic acid and/or their salts; 0.05-20 wt.% of phenylene-1,4-bis (2-benzimidazyl)-3,3',5,5'-tetrasulfonic acid and/or their salts; 0.01-30 wt.% of at least a base; 0-20 wt.% of viscosity improver; water; and optionally further UV filters and preservatives. Independent claims are also included for: (1) the preparation of a cosmetic or dermatological preparation with light protection characteristics comprising mixing (I) with further contents materials; and (2) cosmetic or dermatological preparation comprising (I).

Description

The The present invention relates to preformulations for production cosmetic or dermatological formulations or the preformulations containing cosmetic or dermatological formulations, as well as Process for their preparation and stabilization, in particular the photostabilization of UV filters in cosmetic and dermatological Formulations.

It It is well known that the ultraviolet part of solar radiation a damaging Has an effect on the skin. While Rays with one wavelength less than 290 nm (so-called UVC range) from the ozone layer in the earth's atmosphere be absorbed, causing 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.

Also for the Rays in the range between about 320 nm and 400 nm (UVA range) It has been proven that they cause damage to the elastic and collagen fibers of the connective tissue cause what the skin prematurely age. Furthermore, these rays cause numerous phototoxic and photoallergic reactions. The damaging influence of UVB radiation can be amplified by the UVA radiation.

The UVA radiation can also cause skin damage by: the skin's own keratin or elastin is damaged. This will be elasticity and water storage capacity the skin is reduced, i. The skin becomes less supple and tends for wrinkling. The strikingly high incidence of skin cancer in areas of strong sunlight shows that apparently too damage the genetic information in the cells by sunlight, especially by UVA radiation caused.

The UV radiation can also lead to photochemical reactions, wherein then the photochemical reaction products in the skin metabolism intervention. Furthermore counts UV radiation to ionizing radiation. So there is a risk that ionic species are also formed on UV exposure, which then in turn oxidative in the biochemical processes are able to intervene.

The light protection filters used today in cosmetics and dermatology are therefore also subdivided into UVA or UVB filters. For protection against UVB radiation, numerous compounds are known, which are mostly derivatives of 3-Benzylidencamphers (eg Eusolex ^® 6300), 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and also of 2-phenylbenzimidazole. To protect against UVA radiation often dibenzoylmethane derivatives are used, such as 4- (tert-butyl) -4'-methoxy-dibenzoylmethane (Eusolex ^® 9020) or 4-Isopropyldibenzoylmethan (Eusolex ^® 8020), which, however, in UV irradiation are not unlimitedly stable.

This certain instability to UV radiation is the main disadvantage of these substances. Under the influence of UV light, the 4- (tert-butyl) -4'-methoxydibenzoylmethane - representative of all absorbing in the UV range dibenzoylmethane derivatives - reduced in its UVA absorption performance. The substance is subject to keto-enol tautomerism. The diketo form absorbs in the UVA range while the enol form absorbs in the UVC range. Under the influence of solar radiation or solar simulators, this balance is shifted to the enol form, which leads to a lower absorption performance of the UV filter in the UVA range. Furthermore, it is known that it may come under irradiation in addition to the displacement of the keto-enol equilibrium also to UV-induced decomposition or photodegradation of Eusolex ^® 9020th

There was therefore an urgent need to find substances which stabilize the equilibrium with respect to the diketoform and / or prevent the photodegradation of the dibenzoylmethane derivatives. It is known that octocrylenes (see WO 91/11989, L'Oréal) or flavonoids ( DE 197 55 504 Beiersdorf AG) have been described as substances which can counteract the photolytic decomposition of dibenzoylmethane derivatives.

European Patent Application EP-A-669 323 describes phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid or salts thereof as novel water-soluble UV-A filters. The use in sunscreen preparations, in particular cosmetic sunscreen preparations is recommended. The combination with other conventional UV filters, such as 2-phenylbenzimidazole-5-sulfonic acid or salts thereof is described here. In the preparation of the specified in Examples 15 and 16 Formulations are each used separate pre-solutions of the two water-soluble UV filters.

Out German patent application DE-A-102 30 061 and DE-A-102 30 060 are O / W Emulsions containing a PEG ester or - ether as emulsifier and at least a 2-phenylbenzimidazole-5-sulfonic acid or their salts and at least one phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid or their salts contain. The UV filters should be 0.05-15 Wt .-% be included.

Out German Patent Application DE-A-102 29 526 are aqueous cosmetic Preparations containing at least 50% by weight of water and none Emulsions are described. The preparations contain 0.05-15 % By weight of 2-phenylbenzimidazole-5-sulfonic acid or salts thereof and 0.05 to 15 wt .-% of phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid or salts thereof and, if desired one or more humectants. It should be the UV filters in relation to 5: 1 to 1: 5, particularly preferably in the ratio of about 2 parts of 2-phenylbenzimidazole-5-sulfonic acid to 1 Part phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid used become.

task The present invention was now ready to pre-formulations available provide a simple preparation of sunscreen with preferably long-lasting UV protection over one possible enable broad spectral range.

It was surprised found that formulations containing 0.05-30 wt .-% of 2-phenylbenzimidazole-5-sulfonic acid or their salts and 0.05 to 20 wt .-% of phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid or their salts and at least one 0.01 to 30 wt .-% base, 0 to 20% by weight of viscosity enhancer, water and optionally contain other UV filters and preservatives, these Solve a task.

object The present invention therefore formulations are 0.05-30 % By weight of 2-phenylbenzimidazole-5-sulfonic acid or its salts and 0.05 to 20 wt .-% of phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid or salts thereof and at least one 0.01 to 30 wt .-% base, 0 to 20 wt .-% viscosity enhancer, water and optionally contain other UV filters and preservatives.

In a preferred variant of the present invention is the inventive formulation here from the ingredients mentioned.

One Another object of the present invention is the use a formulation according to the invention for the preparation of a cosmetic or dermatological preparation with light protection properties.

The cosmetic or dermatological preparation with photoprotective properties can exist in different forms. So they can z. B. a solution, a anhydrous preparation, emulsion or microemulsion of the type Water-in-oil (W / O) or oil-in-water type (O / W), a multiple emulsion, for example of the water-in-oil-in-water type (W / O / W), a gel, a solid stick, an ointment or even an aerosol represent.

Prefers It is particularly important when it comes to the cosmetic or dermatological preparation to an aqueous preparation, in particular a gel, or an emulsion, in particular an oil-in-water emulsion (O / W emulsion) because, in the preparation of such preparations, the advantages of formulations according to the invention in a special way.

One Another object of the present invention is accordingly also a method of making a cosmetic or dermatological Preparation with light-protection properties, characterized that a formulation according to the invention is mixed with other ingredients. Especially preferred, while the formulation is emulsified in an oil and so an oil-in-water emulsion (O / W emulsion) produced.

emulsions containing the above-described formulation of the invention in or as the water phase are therefore another object of the present invention Invention. Particularly preferred are oil-in-water emulsion (O / W emulsion).

Emulsions of the invention are advantageous and contain z. As mentioned fats, oils, waxes and other fatty substances, as well as water and an emulsifier, as commonly used for such a type of preparation.

• – Mineralöle, Mineralwachse
• – Öle, wie Triglyceride der Caprin- oder der Caprylsäure, ferner natürliche Öle wie z. B. Rizinusöl;
• – Fette, Wachse und andere natürliche und synthetische Fettkörper, vorzugsweise Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z.B. mit Isopropanol, Propylenglykol oder Glycerin, oder Ester von Fett-Ikoholen mit Alkansäuren niedriger C-Zahl oder mit Fettsäuren;
• – Silikonöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus.

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

• - mineral oils, mineral waxes
• - Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;
• Fats, waxes and other natural and synthetic fatty substances, preferably esters of fatty acids with lower C-number alcohols, for example with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with lower C-number alkanoic acids or with fatty acids;
• - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of Emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms. Such ester oils can then chosen advantageous are from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, Isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, Isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexadecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate as well as synthetic, semi-synthetic and natural mixtures of such esters, z. B. jojoba oil.

Further can the oil phase chosen favorably are from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ether, the group of saturated or unsaturated, branched or unbranched alcohols, as well as 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, especially 12-18 C-atoms. The fatty acid triglycerides can for example, advantageously chosen are 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 more.

Also any mixtures of such oil and wax components are advantageous in the sense of the present Use invention. It may also be advantageous if Waxes, for example cetyl palmitate, as the sole lipid component the oil phase use.

Advantageously, the oil phase is selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C _12-15 alkyl benzoate, caprylic capric acid triglyceride, dicapryl ether.

Particularly advantageous are mixtures of C _12-15 -alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C _12-15 -alkyl benzoate and isotridecyl isononanoate and mixtures of C _12-15 -alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

From The hydrocarbons are paraffin oil, squalane and squalene advantageous to be used in the sense of the present invention.

Advantageous can also the oil phase furthermore have a content of cyclic or linear silicone oils or completely from such oils but it is preferred, except the silicone oil or the silicone oils An additional Content of other oil phase components to use.

Advantageous Cyclomethicone (Octamethylcyclotetrasiloxan) is used as a silicone oil to be used according to the invention. But also other silicone oils are advantageous for the purposes of the present invention to use for example, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

Especially also advantageous are mixtures of cyclomethicone and isotridecyl isononanoate, from cyclomethicone and 2-ethylhexyl isostearate.

If appropriate, the aqueous phase of the preparations according to the invention 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 analogous products, furthermore lower C number alcohols, e.g. As ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickeners, which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous 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.

Especially Mixture of the abovementioned solvents are used. For alcoholic solvents Water can be another ingredient.

Inventive emulsions are advantageous and contain z. As mentioned fats, oils, waxes and other fat bodies, as well as water and an emulsifier, as usually for one such type of formulation is used.

When Emulsifiers can For example, the known W / O and O / W emulsifiers can be used. It is advantageous, more common Coemulsifiers in the preferred O / W emulsions according to the invention to use.

According to the invention advantageous are selected as co-emulsifiers, for example, O / W emulsifiers, mainly from the group of substances with HLB values of 11-16, whole particularly advantageous with HLB values of 14.5-15.5, provided the O / W emulsifiers saturated Radicals R and R 'have. Do the O / W emulsifiers have unsaturated Radicals R and / or R ', or are Isoalkylderivate, so the preferred HLB value such emulsifiers are also lower or higher.

It is advantageous, the fatty alcohol ethoxylates from the group of ethoxylated Stearyl alcohol, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols) to choose. Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), Polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (Steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), Polyethylene glycol (17) stearyl ether (steareth-17), polyethylene glycol (18) stearyl ether (Steareth-18), polyethylene glycol (19) stearyl ether (steareth-19), Polyethylene glycol (20) stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether (isosteareth-12), Polyethylene glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (14) isostearyl ether (Isosteareth-14), polyethylene glycol (15) isostearyl ether (isosteareth-15), Polyethylene glycol (16) isostearyl ether (isosteareth-16), polyethylene glycol (17) isostearyl ether (Isosteareth-17), polyethylene glycol (18) isostearyl ether (isosteareth-18), Polyethylene glycol (19) isostearyl ether (isosteareth-19), polyethylene glycol (20) isostearyl ether (Isosteareth-20), polyethylene glycol (13) cetyl ether (ceteth-13), polyethylene glycol (14) cetyl ether (Ceteth-14), polyethylene glycol (15) cetyl ether (Ceteth-15), polyethylene glycol (16) cetyl ether (Ceteth-16), polyethylene glycol (17) cetyl ether (Ceteth-17), polyethylene glycol (18) cetyl ether (ceteth-18), polyethylene glycol (19) cetyl ether (Ceteth-19), polyethylene glycol (20) cetyl ether (Ceteth-20), polyethylene glycol (13) isocetyl ether (Isoceteth-13), polyethylene glycol (14) isocetyl ether (isoceteth-14), Polyethylene glycol (15) isocetyl ether (Isoceteth-15), polyethylene glycol (16) isocetyl ether (Isoceteth-16), polyethylene glycol (17) isocetyl ether (isoceteth-17), Polyethylene glycol (18) isocetyl ether (isoceteth-18), polyethylene glycol (19) isocetyl ether (Isoceteth-19), polyethylene glycol (20) isocetyl ether (Isoceteth-20), Polyethylene glycol (12) oleyl ether (Oleth-12), polyethylene glycol (13) oleyl ether (Oleth-13), polyethylene glycol (14) oleyl ether (Oleth-14), polyethylene glycol (15) oleyl ether (Oleth-15), polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12) isolauryl ether (Isolaureth-12), polyethylene glycol (13) cetyl stearyl ether (ceteareth-13), Polyethylene glycol (14) cetyl stearyl ether (ceteareth-14), polyethylene glycol (15) cetyl stearyl ether (Ceteareth-15), polyethylene glycol (16) cetyl stearyl ether (ceteareth-16), Polyethylene glycol (17) cetyl stearyl ether (ceteareth-17), polyethylene glycol (18) cetyl stearyl ether (Ceteareth-18), polyethylene glycol (19) cetyl stearyl ether (Ceteareth-19), Polyethylene glycol (20) cetylstearyl ether (Ceteareth-20).

It is also advantageous to choose the fatty acid ethoxylates of the following group:
Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate; Polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, polyethylene glycol (14) isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate, polyethylene glycol ( 20) isostearate, polyethylene glycol (21) isostearate, polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, polyethylene glycol (12) oleate, polyethylene glycol (13) oleate, polyethylene glycol (14) oleate, polyethylene glycol (15) oleate, polyethylene glycol (16) oleate, polyethylene glycol (17) oleate, polyethylene glycol (18) oleate, polyethylene glycol (19) ols at, polyethylene glycol (20) oleate,

When ethoxylated alkyl ether carboxylic acid or its salt may advantageously be the sodium laureth-11-carboxylate be used. As alkyl ether sulfate sodium Laureth1-4sulfat be used advantageously. As an ethoxylated cholesterol derivative Advantageously, polyethylene glycol (30) cholesteryl ether may be used become. Also polyethylene glycol (25) soybean oil has been proven. When ethoxylated triglycerides can Advantageously, the polyethylene glycol (60) Evening Primrose Glycerides be used (Evening Primrose = evening primrose).

Farther is advantageous, the Polyethylenglycolglycerinfettsäureester from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, Polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, Polyethylene glycol (6) glyceryl caprate / cprinate, polyethylene glycol (20) glyceryl oleate, Polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoat to choose.

It is also cheap the sorbitan esters from the group polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, Polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, Polyethylene glycol (20) to choose sorbitan monooleate.

As optional, but according to the invention optionally advantageous W / O emulsifiers can be used:
Fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of one chain length from 8 to 24, in particular 12-18 C-atoms, monoglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, diglycerol ether of saturated and / or unsaturated, branched and or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms and sorbitan esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acid n a chain length of 8 to 24, in particular 12-18 C-atoms.

Especially advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, Glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, Diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, Propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, Sorbitan monolaurate, sorbitan monocaprylate, sorbitan monoisooleate, Sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, Behenyl alcohol, isobehenyl alcohol, selachyl alcohol, chimyl alcohol, Polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, Glyceryl monocaprinate, glyceryl monocaprylate.

The 2-phenylbenzimidazole-5-sulfonic acid or salts thereof are commercially available UV filters and available, for example, under the trade name Eusolex® 232 from Merck. Phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid or the salts thereof are described in the European patent application EP-A-669 323 and under the name ^® Neoheliopan AP from the Company Symrise available. According to the invention, the phenylbenzimidazole-5-sulfonic acid is preferably present in amounts of 5 to 25, preferably 10 to 20 wt .-%, and the phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5.5 Tetrasulfonic acid in amounts of 2 to 15, preferably 5 to 15 wt .-%, each based on the total weight of the formulation contained in this. It is further preferred if the 2-phenylbenzimidazole-5-sulfonic acid and the phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid in the formulation in proportions of 1: 1 to 2: 1, preferably about 3: 2.

All known bases can be used as the base, it being particularly preferred with regard to the preferred use in cosmetic sunscreens, if bases were used, the use of which is harmless in topical preparations. Are organic bases used, so preferably less volatile bases are used, such as low molecular weight alkanolamines such. As ethanolamine, diethanolamine, N-ethylethanolamine, N-methyl-diethanolamine, triethanolamine, diethylamino-ethanol, 2-amino-2-methyl-n-propanol, dimethylaminopropanol, 2-amino-2-methyl-propanediol, tri-isopropanolamine. As further less volatile bases there may be mentioned, for example, ethylenediamine, hexamethylenediamine, morpholine, piperidine, piperazine, cyclohexylamine, tributylamine, dodecylamine, N, N-dimethyl-dodecylamine, stearylamine, oleylamine, benzylamine, dibenzylamine, N-ethylbenzylamine, dimethylstearylamine, N-methylmorpholine, N-methylpiperazine, 4-methylcyclohexylamine, N-hydroxyethylmorpholine. The salts of quaternary ammonium hydroxides, such as. B. trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide or tetraethylammonium hydroxide may be used, as well as guanidine and its derivatives, in particular its alkylation products. However, it is also possible, for example, as a salt former low molecular weight alkylamines, such as. As methylamine, ethylamine or triethylamine use. The hydroxides with cations, such as, for example, alkali metal ions, in particular sodium, potassium or ammonium, alkaline earth ions, in particular the magnesium or calcium ion, and 2 to 4-valent cations, such as, for example, the zinc, aluminum or zirconium salt, are also known into consideration bases to be used according to the invention. According to the invention, NaOH, trihydroxymethylaminomethane (TRIS) or triethanolamine (TEA) are preferably used as the base, with the use of TRIS being particularly preferred. An advantage of the use of TRIS is, in particular, that corresponding formulations appear particularly bright and thus allow the use of larger amounts of yellowing-prone drugs that are well known to those skilled in the art.

there the base is preferably in an amount of 1 to 20 wt .-%, in particular preferably 5 to 15 wt .-% in each case based on the total weight of the formulation.

When Viscosity enhancers can all, those skilled in the art, suitable for increasing the viscosity in aqueous systems Connections are used. In particular, it is advantageous the use of such viscosity enhancers that at the later Use of the preparations in the topical application at the same time act as a humectant. In particular, the invention may be preferred therefore glycerol and 1,2-propanediol be used. Preferably, the one or more viscosity enhancers are included in an amount of 1 to 17 wt .-%, particularly preferably 7 to 15 wt .-% each based on the total weight of the formulation included in this.

• – Die Stabilität der Formulierungen wird verbessert, insbesondere wird das Ausfallen der UV-Filter, insbesondere der 2-Phenylbenzimidazol-5-sulfonsäure, und somit die Bildung von Impfkristallen verhindert. Als besonders vorteilhaft hat sich dabei erwiesen, dass die Bildung von Impfkristallen auch bei pH-Werten kleiner 7,0, insbesondere auch bei pH-Werten kleiner 6,8 bzw. kleiner 6,5 und sogar bei pH-Werten von oder kleiner von 6,0 noch unterbleibt.
• – Die Vorformulierung gewährleistet ein vereinfachtes Einarbeiten der Filter in Zubereitungen, bei guter oder verbesserter Filterleistung der UV-Filter. Insbesondere die aufwändige Neutralisation der Filterlösungen sowie mehrere Mischschritte können so entfallen.
• – Durch Einsatz der Vorformulierung kann die hygroskopische Phenylen-1,4-bis(2-benzimidazyl)-3,3',5,5'-tetrasulfonsäure wesentlich leichter dosiert werden. Der in der Produktion unpraktische Schritt des Abwiegens eines hygroskopischen Feststoffes kann entfallen.
• – Zudem löst sich insbesondere die 2-Phenylbenzimidazol-5-sulfonsäure nur sehr langsam in Wasser, so dass durch die Vorformulierung ein die Herstellung einer kosmetischen Zubereitung wesentlich schneller und damit kostengünstiger erfolgen kann.
• – Aufgrund der bei Einsatz von TRIS verbesserten Farbstabilität können auch zu Gelbfärbung neigende Wirkstoffe, wie z.B. Flavonoide oder Flavonoid-Derivate, ohne Beeinträchtigung des visuellen Erscheinungsbildes der Zubereitungen eingesetzt werden.
• – Die Photostabilität der wasserlöslichen UV-Filter ermöglicht auch eine Stabilisierung lichtempfindlicher Bestandteile, wie z. B. UV-A-Filter, Parfumbestandteile oder Farbstoffe in den Formulierungen.

The use of formulations according to the invention in or for the preparation of cosmetic or dermatological sunscreens leads to the following advantages:

• - The stability of the formulations is improved, in particular the precipitation of the UV filters, in particular the 2-phenylbenzimidazole-5-sulfonic acid, and thus the formation of seed crystals is prevented. It has proven to be particularly advantageous that the formation of seed crystals is also at pH values below 7.0, in particular also at pH values below 6.8 or below 6.5 and even at pH values of or below 6 , 0 still omitted.
• - The pre-formulation ensures a simplified incorporation of the filter in preparations, with good or improved filter performance of the UV filter. In particular, the complex neutralization of the filter solutions and several mixing steps can be omitted.
• By using the preformulation, the hygroscopic phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid can be metered much easier. The impractical in production step of weighing a hygroscopic solid can be omitted.
• - In addition, in particular, the 2-phenylbenzimidazole-5-sulfonic acid dissolves very slowly in water, so that the preparation of a cosmetic preparation can be done much faster and thus cheaper by pre-formulation.
• Due to the improved color stability when TRIS is used, agents which tend to yellowing, such as, for example, flavonoids or flavonoid derivatives, can also be used without impairing the visual appearance of the preparations.
• - The photostability of the water-soluble UV filter also allows stabilization of photosensitive components such. As UV-A filter, perfume ingredients or dyes in the formulations.

worin R¹, R², R³ und R⁴, die identisch oder voneinander verschieden sind, Wasserstoff, eine geradkettige oder verzweigte C_1-8-Alkylgruppe oder eine geradkettige oder verzweigte C_1-8-Alkoxygruppe bedeuten. Gemäß der vorliegenden Erfindung können selbstverständlich ein Dibenzoylmethanderivat oder mehrere Dibenzoylmethanderivate verwendet werden. Von den Dibenzoylmethanderivaten, auf die sich die vorliegende Erfindung spezieller bezieht, können insbesondere:

• – 2-Methyldibenzoylmethan,
• – 4-Methyldibenzoylmethan,
• – 4-Isopropyldigenzoylmethan,
• – 4-tert.-Butyldibenzoylmethan,
• – 2,4-Dimethyldibenzoylmethan,
• – 2,5-Dimethyldibenzoylmethan,
• – 4,4'-Diisopropyldibenzoylmethan,
• – 4,4'-Methoxy-tert.-butyldibenzoylmethan,
• – 2-Methyl-5-isopropyl-4'-methoxydibenzoylmethan,
• – 2-Methyl-5-tert.-butyl-4'-methoxydibenzoylmethan,
• – 2,4-Dimethyl-4'-methoxydibenzoylmethan

und

• – 2,6-Dimethyl-4-tert.-butyl-4'-methoxydibenzoylmethan genannt werden, wobei diese Aufzählung nicht einschränkend ist.

UVA filters whose chemical formula contains the structural feature of dibenzoylmethane are particularly well stabilized. in particular among the dibenzoylmethane derivatives of the following formula:

wherein R ¹ , R ² , R ³ and R ⁴ , which are identical or different, denote hydrogen, a straight-chain or branched C _1-8 -alkyl group or a straight-chain or branched C _1-8 -alkoxy group. Of course, according to the present invention, a dibenzoylmethane derivative or a plurality of dibenzoylmethane derivatives may be used. Of the Dibenzoylmethanderivaten, to which the present invention More specifically, in particular:

• 2-methyldibenzoylmethane,
• 4-methyldibenzoylmethane,
• 4-isopropyldigenoylmethane,
• 4-tert-butyldibenzoylmethane,
• 2,4-dimethyldibenzoylmethane,
• 2,5-dimethyldibenzoylmethane,
• 4,4'-diisopropyldibenzoylmethane,
• 4,4'-methoxy-tert-butyldibenzoylmethane,
• 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,
• 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane,
• 2,4-dimethyl-4'-methoxydibenzoylmethane

and

• - 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane be mentioned, this list is not limiting.

Of the above dibenzoylmethane derivatives according to the invention, in particular the 4,4'-methoxy-t-butyldibenzoylmethane, and in particular the left under the trade name Eusolex ^® 9020 from Merck commercially 4,4'-methoxy-t-butyldibenzoylmethane, said Filter corresponds to the following structural formula:

One further preferred according to the invention Dibenzoylmethane derivative is 4-isopropyldibenzoylmethane.

By following the teaching of the invention, sunscreen formulations are obtainable which have a higher stability, in particular stability against decomposition or reduction of the absorption power under the influence of light, in particular UV light, than would have been expected from the prior art. In particular, the stability of 4- (tert-butyl) -4'-methoxydibenzoylmethane (Eusolex ^® 9020) is remarkably increased.

The total amount of dibenzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (Eusolex ^® 9020) in the formulations is advantageously from 0.1 to 10.0 wt .-%, particularly preferably 0.5 to 6.0 wt .-%, each based on the total weight of the preparation.

Cosmetic and dermatological preparations to be prepared according to the invention also advantageously, but not necessarily, contain inorganic pigments based on metal oxides and / or other sparingly soluble or insoluble metal compounds, in particular the oxides of titanium (TiO ₂ ), zinc (ZnO), iron (eg Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (eg MnO), aluminum (Al ₂ O ₃ ), cerium (eg Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides. Particularly preferred are pigments based on TiO ₂ , and in particular micronized TiO ₂ .

Such formulations, which additionally contain a content of micronized TiO ₂ , are also the subject of this invention.

The content of micronized TiO ₂ is preferably 0.01 to 30 wt .-%, particularly preferably 0.1 to 10 wt .-%, each based on the total weight of the preparations.

The invention also relates to the use of formulations according to the invention for the photostabilization of UV filters in cosmetic or dermatological preparations and to a method for increasing the photostability of UV filters, in particular of substances having the structural feature of the di benzoylmethane, in cosmetic or dermatological preparations.

According to the invention can cosmetic and / or dermatological sunscreen formulations as usual and cosmetic and / or dermatological light protection, furthermore for the treatment, care and cleansing of the skin and / or hair and as a make-up product in decorative cosmetics.

Especially such are preferred according to the invention cosmetic and dermatological preparations prepared in the form of a sunscreen. These can be advantageous additionally at least one further UVA filter and / or at least one other UVB filter and / or at least one inorganic pigment, preferred hydrophobic inorganic micropigments.

• – 3-(4'-Methylbenzyliden)-dl-kampfer (z.B. Eusolex^® 6300),
• – 3-Benzylidenkampfer (z.B. Mexoryl^® SD),
• – Polymere von N-{(2 und 4)-[(2-oxoborn-3-yliden)methyl]benzyl}acrylamid (z.B. Mexoryl^® SW),
• – N,N,N-Trimethyl-4-(2-oxoborn-3-ylidenmethyl)anilinium methylsulfat (z.B. Mexoryl^® SK) oder
• – α-(2-Oxoborn-3-yliden)toluol-4-sulfonsäure (z.B. Mexoryl^® SL),

Benzophenone wie

• – 2-Hydroxy-4-methoxybenzophenon (z.B. Eusolex^® 4360) oder
• – 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und ihr Natriumsalz (z.B. Uvinul^® MS-40),

Methoxyzimtsäureester wie

• – Methoxyzimtsäureoctylester (z.B. Eusolex^® 2292),
• – 4-Methoxyzimtsäureisopentylester, z.B. als Gemisch der Isomere (z.B. Neo Heliopan^® E 1000),

Salicylatderivate wie

• – 2-Ethylhexylsalicylat (z.B. Eusolex^® OS),
• – 4-Isopropylbenzylsalicylat (z.B. Megasol^®) oder
• – 3,3,5-Trimethylcyclohexylsalicylat (z.B. Eusolex^® HMS),
• – 4-Aminobenzoesäure und Derivate wie
• – 4-Aminobenzoesäure,
• – 4-(Dimethylamino)benzoesäure-2-ethylhexylester (z.B. Eusolex^® 6007),
• – ethoxylierter 4-Aminobenzoesäureethylester (z.B. Uvinul^® P25),

und weitere Substanzen wie

• – 2-Cyano-3,3-diphenylacrylsäure-2-ethylhexylester (z.B. Eusolex^® OCR),
• – 3,3'-(1,4-Phenylendimethylen)-bis-(7,7-dimethyl-2-oxobicyclo-[2.2.1]hept-1-ylmethansulfonsäure sowie ihre Salze (z.B. Mexoryl^® SX) und
• – 2,4,6-Trianilino-(p-carbo-2'-ethylhexyl-1'-oxi)-1,3,5-triazin ( z.B. Uvinul^® T 150).

In principle, all UV filters come into question. Particularly preferred are those UV filters whose physiological harmlessness has already been demonstrated. Both for UVA and UVB filters, there are many well-known and proven substances from the literature, eg
Benzylidene camphor derivatives such as

• - 3- (4'-methylbenzylidene) -dl-camphor (for example Eusolex ^® 6300),
• - 3-benzylidenecamphor (for example Mexoryl ^® SD),
• - polymers of N - {(2 and 4) - [(2-oxoborn-3-ylidene) methyl] benzyl} acrylamide (for example Mexoryl ^® SW),
• - N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methylsulfate (for example Mexoryl SK ^®) or
• - α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid (for example Mexoryl SL ^®),

Benzophenones like

• - 2-hydroxy-4-methoxybenzophenone (for example Eusolex ^® 4360) or
• - 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (for example Uvinul ^® MS-40),

Methoxycinnamate as

• - methoxycinnamate (eg Eusolex ^® 2292)
• - 4-methoxycinnamate, for example as a mixture of isomers (for example Neo Heliopan E 1000 ^®)

Salicylate derivatives such as

• - 2-ethylhexyl salicylate (for example Eusolex ^® OS),
• - 4-isopropylbenzyl (for example Megasol ^®) or
• - 3,3,5-trimethylcyclohexyl (eg Eusolex ^® HMS)
• 4-aminobenzoic acid and derivatives such as
• 4-aminobenzoic acid,
• - 4- (dimethylamino) benzoic acid 2-ethylhexyl ester (for example Eusolex ^® 6007),
• - ethoxylated ethyl 4-aminobenzoate (for example Uvinul ^® P25),

and other substances like

• - 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl (for example Eusolex ^® OCR),
• - 3,3 '- (1,4-phenylenedimethylene) bis (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-ylmethanesulfonic acid and salts thereof (for example Mexoryl SX ^®) and
• - 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxi) -1,3,5-triazine (for example Uvinul ^® T 150).

The listed in the list Links are to be considered as examples only. Of course you can too other UV filters are used.

• – 2-(2N-Benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)propyl)phenol (z.B. Silatrizole^®),
• – 4,4'-[(6-[4-((1,1-Dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazin-2,4-diyl)diimino]bis(benzoesäure-2-ethylhexylester) (z.B. Uvasorb^® HEB),
• – α-(Trimethylsilyl)-ω-[trimethylsilyl)oxy]poly[oxy(dimethyl [und ca. 6% methyl[2-[p-[2,2-bis(ethoxycarbonyl]vinyl]phenoxy]-1-methylenethyl] und ca. 1,5 % methyl[3-[p-[2,2-bis(ethoxycarbonyl)vinyl)phenoxy)-propenyl) und 0,1 bis 0,4% (methylhydrogen]silylen]] (n ≈ 60) (CAS-Nr. 207 574-74-1)
• – 2,2'-Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) (CAS-Nr. 103 597-45-1)
• – 2,4-bis-{[4-(2-Ethyl-hexyloxy)-2-hydroxyl]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (CAS-Nr. 103 597-45-, 187 393-00-6).

Other suitable organic UV filters are, for example

• 2- (2N-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyloxy) disiloxanyl) propyl) phenol (eg silatrizole ^® ),
• 4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylamino] -1,3,5-triazine-2,4-diyl) diimino] bis (benzoic acid 2-ethylhexyl ester) (for example Uvasorb HEB ^®),
• Α- (trimethylsilyl) -ω- [trimethylsilyl) oxy] poly [oxy (dimethyl) and about 6% methyl [2- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy] -1-methylenethyl] and about 1.5% methyl [3- [p- [2,2-bis (ethoxycarbonyl) vinyl] phenoxy) propenyl) and 0.1 to 0.4% (methylhydrogen] silylene]] (n≈60) (CAS No. 207 574-74-1)
• 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) (CAS No. 103 597-45-1)
• 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxyl] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (CAS No. 103 597- 45-, 187 393-00-6).

These Organic UV filters are usually in an amount of 0.5 to 20% by weight, preferably 1-15%, in cosmetic formulations incorporated.

preferred Compounds with UV-filtering properties are 3- (4'-methylbenzylidene) dl-camphor, 2-hydroxy-4-methoxybenzophenone, methoxycinnamate, 3,3,5-trimethylcyclohexylsalicylate, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl and their potassium, sodium and triethanolamine salts.

• – Die Hydrophilie der Kapselwand kann unabhängig von der Löslichkeit des UV-Filters eingestellt werden. So können beispielsweise auch hydrophobe UV-Filter in rein wässrige Formulierungen eingearbeitet werden. Zudem wird der häufig als unangenehm empfundene ölige Eindruck beim Auftragen der hydrophobe UV-Filter enthaltenden Zubereitung unterbunden.
• – Bestimmte UV-Filter, insbesondere Dibenzoylmethanderivate, zeigen in kosmetischen Formulierungen nur eine verminderte Photostabilität. Durch Verkapselung dieser Filter oder von Verbindungen, die die Photostabilität dieser Filter beeinträchtigen, wie beispielsweise der oben genannten Zimtsäurederivate, kann die Photostabilität der gesamten Formulierung erhöht werden.
• – In der Literatur wird immer wieder die Hautpenetration durch organische UV-Filter und das damit verbundene Reizpotential beim direkten Auftragen auf die menschliche Haut diskutiert. Durch die hier vorgeschlagene Verkapselung der entsprechenden Substanzen wird dieser Effekt unterbunden.
• – Allgemein können durch Verkapselung einzelner UV-Filter oder anderer Inhaltstoffe Formulierungsprobleme, die durch Wechselwirkung einzelner Formulierungsbestandteile untereinander entstehen, wie Kristallisationsvorgänge, Ausfällungen und Agglomeratbildung vermieden werden, da die Wechselwirkung unterbunden wird.

All these additional UV filters can also be used in encapsulated form. In particular, it is advantageous to use organic UV filters in encapsulated form. In detail, there are the following advantages:

• - The hydrophilicity of the capsule wall can be adjusted independently of the solubility of the UV filter. For example, hydrophobic UV filters can also be incorporated into purely aqueous formulations. In addition, the often perceived as unpleasant oily impression when applying the hydrophobic UV filter containing preparation is suppressed.
• - Certain UV filters, in particular Dibenzoylmethanderivate show in cosmetic formulations only a reduced photostability. By encapsulating these filters or compounds that affect the photostability of these filters, such as the cinnamic acid derivatives mentioned above, the photostability of the entire formulation can be increased.
• In the literature, the skin penetration through organic UV filters and the associated irritation potential during direct application to the human skin is discussed again and again. The encapsulation of the corresponding substances proposed here prevents this effect.
• - In general, encapsulation of individual UV filters or other ingredients formulation problems caused by interaction of individual formulation components with each other, such as crystallization processes, precipitation and agglomeration can be avoided because the interaction is suppressed.

Therefore is it preferred according to the invention if one or more of the above UV filters are encapsulated in Form present. It is advantageous if the capsules so small are they with the naked eye can not be observed. To achieve the o.g. Effects it is still required that the capsules are sufficiently stable and the encapsulated drug (UV filter) not or only to a small extent to the environment.

Suitable capsules may have walls of inorganic or organic polymers. For example, in US 6,242,099 B1 describe the preparation of suitable capsules with walls of chitin, chitin derivatives or polyhydroxylated polyamines. Capsules which are particularly preferred for use in accordance with the invention have walls which can be obtained by a SolGel process, as described in applications WO 00/09652, WO 00/72806 and WO 00/71084. Again, capsules whose walls are made up of silica gel (silica, undefined silicon oxide hydroxide) are preferred. The production of such capsules is known to the skilled worker, for example, from the cited patent applications, whose contents are expressly also part of the subject of the present application.

there the capsules are preferred in formulations according to the invention contained in such quantities, which ensure that the encapsulated UV filters are present in the above-mentioned amounts in the formulation.

According to the invention can UV protection filters described here individually or of course also used in combination, which is preferred, in sunscreens become. You can with UV-B / A chromophores, e.g. combined with all globally approved and known filters are used to improve the protective performance (SPF boost) synergistic effects. They are preferably both in combination with inorganic as well as with organic UV-A and UV-B filters or their Mixtures used.

wobei
R¹ ausgewählt ist aus -C(O)CH₃, -CO₂R³, -C(O)NH₂ and -C(O)N(R⁴)₂;
X is O or NH;
R² steht für einen linearen oder verzweigten C_1-30-Alkylrest;
R³ steht für einen linearen oder verzweigten C_1-20-Alkylrest, alle R⁴ unabhängig voneinander stehen für H oder lineare oder verzweigte C_1-8-Alkylreste
R⁵ steht für H, einen linearen oder verzweigten C_1-8-Alkylrest oder einen linearen oder verzweigten -O-C_1-8-Alkylrest und
R⁶ steht für einen C_1-8-Alkylrest,
wobei es sich bei dem Photostabilisator insbesondere bevorzugt um 2-(4-Hydroxy-3,5-dimethoxy-benzyliden)-malonsäure-bis-(2-ethyl-hexyl)ester handelt, enthalten. Entsprechende Photostabilisatoren, ihre Herstellung und Verwendung sind in der Internationalen Patentanmeldung WO 03/007906 beschrieben, deren Offenbarung ausdrücklich auch zum Gegenstand der vorliegenden Anmeldung gehört.In addition to the compounds described here, the preparations according to the invention may also contain at least one photostabilizer, preferably corresponding to the formula I.

in which
R ^{1 is} selected from -C (O) CH ₃ , -CO ₂ R ³ , -C (O) NH ₂ and -C (O) N (R ⁴ ) ₂ ;
X is O or NH;
R ² is a linear or branched C _1-30 alkyl radical;
R ³ is a linear or branched C _1-20 -alkyl radical, all R ⁴ independently of one another are H or linear or branched C _1-8 -alkyl radicals
R ⁵ is H, a linear or branched C _1-8 -alkyl radical or a linear or branched -OC _1-8 -alkyl radical and
R ⁶ is a C _1-8 -alkyl radical,
wherein the photostabilizer is more preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester. Corresponding photostabilizers, their preparation and use are described in International Patent Application WO 03/007906, the disclosure of which is expressly also included in the subject of the present application.

Further Is it possible and advantageous to the preparations according to the invention with antioxidants combine. Such a combination then shows both protective effect as an antioxidant as well as against burns caused by UV radiation. Thus one can also have a protective Action against oxidative stress or against the action of radicals achieve.

There are many known and proven substances known from the literature which can be used as antioxidants, eg amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocaninic acid) and their derivatives, peptides such as D, L- Carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (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) as well as sulfoximine compounds (eg buthionine sulfoximines, homocysteine nsulfoximin, buthionine sulfones, penta, hexa, heptathionine sulfoximine) in very low compatible dosages (eg pmol to μmol / kg), furthermore (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, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives ( eg vitamin E acetate), vitamin A and derivatives (eg vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylidenglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, Uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and its derivatives ( eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide).

Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention. Known and commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (for example Oxynex ^® AP), natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® K LIQUID), tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® L LIQUID), DL-α-tocopherol, L - (+) -Ascorbylpalmitat, citric acid and lecithin (eg Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) - ascorbyl palmitate and citric acid (eg Oxynex ^® 2004).

The preparations according to the invention may contain vitamins as further ingredients. Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin B ₁ ), riboflavin (vitamin B ₂ ), nicotinamide , Vitamin C (ascorbic acid), Vitamin D, Ergocalciferol (Vitamin D ₂ ), Vitamin E, DL-α-Tocopherol, Tocopherol E-acetate, Tocopherol hydrogen succinate, Vitamin K ₁ , Esculin (Vitamin P active ingredient), Thiamin (Vitamin B ₁ ), nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B ₆ ), pantothenic acid, biotin, folic acid and cobalamin (vitamin B ₁₂ ) in the cosmetic preparations according to the invention, particularly preferably vitamin A palmitate, vitamin C. and its derivatives, DL-α-tocopherol, tocopherol-E-acetate, nicotinic acid, pantothenic acid and biotin.

The preparations according to the invention can about that addition, more usual skin-friendly or skin-care active ingredients. This can be done in principle all agents known to those skilled in the art, in particular flavone derivatives, Chromone derivatives, compatible solutes and other agents.

It be preferred if the inventive preparation at least one Contains repellent, wherein the repellent is preferably selected from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butyl-amino) -propionic acid Ethyl ester, dimethyl phthalate, butopyronoxyl, 2,3,4,5-bis (2-butylene) -tetrahydro-2-furaldehyde, N, N-caprylic acid diethylamide, N, N-diethylbenzamide, o-chloro-N, N-dimethylbenzamide, dimethyl carbate, di-n-propyl isocine chomeronate, 2-ethylhexane-1,3-diol, N-octylbicyclohepetane dicarboximide, piperonyl butoxide, 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) piperidine or mixtures thereof, more preferably selected from N, N-diethyl-3-methylbenzamide, Ethyl 3- (acetyl-butyl-amino) -propionate 1- (2-methylpropyloxycarbonyl) -2- (hydroxyethyl) -piperidine or mixtures thereof.

at the preparations according to the invention, containing the repellents, it is preferably to Insect repellents. Insect repellents are in the form of solutions, Gels, pens, rollers, pump sprays and aerosol sprays offered, being solutions and sprays form the bulk of commercially available products. Base for this Both product forms are usually alcoholic or aqueous-alcoholic solutions with the addition of fatty substances and slight perfuming.

When Flavone derivatives according to the invention are flavonoids and coumaranones Understood. Flavonoids according to the invention are the glycosides of flavanones, Flavones, 3-hydroxyflavones (= flavonoids), aurones, isoflavones and redoids [Römpp Chemie Lexikon, Vol. 9, 1993]. In the context of the present invention however, the aglycones, i. the sugar-free Ingredients, and understood the derivatives of flavonoids and aglycones. Furthermore, in the context of the present invention, the term Flavonoid also understood anthocyanidin (cyanidin). As part of the Coumaranones of the present invention are also derivatives thereof Understood.

preferred Flavonoids are derived from flavanones, flavones, 3-hydroxyflavones, Aurones and isoflavones, in particular flavanones, flavones, 3-hydroxyflavones and aurones, from.

The Flavonoids are preferably selected from the following compounds: 4,6,3 ', 4'-tetrahydroxyaurone, Quercetin, rutin, isoquercetin, eriodictyol, taxifolin, luteolin, Trishydroxyethyl quercetin (Troxequercetin), Trishydroxyethylrutin (Troxerutin), trishydroxyethylisoquercetin (troxeisoquercetin), Trishydroxyethylluteolin (troxeluteolin), α-glycosylrutin, tiliroside as well their sulphates and phosphates. Among the flavonoids are as active ingredients according to the invention in particular rutin, tiliroside, α-glycosylrutin and troxerutin preferred.

Under the phenols with antioxidant effect are partially as natural substances occurring polyphenols for Applications in the pharmaceutical, cosmetic or nutritional field especially interesting. For example, the mainly as Plant dyes commonly known flavonoids or bioflavonoids antioxidant potential. With effects of the substitution pattern Mono- and dihydoxyflavones are the subject of K. Lemanska, N. Szymusiak, B. Tyrakowska, R. Zielinski, I.M.C.M. Rietjens; Current Topics in Biophysics 2000, 24 (2), 101-108. It is observed there that dihydroxyflavones with an OH group adjacent to the keto function or OH groups in 3'4 ' or 6,7- or 7,8-position have antioxidant properties, while other mono- and dihydroxyflavones partially no antioxidants Have properties.

Frequently becomes Quercetin (cyanidanol, cyanidolone 1522, meletin, sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) mentioned as a particularly effective antioxidant (e.g., C. A. Rice-Evans, N.J. Miller, G. Paganga, Trends in Plant Science 1997, 2 (4), 152-159). K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, A.E.M.F. Soffers, I.M.C.M. Rietjens; Free Radical Biology & Medicine 2001, 31 (7), 869-881 the pH dependence the antioxidant effect of Hydoxyflavones. Over the entire pH range Quercetin shows the highest activity of the examined structures.

wobei R¹ bis R¹⁰ gleich oder verschieden sein können und ausgewählt sind aus

• – H
• – OR¹¹
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkylgruppen und/oder C₃- bis C₁₂-Cycloalkenylgruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können,
• – wobei alle OR¹¹ unabhängig voneinander stehen für
• – OH
• geradkettige oder verzweigte C₁- bis C₂₀-Alkyloxygruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenyloxygruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkoxygruppen, wobei die Hydroxygruppe(n) an ein primäre oder sekundäre Kohlenstoffatome der Kette gebunden sein können und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkyloxygruppen und/oder C₃- bis C₁₂-Cycloalkenyloxygruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können und/oder,
• – Mono- und/oder Oligoglycosylreste, mit der Maßgabe, dass mindestens 4 Reste aus R¹ bis R⁷ stehen für OH und dass im Molekül mindestens 2 Paare benachbarter Gruppen -OH vorliegen,
• – oder R², R⁵ und R⁶ für OH und die Reste R¹, R³, R⁴ und R^7-10 für H stehen,

wie sie in der Deutschen Patentanmeldung DE-A-10244282 beschrieben sind.Suitable antioxidants are furthermore compounds of the formula II

wherein R ¹ to R ^{10 may be the} same or different and are selected from

• - H
• - OR ¹¹
• Straight-chain or branched C ₁ - to C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ -C ₂₀ -alkenyl groups,
• Straight-chain or branched C ₁ to C ₂₀ hydroxyalkyl groups, where the hydroxy group may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen, and / or
• C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3,
• Where all OR ^{11 are} independent of each other
• - OH
• straight-chain or branched C ₁ -C ₂₀ -alkyloxy groups,
• Straight-chain or branched C ₃ - to C ₂₀ -alkenyloxy groups,
• Straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkoxy groups, where the hydroxy group (s) may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen, and / or
• C ₃ - to C ₁₀ -cycloalkyloxy groups and / or C ₃ - to C ₁₂ -cycloalkenyloxy groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3 and / or
• Mono- and / or oligoglycosyl radicals, with the proviso that at least 4 radicals from R ¹ to R ⁷ are OH and that at least 2 pairs of adjacent groups -OH are present in the molecule,
• Or R ² , R ⁵ and R ^{6 are} OH and the radicals R ¹ , R ³ , R ⁴ and R ^{7-10 are} H,

as described in the German patent application DE-A-10244282.

Under the coumaranones is 4,6,3 ', 4'-tetrahydroxybenzylcoumaranone-3 prefers.

wobei
R¹ und R² gleich oder verschieden sein können und ausgewählt sind aus

• – H, -C(=O)-R⁷, -C(=O)-OR⁷,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen, geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkylgruppen und/oder C₃- bis C₁₂-Cycloalkenylgruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können,

R³ steht für H oder geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen,
R⁴ steht für H oder OR⁸,
R⁵ und R⁶ gleich oder verschieden sein können und ausgewählt sind aus

• – -H, -OH,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Alkylgruppen,
• – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenylgruppen,
• – geradkettigen oder verzweigten C₁- bis C₂₀-Nydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann und

R⁷ steht für H, geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen, eine Polyhydroxy-Verbindung, wie vorzugsweise einen Ascorbinsäurerest oder glycosidische Reste und
R⁸ steht für H oder geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen, wobei mindestens 2 der Substituenten R¹, R², R⁴-R⁶ verschieden von H sind oder mindestens ein Substituent aus R¹ und R² für -C(=O)-R⁷ oder -C(=O)-OR⁷ steht.Chromone derivatives are preferably understood as meaning certain chromene-2-one derivatives which are useful as active ingredients for the preventive treatment of human skin and hair against aging processes and harmful environmental influences. At the same time they show a low irritation potential for the skin, positively influence the water binding in the skin, maintain or increase the elasticity of the skin and thus promote a smoothing of the skin. These compounds preferably correspond to the formula III

in which
R ¹ and R ^{2 may be the} same or different and are selected from

• - H, -C (= O) -R ⁷ , -C (= O) -OR ⁷ ,
• Straight-chain or branched C ₁ - to C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ - to C ₂₀ -alkenyl groups, straight-chain or branched C ₁ - to C ₂₀ hydroxyalkyl groups, wherein the hydroxy group may be bonded to a primary or secondary carbon atom of the chain and further the alkyl chain may also be interrupted by oxygen, and / or
• C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3,

R ³ is H or straight-chain or branched C ₁ - to C ₂₀ -alkyl groups,
R ⁴ is H or OR ⁸ ,
R ⁵ and R ^{6 may be the} same or different and are selected from

• - -H, -OH,
• Straight-chain or branched C ₁ - to C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ -C ₂₀ -alkenyl groups,
• Straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkyl groups, it being possible for the hydroxy group to be bonded to a primary or secondary carbon atom of the chain, and furthermore for the alkyl chain also to be interrupted by oxygen, and

R ⁷ is H, straight or branched C ₁ to C ₂₀ alkyl groups, a polyhydroxy compound, such as preferably an ascorbic acid residue or glycosidic residues and
R ⁸ is H or straight-chain or branched C ₁ - to C ₂₀ -alkyl groups, where at least 2 of the substituents R ¹ , R ² , R ⁴ -R ^{6 are} different from H or at least one substituent from R ¹ and R ² for - C (= O) -R ⁷ or -C (= O) -OR ⁷ .

Of the Proportion of one or more compounds selected from Flavonoids, Cromon derivatives and Coumaranonen in the inventive preparation is preferably from 0.001 to 5% by weight, more preferably from 0.01 up to 2% by weight, based on the total preparation.

Particularly preferred active ingredients are, for example, also so-called compatible solutes. These are substances that are involved in the osmoregulation of plants or microorganisms and can be isolated from these organisms. Under the generic term compatible solutes also the described in the German patent application DE-A-10133202 osmolytes are taken. Suitable osmolytes are, for example, the polyols, methylamine compounds and amino acids, and in each case their precursors. Within the meaning of the German patent application DE-A-10133202, osmolytes are understood as meaning, in particular, substances from the group of polyols, such as, for example, myo-inositol, mannitol or sorbitol and / or one or more of the osmolytically active substances mentioned below:
Taurine, choline, betaine, phosphorylcholine, glycerophosphorylcholine, glutamine, glycine, α-alanine, glutamate, aspartate, proline, and taurine. Precursors of these substances are, for example, glucose, glucose polymers, phosphatidylcholine, phosphatidylinositol, inorganic phosphates, proteins, peptides and polyamic acids. Precursors are z. B. Compounds that are converted to osmolytes by metabolic steps.

Preferably are according to the invention as compatible Solute substances chosen from the group consisting of pyrimidinecarboxylic acids (such as ectoine and hydroxyectoine), Proline, betaine, glutamine, cyclic diphosphoglycerate, N. acetylornithine, Trimethylamine N-oxide Di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), β-mannosylglycerate (Firoin), β-Mannosylglyceramide (Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP) or an optical Isomer, derivative, e.g. an acid, a salt or ester of these compounds or combinations thereof used.

there are among the pyrimidinecarboxylic acids in particular ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and Hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5-hydroxy-2-methyl-4-pyrimidinecarboxylic acid and to name their derivatives. These compounds stabilize enzymes and other biomolecules in aqueous solutions and organic solvents. Furthermore, they stabilize especially enzymes against denaturing Conditions such as salts, extreme pH, surfactants, urea, guanidinium chloride and other connections.

Ectoine and ectoine derivatives such as hydroxyectoine can be used to advantage in medicines. In particular, hydroxyectoine can be used for the manufacture of a medicament for the treatment of skin diseases. Other fields of use of hydroxyectoine and other ectoin derivatives are typically in areas in which, for example, trehalose is used as an additive. Thus, ectoine derivatives, such as hydroxyectoine, can be used as a protective substance in dried yeast and bacterial cells. Also pharmazeu Products such as non-glycosylated, pharmaceutically active peptides and proteins such as t-PA can be protected with ectoine or its derivatives.

Under The cosmetic applications in particular is the use of Ectoin and ectoin derivatives for the care of aged, dry or call irritated skin. Thus, in the European patent application EP-A-0 671 161 specifically describes that ectoine and hydroxyectoine in cosmetic preparations such as powders, soaps, surfactant-containing Cleansing products, lipsticks, blushes, make-up, skin care creams and sunscreen preparations be used.

worin R¹ ein Rest H oder C1-8-Alkyl, R² ein Rest H oder C1-4-Alkyl und R³, R⁴, R⁵ sowie R⁶ jeweils unabhängig voneinander ein Rest aus der Gruppe H, OH, NH₂ und C1-4-Alkyl sind. Bevorzugt werden Pyrimidincarbonsäuren eingesetzt, bei denen R² eine Methyl- oder eine Ethylgruppe ist und R¹ bzw. R⁵ und R⁶ H sind. Insbesondere bevorzugt werden die Pyrimidincarbonsäuren Ectoin ((S)-1,4,5,6-Tetrahydro-2-methyl-4-pyrimidin-carbonsäure) und Hydroxyectoin ((S, S)-1,4,5,6-Tetrahydro-5-hydroxy-2-methyl-4-pyrimidin-carbonsäure) eingesetzt. Dabei enthalten die erfindungsgemäßen Zubereitungen derartige Pyrimidincarbonsäuren vorzugsweise in Mengen bis zu 15 Gew.-%.In this case, a pyrimidinecarboxylic acid according to formula IV below is preferably used,

wherein R ^{1 is} a radical H or C 1-8 -alkyl, R ^{2 is} a radical H or C 1-4 -alkyl and R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently a radical from the group H, OH, NH ₂ and C1-4 alkyl. Preference is given to using pyrimidinecarboxylic acids in which R ^{2 is} a methyl or an ethyl group and R ¹ or R ⁵ and R ^{6 are} H. Particular preference is given to the pyrimidinecarboxylic acids ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydrocarboxylic acid). 5-hydroxy-2-methyl-4-pyrimidine-carboxylic acid). The preparations according to the invention contain such pyrimidinecarboxylic acids, preferably in amounts of up to 15% by weight.

In particular according to the invention it is preferred if the compatible solutes are selected Di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), β-mannosylglycerate (firoin), β-mannosylglyceramide (Firoin-A) or / and dimannosyl-di-inositol phosphate (DMIP), ectoine, Hydroxyectoine or mixtures thereof.

Under The aryloxime also preferably used is preferably 2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO, LPO or F5 is used. Its suitability for use in cosmetic Means is for example from the German Offenlegungsschrift DE-A-41 16 123 known. Preparations containing 2-hydroxy-5-methyllaurophenone oxime, are therefore used to treat skin conditions that cause inflammation go along, suitable. It is known that such preparations, e.g. for the treatment of psoriasis, different types of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory Diseases of the skin and the appendages can be used can. Preparations according to the invention, which is an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime contain, show surprising anti-inflammatory suitability. The preparations contain preferably 0.01 to 10% by weight of the aryloxime, in particular preferred is when the preparation contains 0.05 to 5 wt% aryloxime.

In another also preferred embodiment of the present invention Invention contains the preparation according to the invention at least one self-tanner.

As advantageous self-tanner may be used, inter alia:

5-Hydroxy-1,4-naphtochinon (Juglon) sowie das in den Henna-Blättern vorkommende 2-Hydroxy-1,4-naphtochinon (Lawson).Further, 5-hydroxy-1,4-naphthoquinone (juglone), which is extracted from the shells of fresh walnuts

5-hydroxy-1,4-naphthoquinone (juglone) and the 2-hydroxy-1,4-naphthoquinone (Lawson) found in henna leaves.

2-Hydroxy-1,4-naphtochinon (Lawson)

2-Hydroxy-1,4-naphthoquinone (Lawson)

1,3-Dihydroxyaceton (DHA) Very particular preference is given to 1,3-dihydroxyacetone (DHA), a trivalent sugar occurring in the human body and its derivatives.

1,3-dihydroxyacetone (DHA)

Furthermore, the preparations according to the invention may also contain dyes and colored pigments. The dyes and pigments can be selected from the corresponding positive list of the Cosmetics Regulation or EC List of cosmetic colorants. In most cases, they are identical to the food-approved dyes. Examples of advantageous color pigments are titanium dioxide, mica, iron oxides (eg Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the following list. The Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971.

It may also be favorable to choose as the dye one or more substances from the following group:
2,4-dihydroxyazobenzene, 1- (2'-chloro-4'-nitro-1'phenylazo) -2-hydroxynaphthalene, ceric red, 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, Calcium salt of 2-hydroxy-1,2'-azonaphthalene-1'-sulfonic acid, calcium and barium salts of 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2- Sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt of 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, aluminum salt of 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid, 1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -2- ( 4-sulfophenyl) -5-hydroxy-pyrazolone-3-carboxylic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluorescein, 3 ', 4', 5 ', 6'-tetrachloro-2,4,5,7-tetrabromo-fluorescein and its aluminum salt, aluminum salt of 2,4,5,7-tetraiodofluorescein, aluminum salt of quinophthalone di sulfonic acid, aluminum salt of indigo-disulfonic acid, red and black iron oxide (CIN: 77 491 (red) and 77 499 (black)), iron oxide hydrate (CIN: 77492), manganese ammonium diphosphate and titanium dioxide.

Further advantageous are oil-soluble natural dyes, such as B. Paprika extract, β-carotene or cochineal.

• 1. Natürliche Perlglanzpigmente; wie z. B. 1. "Fischsilber" (Guanin/Hypoxanthin-Mischkristalle aus Fischschuppen) und 2. "Perlmutt" (vermahlene Muschelschalen)
• 2. Monokristalline Perlglanzpigmente wie z. B. Bismuthoxychlorid (BiOCl)
• 3. Schicht-Substrat Pigmente: z. B. Glimmer/Metalloxid

Gelcrémes containing pearlescent pigments are also advantageous for the purposes of the present invention. Particularly preferred are the types of pearlescent pigments listed below:

• 1. Natural pearlescent pigments; such as B. 1. "fish-silver" (guanine / hypoxanthine mixed crystals from fish scales) and 2. "mother-of-pearl" (ground mussel shells)
• 2. Monocrystalline pearlescent pigments such. B. bismuth oxychloride (BiOCl)
• 3rd layer substrate pigments: z. Mica / metal oxide

Base for pearlescent pigments are for example powdered Pigments or castor oil dispersions of Bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or Titanium dioxide on mica. Particularly advantageous is z. B. the listed under the CIN 77163 luster pigment.

Also advantageous, for example, are the following pearlescent pigment types based on mica / metal oxide:

Especially preferred are z. As the Merck under the trade name Pearlescent pigments available from Timiron, Colorona or Dichrona.

Of course, the list of pearlescent pigments mentioned should not be limiting. Pearlescent pigments which are advantageous in the context of the present invention are obtainable in numerous ways known per se. For example, other substrates except mica can be coated with other metal oxides such. As silica and the like. Advantageous z. B. with TiO ₂ and Fe ₂ O ₃ coated SiO ₂ particles ("Ronaspheren"), which are sold by Merck and are particularly suitable for the optical reduction of fine wrinkles.

It may also be advantageous to completely dispense with a substrate such as mica. Particularly preferred are pearlescent pigments, which are prepared using SiO ₂ : Such pigments, which may also have additional gonichromatic effects are, for. B. under the trade name Sicopearl Fantastico available from BASF.

Farther can be advantageous Pigments of Engelhard / Mearl based on calcium sodium Borosilicate, which are coated with titanium dioxide, can be used. These are available under the name Reflecks. They point through their Particle size of 40-80 μm in addition to the color of a glittering effect.

Especially Also advantageous are also effect pigments which are sold under the trade name Metasomes Standard / Glitter in different colors (yellow, red, green, blue) are available from Flora Tech. The glitter particles lie here in mixtures with various auxiliaries and dyes (such as the dyes with the Color Index (Cl) numbers 19140, 77007, 77289, 77491).

The Dyes and pigments can both individually and in mixture and with each other be coated, with different coating thicknesses In general, different color effects are caused. The Total amount of the dyes and coloring pigments will be advantageous from the range of z. B. 0.1 wt.% To 30 wt.%, Preferably from 0.5 to 15 wt.%, In particular selected from 1.0 to 10 wt.%, Respectively based on the total weight of the preparations.

All Compounds or components used in the preparations can be are either known and commercially available acquirable or can be synthesized by known methods. The preparation may contain any customary carrier substances, Additives and optionally other active ingredients may be added.

preferable Excipients come from the group of preservatives, antioxidants, Stabilizers, solubilizers, Vitamins, colorants, Odor.

Solutions and Emulsions can the usual excipients like solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, Ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol, oils, in particular cottonseed, Peanut oil, Corn oil, Olive oil, castor oil and sesame oil, Glycerinfettsäureester, Polyethylene glycols and fatty acid esters of sorbitan or mixtures of these substances.

In a preferred embodiment contain the preparations according to the invention hydrophilic surfactants.

The hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.

auszeichnen, wobei R einen verzweigten oder unverzweigten Alkylrest mit 4 bis 24 Kohlenstoffatomen darstellt und wobei DP einen mittleren Glucosylierungsgrad von bis zu 2 bedeutet.The alkylglucosides in turn are advantageously selected from the group of alkylglucosides, which are represented by the structural formula

wherein R is a branched or unbranched alkyl radical having 4 to 24 carbon atoms and wherein DP means a mean degree of glucosylation of up to 2.

The value DP represents the degree of glucosidation of the alkylglucosides used in the invention and is defined as

In this case, p ₁ , p ₂ , p ₃ ... Or p _{i represent} the proportion of the single, double-threefold-fold glucosylated pro In accordance with the invention, products with degrees of glucosylation of 1-2, in particular advantageous from 1.1 to 1.5, very particularly advantageously from 1.2 to 1.4, in particular from 1.3, are chosen.

Of the Value DP carries account for the fact that alkylglucosides are manufactured in usually represent mixtures of mono- and oligoglucosides. According to the invention advantageous is a relatively high content of monoglucosides, typically in of the order of magnitude from 40-70 Wt .-%.

Particularly according to the invention Advantageously used alkyl glycosides are selected from the group octylglucopyranoside, nonylglucopyranoside, decyl glucopyranoside, Undecylglucopyranoside, dodecylglucopyranoside, tetradecylglucopyranoside and hexadecyl glucopyranoside.

It is likewise advantageous to employ natural or synthetic raw materials and assistants or mixtures which are distinguished by an effective content of the active ingredients used according to the invention, for example Plantaren ^® 1200 (Henkel KGaA), Oramix NS ^® 10 (Seppic).

auszeichnen, wobei R¹ einen verzweigten oder unverzweigten Alkylrest mit 1 bis 30 Kohlenstoffatomen bedeutet und M⁺ aus der Gruppe der Alkaliionen sowie der Gruppe der mit einer oder mehreren Alkyl- und/oder mit einer oder mehreren Hydroxyalkylresten substituierten Ammoniumionen gewählt wird bzw. dem halben Äquivalent eines Erdalkalions entspricht.In turn, the acyl lactylates are advantageously selected from the group of substances which are defined by the structural formula

in which R ^{1 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M ^{+ is selected} from the group of the alkali metal ions and the group of ammonium ions substituted by one or more alkyl and / or by one or more hydroxyalkyl radicals or half Equivalent to an alkaline earth metal equivalent.

For example, sodium is advantageous, for example the product Pathionic ^® ISL from the American Ingredients Company.

auszeichnen, wobei R² einen verzweigten oder unverzeigten Alkylrest mit 1 bis 30 Kohlenstoffatomen bedeutet.The betaines are advantageously selected from the group of substances which are defined by the structural formula

characterized in that R ^{2 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms.

Particularly advantageously, R ^{2 is} a branched or unbranched alkyl radical having 6 to 12 carbon atoms.

Capramidopropylbetaine, for example the product Tego ^® Betaine is advantageous, for example 810 from Th. Goldschmidt AG.

For example, sodium elected cocoamphoacetate invention beneficial as under the name Miranol ^® Ultra C32 from Miranol Chemical Corp. is available.

The preparations according to the invention are advantageously characterized in that the one or more hydrophilic surfactants in concentrations of 0.01-20 wt .-%, preferably 0.05-10 wt .-%, particularly preferably 0.1-5 wt .-%, each based on the total weight of the composition, is present or present.

To Application are the cosmetic and dermatological according to the invention Preparations in the for Cosmetics usual Applied to the skin and / or hair in sufficient quantity.

The Preparation may contain cosmetic adjuvants present in this Type of preparations usually can be used, e.g. Thickening agents, softening agents, Humectant, surface-active Agents, emulsifiers, preservatives, antifoaming agents, Perfumes, waxes, lanolin, propellants, dyes and / or pigments, which dye the agent itself or the skin, and others in cosmetics usually used ingredients.

you can as dispersing or solubilizing an oil, wax or other fats, a low monoalcohol or a lower polyol or mixtures use of it. To the particularly preferred monoalcohols or Count polyols Ethanol, i-propanol, propylene glycol, glycerol and sorbitol.

A preferred embodiment The invention is an emulsion which is used as a protective cream or milk is present and, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, Lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.

is a preparation prepared as an aerosol, is used in the Usually the usual Propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes.

The Cosmetic preparation can also protect the hair against photochemical damage used to change of shades, a discoloration or damage mechanical nature. In this case, it is suitable a formulation as a shampoo, lotion, gel or emulsion for rinsing, wherein the respective preparation before or after shampooing, before or after dyeing or decolorizing or before or after the permanent wave is applied. It can also a preparation as a lotion or gel for styling and treating, as a lotion or gel for brushing or laying a water wave, as a hair coat, permanent wave, dyeing or bleach for the hair chosen become. The preparation with photoprotective properties can be different, containing adjuvants used in this type of medium, such as active surface Agents, thickeners, polymers, emollients, preservatives, Foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils, waxes, Antifettmittel, dyes and / or pigments containing the agent itself or dye your hair or others for Hair care usually used ingredients.

The preparations according to the invention can In doing so, they are manufactured using techniques that are familiar to those skilled in the art well known. The substances of the invention can be directly without further preparatory measures in cosmetic preparations incorporated.

Advantageous can the preparations according to the invention, as above already described, contain additional UV filter substances, wherein the total amount of filter substances e.g. 0.1% by weight to 30% by weight, preferably 0.5 to 10 wt .-%, in particular 1 to 6 wt .-%, based on the total weight of the preparations.

Farther can the preparations according to the invention also as a pharmaceutical agent for the preventive treatment of inflammation and allergies of the skin as well as in certain cases Prevention of certain Cancers are used. The pharmaceutical agent according to the invention can be administered orally or topically.

The preparations according to the invention can be made with the help of techniques well suited to the skilled person are known. Even without further explanation it is assumed that a person skilled in the art will make the most of the above description can. The preferred embodiments are therefore merely descriptive, not by any means Way limiting disclosure to understand. The following examples intended the present invention; clarify without restricting it. All quantities, Shares and percentages are, unless otherwise stated, on the weight and the total amount or the total weight of the preparations based. The complete Disclosure of all applications and publications listed above and below are incorporated by reference into this application.

to Designations of compounds are the INCI names of the commercial ones Compounds indicated.

Preformulation 1 15% by weight Phenylbenzimidazole Sulfonic Acid (Eusolex ^® 232) 10% by weight Disodium Phenyl Dibenzimidazole Tetrasulfonate (Neo Neliopan ^® AP) 10.3% by weight tromethamine 12.0% by weight 1,2-Propanediole ad 100% by weight Water (aqua)

The Pre-formulation is obtained by mixing the individual components and stirring until the clear solution, to the full Neutralization of phenylbenzimidazole sulfonic acid and disodium Phenyl dibenzimidazole tetrasulfonates to ensure.

Storage stability of the preformulation:

rehearse Preformulation 1 are adjusted to pH = 7.1, or 6.8 and 6.0, respectively and 3 months at 5 ° C or Room temperature or 40 ° C stored. No crystals are formed. For comparison: A solution of Phenylbenzimidazole sulfonic acid forms at pH = 6.0 and 6.5, respectively Store at 5 ° C for 3 months Crystals off.

Preformulation 2 15% by weight Phenylbenzimidazole sulfonic acid (Eusolex® 232) 10% by weight Disodium Phenyl Dibenzimidazole Tetrasulfonate (Neo Heliopan AP ^®) 10.3% by weight tromethamine 12.0% by weight 1,2-Propanediole 2.0% by weight Propylene Glycol, Diazolidinyl Urea, Methylparaben, Propylparaben (Germaben ^® II) ad 100% by weight Water (aqua)

The Pre-formulation is obtained by mixing the individual components and stirring until the clear solution, to the full Neutralization of phenylbenzimidazole sulfonic acid and disodium Phenyl dibenzimidazole tetrasulfonates to ensure.

Sunscreen fluid (O / W emulsion) (in vitro SPF (Diffey method) 15.9 (± 2.7) phase A) 6.0% by weight Cetyl Palmitate, Glyceryl Stearate, Ceteareth-20, Ceteareth-12, Cetearyl Alcohol (Emulgade SE ^®) 1.5% by weight Cetearyl alcohol (Lanette ^® O) 4.0% by weight Decyl oleate (Cetiol ^® V) 8.0% by weight Ethylhexyl Stearate (Cetiol ^® 868) 3.0% by weight Butyrospermum Parkii (Shea Butter)

Phase B 22.0% by weight Preformulation 2 ad 100% by weight Water (aqua)

• Phase A and Phase B (the above preformulation 2) separately at 80 ° C heated; Phase B while stirring added to phase A, the mixture homogenized and stirred cold.
• pH (24 ° C) = 6.8

Claims (14)

Containing formulation - 0.05-30 Wt .-% 2-phenylbenzimidazole-5-sulfonic acid or salts thereof and - 0.05 to 20% by weight of phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid or their salts as well - 0,01 up to 30% by weight of at least one base, From 0 to 20% by weight of viscosity enhancer, - Water and - possibly. additional UV filters and preservatives. Formulation according to claim 1, characterized in that that the 2-phenylbenzimidazole-5-sulfonic acid in quantities from 5 to 25, preferably 10 to 20 wt .-%, and the phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid in amounts of 2 to 15, preferably 5 to 15 wt .-%, each based on the total weight the formulation are included. Formulation according to at least one of the preceding Claims, characterized in that the 2-phenylbenzimidazole-5-sulfonic acid and the phenylene-1,4-bis (2-benzimidazyl) -3,3 ', 5,5'-tetrasulfonic acid in the Formulation in proportions from 1: 1 to 2: 1, preferably from about 3: 2. Formulation according to at least one of the preceding Claims, characterized in that at least one base is selected from NaOH, trihydroxymethylaminomethane (TRIS) or triethanolamine (TEA), the base particularly preferably tris (hydroxymethyl) aminomethane (TRIS) and the base is preferably in an amount of 1 to 20 Wt .-%, particularly preferably 5 to 15 wt .-% in each case based on the Total weight of the formulation is included. Formulation according to at least one of the preceding Claims, characterized in that viscosity enhancers are used which simultaneously act as a humectant, with particular preference Glycerol and / or 1,2-propanediol are used and the or the viscosity enhancers preferably in an amount of 1 to 17 wt .-%, particularly preferably 7 to 15 wt .-% each based on the total weight of the formulation are included. Formulation according to at least one of the preceding Claims, characterized in that at least one further UV filter a is cosmetically or dermatologically harmless substance whose chemical Formula containing the structural feature of dibenzoylmethane, wherein the formulation preferably 0.1 to 10.0 wt .-%, more preferably From 0.5 to 6.0% by weight, in each case based on the total weight of the preparation, Dibenzoylmethane derivatives contains and which are the substances that are the structural feature of dibenzoylmethane have, preferably selected are from the group 4-Isopropyldibenzoylmethan and 4- (tert-butyl) -4'-methoxydibenzoylmethane. Use of a formulation after at least one the claims 1 to 6 for the preparation of a cosmetic or dermatological Preparation with light protection properties. Use according to claim 7, characterized that it is the cosmetic or dermatological preparation around a watery Preparation, in particular a gel, or an oil-in-water emulsion (O / W emulsion) is. Process for the preparation of a cosmetic or dermatological preparation with photoprotective properties, thereby in that a formulation according to at least one of claims 1 to 6 is mixed with other ingredients. Method according to claim 9, characterized in that that it is the cosmetic or dermatological preparation an oil-in-water emulsion (O / W emulsion) and the formulation according to at least one of claims 1 to 6 in an oil is emulsified. Cosmetic or dermatological preparation containing A formulation according to at least one of claims 1 to 6th Preparation according to claim 11, characterized in that that it is an aqueous Preparation, in particular a gel, or an emulsion, in particular an oil-in-water emulsion (O / W emulsion). Emulsion according to Claim 11 or 12, characterized that the water phase of a formulation after at least one the claims 1 to 6 is formed. Use of a formulation after at least one the claims 1 to 6 for photostabilization of UV filters, in particular dibenzoylmethane derivatives.