EP2144595A1

EP2144595A1 - Uv light-protective agent based on mixed inorganic-organic systems

Info

Publication number: EP2144595A1
Application number: EP08717790A
Authority: EP
Inventors: Stephan Lehmann; Richard Riggs; Valerie Andre
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2007-04-04
Filing date: 2008-03-13
Publication date: 2010-01-20
Also published as: CN101663020A; JP2010523513A; WO2008122481A1; US20100135939A1

Abstract

The present invention relates to light-protective preparations, particularly in the field of cosmetics, based on mixed inorganic-organic systems. The present invention relates particularly to light-protective preparations containing nanoparticles of at least one metal derivative, at least one light-protective compound chemically bound to said metal derivative nanoparticles, and at least one additional organic UV light-protective agent which is different from the light-protective compound which is bound to the metal derivative nanoparticles.

Description

UV light stabilizer based on inorganic-organic mixing systems

description

The present invention relates to photoprotective preparations, in particular in the field of cosmetics based on inorganic-organic mixing systems. In particular, the present invention relates to photoprotective preparations comprising nanoparticles of at least one metal derivative, at least one photoprotective compound chemically bonded to these metal derivative nanoparticles and at least one further organic UV photoprotective agent which is different from the photoprotective compound bound to the metal derivative nanoparticles.

Metal oxides find use for a variety of purposes, e.g. as a white pigment, as a catalyst, as a component of antibacterial skin protection creams and as an activator for rubber vulcanization. In cosmetic sunscreens there are finely divided zinc oxide or titanium dioxide as UV-absorbing pigments.

For the purposes of the present application, the term "nanoparticles" refers to particles having an average diameter of 2, preferably from 5 to 10000 nm, determined by means of electron microscopic methods.

WO 2007/017587 describes the cosmetic use of a composite material comprising a metal derivative and an organic UV light protection filter, wherein the UV light protection filter is chemically bonded to the metal derivative. Preferably, the chemical bond is a covalent bond. WHERE

2007/017586 describes a process for producing such composite materials.

It is an object of the present invention to provide compositions which are active in the protection of light and which have a property profile which is improved compared to the light-protection compositions known from the prior art.

This object has been achieved by compositions containing photoprotective compositions

Nanoparticles of at least one metal derivative

at least one structural unit chemically bound to the nanoparticles of at least one metal derivative selected from the group consisting of

Derivatives of triazine, derivatives of hydroxybenzophenone and derivatives of 4,4'-diarylbutadiene.

The object has been achieved in particular by compositions containing photoprotective compositions

Nanoparticles of at least one metal derivative at least one triazine derivative chemically bound to the nanoparticles of at least one metal derivative.

For example, the chemically bonded triazine derivatives are chemically bound to the metal derivative nanoparticles via at least one - COO or -SO 2 O function. The -COO- or -Sθ2θ-structural elements can be obtained for example from the free acid or its salt. This is described, for example, in sections [0015] to [0018] of WO 2007/017586, to which reference is hereby made in its entirety.

Suitable triazines contain, in addition to at least one or in a -COO- and / or -Sθ2θ group convertible group, for example, the following structural motif:

Thus, for example, the s-triazine derivatives described in the European patent application EP 570 838 A1 can be used, their chemical structure by the generic formula

is reproduced, wherein

R ^{13 * is} a branched or unbranched C ¹ -C 6 -alkyl radical, a

C 5 -C 12 -cycloalkyl radical, optionally substituted by one or more C 1 -C 4 -alkyl groups,

represents an oxygen atom or an NH group, R ^{14 *} a branched or unbranched Ci-Cis-alkyl radical, a

C 5 -C 12 -cycloalkyl radical, optionally substituted by one or more C 1 -C 4 -alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which

A ^{* is} a branched or unbranched Ci-Cis-alkyl radical, a

C 5 -C 12 -cycloalkyl or aryl radical, optionally substituted by one or more C 1 -C 4 -alkyl groups,

R ^{16 * represents} a hydrogen atom or a methyl group,

n ^{* represents} a number from 1 to 10,

R ^{15 * is} a branched or unbranched C 1 -C 6 -alkyl radical, a C 5 -C 12 -cycloalkyl radical, optionally substituted by one or more

C 1 -C 4 -alkyl groups, when X represents the NH group, and a branched or unbranched C 1 -C 6 -alkyl radical, a C 5 -C 12 -cycloalkyl radical, optionally substituted by one or more C 1 -C 4 -alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which

A ^{* is} a branched or unbranched Ci-Cis-alkyl radical, a

R ^{16 * represents} a hydrogen atom or a methyl group, n ^{* represents} a number from 1 to 10,

when X represents an oxygen atom.

The aforementioned triazines are converted by cleavage of at least one of the ester and / or amide bonds into a form capable of forming a chemical, preferably covalent bond to the metal derivative. The manner in which the triazines are to be converted into the corresponding derivatives is known to the person skilled in the art.

A preferred triazine derivative in the context of the present invention is furthermore an unsymmetrically substituted s-triazine whose chemical structure is represented by the formula

which is also referred to below as Dioctylbutylamidotriazon (INCI: Diethylhexylbutamidotriazone) and is available under the trade name UVASORB ^® HEB at 3V Sigma. By cleavage of at least one of the ester and / or amide bonds, this triazine is converted to a form which is then capable of forming a chemical, preferably covalent bond to the metal derivative nanoparticle. It is preferred to hydrolytically cleave at least one of the ester bonds and to allow binding to the metal derivative by the resulting free acid or salt.

Also advantageous in the context of the present invention is a symmetrically substituted s-triazine which comprises 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2 ethyl hexyl ester), synonym: 2,4,6-tris [anilino (p-carbo-2'-ethyl-1 '-hexyloxy)] - 1, 3,5-triazine (INCI: ethylhexyl triazone), which BASF Aktiengesellschaft under the Wa- renamed UVINUL ^® T 150 is sold. By cleavage of at least one of the ester bonds, this triazine is converted to a form which is then capable of forming a chemical, preferably covalent bond to the metal derivative.

The problem underlying this invention has been solved in particular also by cosmetic preparations containing

Nanoparticles of at least one metal derivative

at least one hydroxybenzophenone derivative chemically bound to the nanoparticles of at least one metal derivative.

A particularly advantageous hydroxybenzophenone for the purposes of the present invention is 2- (4 '- (diethylamino) -2'-hydroxybenzoyl) benzoate (Uvinul A Plus ^®) of the following formula: (n-hexyl)

For the attachment to the metal derivative nanoparticles, for example, the hexyl ester is converted into the -COOH or the salt form.

Nanoparticles of at least one metal derivative

at least one 4,4'-diarylbutadiene derivative chemically bound to the nanoparticles of at least one metal derivative.

The 4,4-diarylbutadiene derivatives are described in Tables 1, 2, 3 and 4 of EP-A 916 335, to which reference is hereby made. Particularly suitable are the 4,4-diarylbutadiene derivatives mentioned in Tables 1, 2 and 3. A particularly suitable 4,4'-diarylbutadiene compound is 1, 1 - [(2,2 ^{'-Dimethylpropoxy)} carbonyl], 3-butadiene, 4,4-diphenyl. 1

It is particularly preferred if the preparations contain, in addition to the nanoparticles of at least one metal derivative, the at least one organic UV light stabilizer which is chemically bound to the metal derivative nanoparticles, at least one further organic UV light stabilizer which is different from that of the Metal-derivative nanoparticles bound photoprotective compound. Such other suitable ultraviolet light stabilizers are mentioned in the following table, but are not limited thereto:

In a particularly preferred embodiment, the further organic UV light stabilizer is selected from the group consisting of octocrylene (2-ethylhexyl 2-cyano-3,3-diphenylacrylate, CAS No. 6197-30), ethylhexyl salicylate (CAS No. 118 -60-5), dimethicodiethylbenzalmalonate (polysilicone-15, CAS No. 207574-74-1), homosalates (CAS No. 1 18-56-9) and mixtures thereof. Octocrylene is available commercially for example as Uvinul ^® N 539 T. Ethylhexyl salicylate is commercially available for example as Eusolex ^® OS. Dimethicodiethylbenzalmalonat is commercially available for example as Parsol ^® SLX. Homo salads is commercially available for example as Eusolex ^® HMS.

Accordingly, the following combinations are particularly preferred:

TiO 2 nanoparticles plus - chemically bound derivative of dioctylbutylamidotriazone plus

octocrylene

TiO 2 nanoparticles plus chemically bonded derivatives of dioctylbutylamidotriazone plus - ethylhexyl salicylate

TiO 2 nanoparticles plus chemically bonded derivative of dioctylbutylamidotriazone plus dimethicodiethylbenzalmalonate

TiO 2 nanoparticles plus chemically bonded derivative of dioctylbutylamidotriazone plus

Homosalate

TiO 2 nanoparticles plus chemically bound derivative of 4,4 ', (4,3 - (1,3,5-triazine-2,4,6-triyltriimino) -tris-benzoic acid tris (2-ethylhexyl ester) plus octocrylene

TiO 2 nanoparticles plus chemically combined derivative of 4,4 ', (1, 3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) plus ethylhexyl salicylate

TiO 2 nanoparticles plus chemically bound derivative of 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) plus dimethicodiethylbenzalmalonate

TiO 2 nanoparticles plus chemically bound derivative of 4,4 ', 4 "- (1, 3,5-triazine-2,4,6-triyltriimino) -tris-benzoic acid tris (2-ethylhexyl ester) plus Homosalate

TiO 2 nanoparticles chemically bonded derivative of 2- (4 '- (diethylamino) -2'-hydroxybenzoyl) benzoic acid plus

octocrylene

ethylhexyl

dimethicodiethylbenzalmalonate

Homosalate

TiO 2 nanoparticles chemically bonded to 4,4'-diarylbutadiene derivative plus octocrylene

TiO 2 nanoparticles chemically bonded to 4,4'-diarylbutadiene derivative plus ethylhexyl salicylate

TiO 2 nanoparticles chemically bonded 4,4'-diarylbutadiene derivative plus

dimethicodiethylbenzalmalonate

TiO 2 nanoparticles chemically bonded to 4,4'-diarylbutadiene derivative plus homosalates

According to the invention, ZnO is also used as the metal derivative in addition to or instead of TΪO 2. The object underlying this invention was further solved by containing cosmetic preparations

Nanoparticles of at least one metal derivative, chemically bonded organic UV light stabilizer and - at least one further organic UV light stabilizer, which from the to the

Nanoparticles bound and different from Octylmethoxycinnamat.

WO 2007/017586 and WO 2007/017587 describe how an organic UV light stabilizer can be chemically bonded to nanoparticles of at least one metal derivative. The metal derivatives themselves are also suitable for absorbing UV radiation. Furthermore, the metal derivatives are able to form a chemical bond with organic UV photoprotective filters.

Preferred metal derivatives are derivatives of the metals titanium, cerium, zinc, zirconium, copper and mixtures thereof, more preferably derivatives of titanium, cerium, copper and mixtures thereof, most preferred are derivatives of titanium or zinc. Especially preferred are derivatives of titanium.

Preferred derivatives are the oxides of the respective metals as described in WO 2007/017587, section [0027], which is hereby incorporated by reference in its entirety. In a particularly preferred embodiment of the invention, the abovementioned photoprotective substances are chemically grafted onto the surface of titanium dioxide (TiO.sub.2).

Analogously to section [0045] of WO 2007/017587, to which reference is made in its entirety, all or some of the nanoparticles may be chemically bonded to the photoprotective substances and none or a part of the nanoparticles without such binding to the light-protective substances are present.

The photoprotective structural element of the known UV photoprotective filters is preferably bound to the metal derivative nanoparticles by a -COO- or -SO 2 -O- bond. The precursors suitable for this purpose are obtainable, for example, by reacting a metal alkoxide with the UV light protection filter carrying at least one -COOH or -SO 2 -OH functionality (modified metal alkoxides, for example described in WO 2007/017586, Sections [0059], [0062]). , The UV photoprotective filter carrying COOH or -SO 2 -OH functionality, in turn, is either commercially available on its own or else accessible, for example, by hydrolysis of the corresponding ester.

The metal derivative nanoparticles which are chemically bonded to the photoprotective substances are then obtainable, for example, via a so-called inorganic polymerisation (sol-gel process) of the suitable precursors described above. This process is described in detail in WO 2007/017586, Sections [0029] to [0054], to which reference is hereby fully made. As a general rule For example, S. Danielle, J. Mat. Chem. 13 (2003), 342-346 describes processes for preparing the nanoparticles starting from metal alkoxides.

The degree of functionalization, that is to say the amount of light-protective substance, based on the amount of metal derivative, can be adjusted, for example, by the ratio of metal alkoxide to modified metal alkoxide (ie metal alkoxide with photoprotective structural element bound thereto) subjected to the sol-gel polymerization.

The following table describes photoprotective compositions according to the invention which contain combinations of UV filters bound to metal-derivative nanoparticles and other UV filters not bound to metal-derivative nanoparticles and different from the UV-filters bound to the metal-derivative nanoparticles.

^* The UV light protection filter mentioned in the table is first converted into an acid by hydrolysis of at least one ester bond, via which the binding to the nanoparticles can then take place.

Instead of ÜO2 or ZnO, other metal oxides are also suitable.

According to a preferred embodiment of the present invention, the metal derivative, in particular titanium dioxide and / or zinc oxide, which contains at least partially photoprotective structural elements chemically bound, redispersible in a liquid medium and forms stable dispersions.

According to a preferred embodiment of the present invention, the modified nanoparticles are redispersible in polar organic solvents and form stable dispersions. This is particularly advantageous, as a uniform incorporation, for example, in areas outside the cosmetics as in plastics, paints or films is possible.

According to another preferred embodiment of the present invention, the modified nanoparticles are redispersible in water and form stable dispersions there. This is particularly advantageous since this opens up the possibility of using the modified nanoparticles, for example in cosmetic formulations. Also conceivable are mixtures of water and polar organic solvents.

According to a preferred embodiment of the present invention, the modified nanoparticles have a diameter of 10 to 200 nm. This is particularly advantageous since good redispersibility is ensured within this size distribution.

According to a further preferred embodiment of the present invention, the modified nanoparticles have a diameter of 10 to 100 nm. This size range is particularly advantageous since, after redispersion of such modified nanoparticles, the resulting dispersions are transparent and thus do not influence the coloring, for example when added to cosmetic formulations. In addition, this results in the possibility for use in transparent films.

If the modified nanoparticles, in particular titanium dioxide or zinc oxide, are to be used as UV absorbers, it is advisable to use particles with a diameter of more than 5 nm, since below this limit there is a shift of the absorption edge into the short-wave range (L. Brus, J. Phys., Chem. (1986), 90, 2555-2560).

The preparations according to the present invention may preferably additionally comprise one or more water phases in addition to one or more oil phases and, for example, in the form of W / O, O / W, Si / W, W / Si, W / O / W or O / W / O emulsions are present. Such formulations may also preferably be a microemulsion (eg a PIT emulsion), a solid state emulsion (ie an emulsion stabilized by solids, eg a Pickering emulsion), a sprayable emulsion or a hydrodispersion , Furthermore, for the purposes of the present invention, the preparations may also be virtually anhydrous (water content below 5% by weight, based on the total weight of the preparation). The preparations according to the invention are in every respect extremely satisfactory preparations, which are not limited to a limited choice of raw materials. Accordingly, they are suitable especially to serve as a basis for multi-purpose forms of preparation. The preparations according to the invention show very good sensory and cosmetic properties, such as, for example, the spreadability on the skin or the ability to absorb into the skin, and are also distinguished by a very good light-protection effectiveness coupled with outstanding skincare data.

The cosmetic or dermatological photoprotective preparations according to the invention may be composed as usual and serve for cosmetic or dermatological photoprotection, furthermore for the treatment, care and cleansing of the skin and / or the hair and as a make-up product in decorative cosmetics. In particular, the cosmetic photoprotective preparations can also be used as self-tanning preparations and then contain substances which promote self-tanning, in particular dihydroxyacetone (CAS No. 96-26-4).

According to a further embodiment of the invention, the photoprotective preparation of the care or protection of the skin is used in particular for sun protection or care in sunlight exposure and is in the form of an emulsion, a dispersion, a suspension, an aqueous surfactant preparation, a milk, a lotion , a cream, a balm, an ointment, a gel, a granule, a powder, a stick preparation, such as a lipstick, a foam, an aerosol or a spray. Such formulations are well suited for topical preparations. This is particularly advantageous because the UV-absorbing and soothing effect of, for example, zinc oxide can be used simultaneously by use in sunscreen agents. In addition, the modified nanoparticles are very well suited for use in sunscreens, since the particles can be produced in a size that makes them appear transparent to the human eye. This results in the application no unwanted white veil on the skin.

As a rule, the cosmetic agent is used for topical application on the skin. Topical preparations are to be understood as meaning those preparations which are suitable for applying the active ingredients to the skin in fine distribution and preferably in a form absorbable by the skin. For this purpose, e.g. aqueous and aqueous-alcoholic solutions, sprays, foams, foam aerosols, ointments, aqueous gels, emulsions of the O / W or W / O type, microemulsions or cosmetic stick preparations.

The UV protection performance of sunscreen or its underlying UV filter is usually determined in biological efficacy tests under standardized conditions. With "UV protection performance" is within the meaning of the present Invention means both the protection against UV-A radiation and UV-B radiation. For the purposes of the present invention, a measure of the UV protection performance is, for example, the sun protection factor (SPF or SPF) or also IPD values and the like. The sun protection factor (SPF, often also called SPF (sun protection factor)) gives the Prolongation of sun exposure, which is made possible by using the sunscreen. It is the quotient of erythema threshold with sunscreen and erythema threshold without sunscreen. To test the UV-A protection performance, the IPD method is usually used (IPD = immediate pigment darkening). Here, similar to the determination of the sun protection factor, a value is determined which indicates by how much longer the skin protected by the sunscreen can be irradiated with UV-A radiation until the same pigmentation occurs as with the unprotected skin. Another, Europe-wide established testing method is the Australian Standard AS / NZS 2604: 1997. The absorption of the preparation in the UV-A range is measured. To meet the standard, the preparation must absorb at least 90% of the UV-A radiation in the range of 320 to 360 nm.

According to a preferred embodiment of the invention, the photoprotective preparation contains a cosmetically acceptable carrier. Preferred as a carrier is water, an alcohol, a fat, oil or wax, a gas, a water-based liquid, a gel, an emulsion or a microemulsion, a dispersion or a mixture thereof. The mentioned carriers show good skin tolerance. Particularly advantageous for topical preparations are aqueous gels, emulsions or microemulsions. The cosmetic and dermatological preparations according to the invention may contain cosmetic auxiliaries, as are commonly used in such preparations, for. As preservatives, preservatives, bactericides, perfumes, substances to prevent foaming, dyes, pigments that have a coloring effect, thickeners, wetting and / or moisturizing substances, fillers that improve the feel of the skin, fats, oils, waxes or other common ingredients of a cosmetic or dermatological formulation, such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde donors (such as, for example, DMDM hydantoin, which, for example, under the trade name Glydant ™ (Lonza) is available), lodopropylbutylcar- bamate (for. Example, under the trade designations Glydant ^® -2000, Glycacil ^® -L, glycidyl CACIL ^® -S (Lonza) available and / or Dekaben ^® LMB (Jan Dekker)), parabens (ie, p-hydroxybenzoates such as methyl, ethyl, propyl and / or butylparaben), phenoxyethanol , Ethanol, benzoic acid and the like. Usually, the preservation system according to the invention also advantageously also preservation aids, such as ethylhexyloxyglycerol, glycine soy etc.

Particularly advantageous preparations are also obtained when antioxidants are used as additives or active ingredients. According to the invention, the preparations advantageously contain one or more antioxidants. As favorable, but nevertheless optional to be used antioxidants all suitable or customary for cosmetic and / or dermatological applications or conventional antioxidants can be used. Particularly advantageous for the purposes of the present invention, water-soluble antioxidants can be used, such as vitamins, eg. As ascorbic acid and its derivatives.

Further preferred antioxidants are vitamin E and its derivatives as well as vitamin A and its derivatives. The amount of the 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 the preparation. If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation. If vitamin A or vitamin A derivatives, or carotenes or derivatives thereof, are the 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 choose.

It is particularly advantageous if the cosmetic preparations according to the present invention contain cosmetic or dermatological active ingredients, where preferred active ingredients are antioxidants which can protect the skin against oxidative stress.

Further advantageous active ingredients in the context of the present invention are natural active ingredients and / or derivatives thereof, such as. Alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, taurine and / or D-alanine. Formulations according to the invention, which contain, for example, known anti-wrinkle active ingredients such as fumarglycosides (in particular U-glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for the prophylaxis and treatment of cosmetic or dermatological skin changes, as described, for example, in US Pat. Skin aging (such as dryness, roughness, dryness wrinkles, itching, decreased refatting (eg, after washing), visible vascular dilation (telangiectasia, cuperosis), slackness and wrinkle and wrinkle formation, localized hypersensitivity). , Hypo- and false pigmentation (eg, age spots), increased susceptibility to mechanical stress (eg, cracking), and the like). Furthermore, they are advantageously suitable against the appearance of dry or rough skin.

The aqueous phase of the preparations according to the invention may advantageously comprise customary cosmetic auxiliaries, for example alcohols, in particular those of low C number, preferably ethanol and / or isopropanol, diols or polyols of low C number and their ethers, preferably 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, polymers, foam stabilizers, electrolytes, dihydoxyacetone and, in particular, one or more thickening agents which can be advantageously selected from the group silicon dioxide, aluminum silicates , Polysaccharides or their derivatives, for. As hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of the so-called Carbopole ^® , for example carbopoles of the types 980, 981, 1382, 2984, 5984, each individually or in combination , As thickeners from the group of the polyacrylates also Luvigel EM suitable ^® (caprylic lic / Capric Triglyceride / Sodium Acrylates Copolymer) is. Also advantageous are copolymers of Cio-30-alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters. Advantageously, compounds which carry the INCI name "Acrylates / Cio-3oAlkyl 'Acrylate Crosspolymer". Particularly advantageous are those available under the trade names Pemulen ^® TR1 and Pemulen ^® TR2 (Noveon). Advantageously, compounds having the INCI name Ammoniumacryloyldimethyl - Taurate / Vinylpyrrolidoncopolymere wear.

According to the invention, the ammoniumacryloyldimethyltaurate / vinylpyrrolidone copolymer (s) has the empirical formula [CrH-ielNbSCuJn [CβHgNO] m. Preferred species for the purposes of the present invention are shown in Chemical Abs tracts under the Registry numbers (CAS no.) 58374-69-9, 13162-05-5 and 88-12-0, available (under the trade name Aristoflex ^® AVC Clariant). Copolymers / crosspolymers are advantageous further comprising Acryloyldimethyl Taurate such as Simugel® ^® EC (Seppic). Other thickeners which are advantageously used according to the invention are also water-soluble or dispersible anionic polyurethanes. Advantageous in the context of the present invention are z. As polyurethane-1 and / or polyurethane-4. Particularly advantageous polyurethanes in the sense of the present invention are available under the trade designation Avalure UR ^® types, such as Avalure UR 445 ^®, Avalure UR 450 ^® and the like. Also advantageous for the purposes of the present invention is also under the trade name Luviset ^® Pur (BASF) available polyurethane. Nonionic surfactants, zwitterionic surfactants, ampholytic surfactants or anionic emulsifiers can be used as emulsifiers. The emulsifiers may be present in the preparation according to the invention in amounts of from 0.1 to 10, preferably from 1 to 5,% by weight, based on the preparation.

As a nonionic surfactant, for example, a surfactant of at least one of the following groups may be used:

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group;

C 12/18 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;

Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids of 6 to 22 carbon atoms and their ethylene oxide imidazole products;

Alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;

Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

Polyol and especially polyglycerol esters, e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds of several of these classes of substances;

Addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

Partial esters based on linear, branched, unsaturated or saturated Cβ / 22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside ) as well as polyglucosides (eg cellulose);

Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

Lanolin alcohol; Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE PS 1165574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and

polyalkylene glycols;

Betaine.

Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxy or sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethylimidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethyl-hydroxyethyl-carboxymethylglycinate. Particularly preferred is the known under the CTFA name Cocamidopropylbetaine fatty acid amide derivative.

Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a Cs.is-alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SOsH group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamido-propylglycines, N-alkyltaurines, N alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group.

Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12/18 acylsarcosine. In addition to the ampholytic, quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred. Furthermore, as anionic emulsifiers, it is possible to use alkyl ether sulfates, monoglyceride sulfates, fatty acid sulfates, sulfosuccinates and / or ether carboxylic acids.

Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C 6 -C 22 -fatty acids with linear C6-C22 fatty alcohols, esters of branched C6-C13 carboxylic acids with linear Cβ-C22 fatty alcohols, esters of linear C6-C22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyvalent ones Alcohols (such as propylene glycol, dimerdiol or trimer triol) and / or Guerbet alcohols, triglycerides based on Cβ-do fatty acids, liquid mono- / di-, triglyceride mixtures based on Cβ-C-is fatty acids, esters of C6-C22 Fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C 2 -C 12 -dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexyl Xane, linear C6-C22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C6-C22-alcohols (for example Finsolv ^® TN) Dialkyl ethers, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons into consideration. Also suitable as oil bodies are silicone compounds, for example dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and also amino, fatty acid, alcohol, polyether, epoxy, fluorine, alkyl and / or glycoside-modified silicone compounds which may be both liquid and resinous at room temperature. The oil bodies may be present in the compositions according to the invention in amounts of from 1 to 90, preferably from 5 to 80, and in particular from 10 to 50,% by weight, based on the preparation.

In particular, reference should be made at this point in full to the disclosure of WO 03/039507, p.21, Z.25 to p. 24, Z.13.

According to a particularly preferred embodiment, the preparation according to the invention contains further UV light protection filters in the form of soluble compounds or other pigments.

In individual cases, it may be desirable to add other UV filter substances to the cosmetic agent or sunscreen in addition to the existing photoprotective compounds. This can e.g. be necessary if a special emphasis should be placed on filter performance. One or more further UV light protection filters can be added to the preparation according to the invention.

In particular, reference should be made at this point to the disclosure of WO 03/039507, page 25, Z.24 to page 29, Z.12, where further suitable UV filter substances are mentioned.

The UV light protection filters shown in the following table are suitable as further UV light protection filters for the preparations according to the invention.

As oil-soluble UV-B filters, e.g. the following substances are used:

3-benzylidene camphor and its derivatives, e.g. 3- (4-methylbenzylidene) camphor;

4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-propyl methoxy cinnamate, isoamyl 4-methoxycinnamate, 4-isoacetyl methoxycinnamate, 2-cyano-3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene);

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-methoxybenzmalonate;

Triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1 ^'-hexyloxy) -1, 3,5-triazine (Octyltriazone) and Dioctyl Butamido Triazone (Uvasorb HEB ^®);

Propane-1,3-diones, e.g. 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;

2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;

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

Sulfonic acid derivatives of the 3-benzylidene camphor, e.g. 4- (2-Oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) -sulfonic acid and its salts.

Especially preferred is the use of esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid isopentyl ester, 2-cyano-3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene).

Furthermore, the use of derivatives of benzophenone, in particular 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4 ^{'-methylbenzophenon,} 2,2'-dihydroxy-4-methoxybenzophenone, and the use of propane-1, 3-diones, such as 1- (4-tert-butylphenyl) -3- (4-methethoxyphenyl) propane-1,3-dione.

Typical UV-A filters are: Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane or 1-phenyl-3 - (4'-isopropylphenyl) -propane-1,3-dione;

Amino-hydroxy-substituted derivatives of benzophenones, e.g. N, N-diethylamino-hydroxybenzoyl-n-hexylbenzoate;

2,2 '- (1, 4-phenylene) -bis-disulfonic acid 1 H-benzimidazole-4,6, Na salt (Neo Helio- pan ^® AP, CAS No. 180898-37-7.).

Of course, the UV-A and UV-B filters can also be used in mixtures.

As other light stabilizers, however, other insoluble pigments, e.g. finely dispersed metal oxides or salts, for example titanium dioxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate. The particles should have an average diameter of less than 200 nm, preferably less than 100 nm.

In addition to the two aforementioned groups of primary light stabilizers, it is also possible to use secondary light stabilizers of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates into the skin. Typical examples are superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C).

The total amount of light stabilizer in the sunscreen according to the invention is usually from 1 to 20, preferably 5 to 15 wt .-%.

As such, a preferred preparation according to the invention may contain from 1 to 95, preferably from 5 to 80, and in particular from 10 to 60,% by weight of water.

According to a particularly preferred embodiment, the cosmetic preparation according to the invention further contains nourishing substances, other cosmetic active ingredients and / or auxiliaries and additives.

Skin-moisturizing agents, antimicrobial substances and / or deodorising or antiperspirant substances are used in particular as further cosmetic active ingredients. This has the advantage that it is possible to achieve further desired effects which contribute to the care or treatment of the skin or, for example, increase the sense of well-being of the user of the cosmetic preparation when using this preparation. In addition to the carrier, the metal derivative nanoparticles, the light-protective compounds, water and physiologically suitable solvents which are associated with them, the cosmetic preparation may also contain, among others, care components such as oils, waxes, fats, replenishers, thickeners, emulsifiers and so on Contain fragrances. A high proportion of nourishing substances is particularly advantageous for topical prophylactic or cosmetic treatment of the skin.

It is particularly advantageous if the preparation contains, in addition to the animal and vegetable fats and oils which in many cases also have care properties, further care components. The group of nourishing active ingredients that can be used includes, for example: fatty alcohols having 8-22 C atoms, especially fatty alcohols of natural fatty acids; animal and vegetable protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein, silk protein, oat protein, pea protein, almond protein and wheat protein hydrolysates; Vitamins and vitamin precursors, in particular those of vitamin groups A and B; Mono-, di- and oligosaccharides; Plant extracts; Honey extracts; ceramides; phospholipids; Vaseline, paraffin and silicone oils; Fatty acid and fatty alcohol esters, in particular the monoesters of the fatty acids with alcohols having 3 to 24 carbon atoms. The preferred vitamins, provitamins or vitamin precursors to be used in the preparation according to the invention include, among others:

Vitamins, provitamins and vitamin precursors from groups A, C, E and F, in particular 3,4-didehydroretinol, ß-carotene (provitamin of vitamin A), ascorbic acid (vitamin C), and the palmitic acid esters, glucosides or phosphates of ascorbic acid , Tocopherole, in particular α-tocopherol and its esters, eg the acetate, nicotinate, phosphate and succinate; vitamin F, which is understood as meaning essential fatty acids, especially linoleic acid, linolenic acid and arachidonic acid;

Vitamin A and its derivatives and provitamins advantageously show a particular skin-smoothing effect.

Among the vitamins, provitamins or vitamin precursors of the vitamin B group or derivatives thereof which may preferably be used in the preparation according to the invention and the derivatives of 2-furanone include, inter alia:

Vitamin Bi, common name thiamine, chemical name 3 - [(4'-amino-2'-methyl-5'-pyrimidinyl) methyl] -5- (2-hydroxyethyl) -4-methylthiazolium chloride. Thiamine hydrochloride is preferably used in amounts of from 0.05 to 1% by weight, based on the total agent. Vitamin B2, common name riboflavin, chemical name 7,8-dimethyl-10- (1-D-ribityl) -benzo [g] pteridine-2,4 (3H, 10H) -dione. In free form riboflavin z. As in whey, other riboflavin derivatives can be isolated from bacteria and yeasts. A stereoisomer of riboflavin which is also suitable according to the invention is lyxoflavin which can be isolated from fishmeal or liver and carries a D-arabityl residue instead of D-ribityl. Riboflavin or its derivatives are preferably used in amounts of from 0.05 to 1% by weight, based on the total agent.

Vitamin B3. Under this name, the compounds nicotinic acid and nicotinamide (niacinamide) are often performed. Preferred according to the invention is the nicotinic acid amide, which is preferably present in the agents according to the invention in amounts of from 0.05 to 1% by weight, based on the total agent.

Vitamin B5 (pantothenic acid and panthenol). Panthenol is preferably used. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and also cationically derivatized panthenols. In a further preferred embodiment of the invention, it is also possible to use derivatives of 2-furanone in addition to pantothenic acid or panthenol. Particularly preferred derivatives are the commercially available substances dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone with the trivial name pantolactone (Merck), 4-hydroxy-methyl-γ-butyrolactone (Merck), 3 , 3-dimethyl-2-hydroxy-γ-butyrolactone (Aldrich) and 2,5-dihydro-5-methoxy-2-furanone (Merck), expressly including all stereoisomers.

Advantageously, these compounds of the cosmetic preparation according to the invention provide moisturizing and soothing properties.

The said compounds of the vitamin Bs type and the 2-furanone derivatives are contained in the agents according to the invention preferably in a total amount of 0.05 to 10 wt .-%, based on the total agent. Total amounts of 0.1 to 5 wt .-% are particularly preferred.

Vitamin Bβ, which is not understood to be a uniform substance but the derivatives of 5-hydroxymethyl-2-methylpyridin-3-ol known by the common names pyridoxine, pyridoxamine and pyridoxal. Vitamin Bβ is preferably present in the agents according to the invention in amounts of from 0.0001 to 1.0% by weight, in particular in amounts of from 0.001 to 0.01% by weight.

Vitamin B7 (biotin), also known as vitamin H or "skin vitamin". Biotin is (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-d] imidazole-4-valeric acid. Biotin is preferably present in the compositions according to the invention in amounts of from 0.0001 to 1.0% by weight, in particular in amounts of from 0.001 to 0.01% by weight.

Panthenol, pantolactone, nicotinamide and biotin are very particularly preferred according to the invention.

Auxiliaries and additives are substances which are suitable for improving the aesthetic, performance and / or cosmetic properties, such as z.6. Co-emulsifiers, organic solvents, superfatting agents, stabilizers, antioxidants, waxes or fats, bodying agents, thickeners, tanning agents, vitamins, cationic polymers, biogenic agents, preservatives, hydrotopes, solubilizers, dyes and fragrances.

For example, the following auxiliaries and additives can be used: Allantoin,

- Aloe Vera,

- bisabolol,

Ceramides and pseudoceramides,

Antioxidants advantageously improve the stability of the preparations according to the invention. Antioxidants are, for example, amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole and imidazole derivatives (eg urocaninic acid), peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg. Anserine), carotenoids, carotenes (eg, 6-α-carotene, β-carotene, lycopene) and their derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), rothioglucose, propylthiouracil and other thio compounds (eg thioglycerol, thio sorbitol, thioglycolic acid, thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, γ- Linoleyl, cholesteryl and glyceryl esters) and their salts, dilaurylthio dipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteinsulfoximine, buthionine sulfones , Penta-, hexa-, Heptathionin- sulfoximine) in very low tolerated dosages (eg. Pmol / kg to pmol / kg), furthermore metal chelators (eg α-hydroxyfatty acids, EDTA, EGTA, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acids, bile acid, bile extracts Gallic acid esters (eg propyl, octyl and dodecyl gallate), flavonoids, catechins, bilirubin, biliverdin and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid and derivatives thereof, Hydroquinone and its derivatives (eg arbutin), ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (eg ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphates, sodium and magnesium ascorbate, disodium ascorbyl phosphate and sulfate, potassium ascorbyl tocopheryl phosphate, chitosan ascorbate), isoascorbic acid and its derivatives, tocopherols and their derivatives (eg tocopheryl acetate, linoleate, oleate and succinate, tocophereth-5, tocophereth-10, tocophereth-12, tocophereth-18, tocophereth-50 , Tocopherol), vitamin A and derivatives (eg vitamin A palmitate), the coniferyl benzoate of benzoin, rutin, rutinic acid and its derivatives, disodium rubynyldisulfate, cinnamic acid and its derivatives (eg ferulic acid, ethyl ferulate, caffeic acid ), Kojic acid, chitosanglycolate and salicylate, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid, nordihydroguiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and zinc derivatives (eg ZnO, ZnSO 4), selenium and selenium Derivatives (eg selenomethionine), stilbenes and stilbene derivatives (eg stilbene oxide, trans-stilbene oxide).

According to the invention, suitable derivatives (salts, esters, sugars, nucleotides, nucleosides, peptides and lipids) and mixtures of said active substances or plant extracts (for example tea tree oil, rosemary extract and rosmarinic acid) containing these antioxidants can be used. Preferred lipophilic, oil-soluble antioxidants from this group are tocopherol and its derivatives, gallic acid esters, flavonoids and carotenoids, and butylhydroxytoluene / anisole. As water-soluble antioxidants are amino acids, eg. As tyrosine and cysteine and their derivatives and tanning agents, especially those of plant origin are preferred. The total amount of the antioxidants in the cosmetic preparations according to the invention is 0.001-20% by weight, preferably 0.05-10% by weight, in particular 0.1-5% by weight and very particularly preferably 0.1-2% by weight. -%.

Triterpenes, in particular triterpenic acids such as ursolic acid, rosmarinic acid, betulinic acid, boswellic acid and bryonic acid,

Monomeric catechins, especially catechin and epicatechin, leucoanthocyanidins, catechin polymers (catechin tannins) and gallotannins,

Thickener, z. Gelatin, plant gums such as agar-agar, guar gum, alginate, xanthan gum, gum arabic, karaya gum or locust bean gum, natural and synthetic clays and phyllosilicates, e.g. B. bentonite, hectorite, montmorillonite or Laponite ^® , fully synthetic hydrocolloids such as polyvinyl alcohol, and also Ca, Mg or Zn soaps of fatty acids, plant glycosides,

Structurants such as maleic acid and lactic acid, dimethyl isosorbide, alpha, beta and gamma cyclodextrins, in particular for the stabilization of retinol,

Solvents, swelling and penetrating substances such as ethanol, isopropanol, ethylene glycol, propylene glycol, propylene glycol monoethyl ether, glycerol and diethylene glycol, carbonates, Hydrogencarbonates, guanidines, ureas and primary, secondary and tertiary phosphates

Perfume oils, pigments and dyes for staining the composition, pH adjusters, e.g. α- and β-hydroxycarboxylic acids, complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphoric acids, opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers, pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate, blowing agents such as Propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

The addition of allantoin, bisabolol and / or aloe vera also in the form of extracts to the cosmetic preparations according to the invention further improves the skin-soothing, moisturizing and skin-care properties of the formulations and is therefore particularly preferred.

As further ingredients, the cosmetic preparation according to the invention may contain, in minor amounts, further surfactants compatible with the other ingredients.

Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-

Methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide sisides, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, Fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether) phosphates.

If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, optionally partially oxidized

Alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkyliglucamides, protein hydrolysates (in particular wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, especially quaternized fatty acid trialkanolamine ester salts.

Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

The use of the photoprotective preparations according to the invention is also possible in particular in hair cosmetics such as shampoos, conditioners, rinses, hair lotions, hair gels, hair sprays etc. In particular leave-on products which remain on the hair or scalp after application are particularly well suited. The so applied to the scalp and the hair preparation can therefore also act there as a UV protective agent or unfold on the scalp its soothing effect.

The preparations according to the invention can also be used in the field of washing, showering and bathing preparations.

According to a preferred embodiment of the cosmetic agent according to the invention, the cosmetic agent is applied topically to the surface of the body to be treated or protected. This form of application is particularly advantageous because it is easy to handle, so that incorrect dosages are largely excluded. Furthermore, an additional nourishing effect for the skin can be achieved. In addition, if only a few parts of the body are exposed to solar radiation, the sunscreen can only be applied specifically to these parts of the body.

Another object of the present invention is the use of the present invention surface-modified metal oxides for UV protection. This is particularly advantageous since due to the fineness, for example of the surface-modified metal oxide and the good distribution, a particularly high UV absorption is achieved.

A further subject of the present invention is the use of the surface-modified metal oxides according to the invention, in particular of zinc oxide as an antimicrobial active ingredient. The use of these particles is particularly advantageous for this purpose, because due to the fineness of the particles and the resulting large surface, the antimicrobial effect is greatly improved and on the other hand, due to the good dispersing properties of the material, the zinc oxide is present in finely divided form. Thus, the zinc oxide can be easily used in various dosage forms such as creams, skin milk, lotions or Tonics. Another object of the present invention is a pharmaceutical agent containing a surface-modified metal oxide according to the invention. This pharmaceutical agent is characterized in that due to the fineness of the particles, the pharmaceutical activity is greatly increased.

In addition, the pharmaceutical agent according to the invention has the advantage that due to the good long-term stability already described above, for example, the zinc oxide dispersions can be dispensed with the addition of stabilizers, which prevent segregation. Thus, in addition, the compatibility of the pharmaceutical agent is increased.

The invention will be explained in more detail with reference to the following examples.

Examples of cosmetic formulations

The following preparations according to the invention contain as component modified metal derivative nanoparticles.

In the examples given below for cosmetic preparations according to the invention, the term "hybrid" for at least one combination is selected from:

1) nanoparticles of at least one metal derivative - at least one chemically bonded to the nanoparticles of at least one metal derivative (TΪO2 or ZnO) triazine derivative.

2) nanoparticles of at least one metal derivative

- At least one to the nanoparticles of at least one metal derivative (TΪO2 or ZnO) chemically bonded hydroxybenzophenone derivative.

3) - Nanoparticles of at least one metal derivative

at least one compound chemically bonded to the nanoparticles of at least one metal derivative (TΪO2 or ZnO) selected from the light-protective compounds mentioned in WO 2007/017587, Sections [0036] and [0037].

4) - nanoparticles of at least one metal derivative

- At least one to the nanoparticles of at least one metal derivative (TΪO2 or ZnO) chemically bonded 4,4'-diarylbutadiene derivative. The quantities given below are parts by weight. The manner in which the preparations can be prepared are known to the person skilled in the art.

Preparation 1

Preparation 3 Preparation 4

Preparation 5 Preparation 6

Preparation 7 Preparation 8

Preparation 9 Preparation 10

Preparation 1 1

Preparation 13

Preparation 14

Preparation 16

Preparation 17

Preparation 18

Preparation 21

Preparation 22

Preparation 23

Preparation 25

Preparation 26

Preparation 27 Preparation 28

Preparation 29 Preparation 30

Preparation 31 Preparation 32

Preparation 33 Preparation 34

Preparation 35

Preparation 37

Preparation 38

Preparation 40

Preparation 42 Preparation 43 Preparation 43

Preparation 45

Preparation 46

Preparation 47

Preparation 47a

Preparation 48

Claims

claims

1) containing sunscreen effective preparation

At least one structural unit chemically bound to the nanoparticles of at least one metal derivative selected from the group consisting of derivatives of triazine, derivatives of hydroxybenzophenone and derivatives of 4,4'-diarylbutadiene.

2) Sunscreen-effective preparation according to claim 1, containing at least one further, from the UV-light stabilizer bound to the nanoparticles different organic UV light stabilizer.

3) photoprotective composition comprising - nanoparticles of at least one metal derivative,

at least one organic UV light stabilizer chemically bound to the nanoparticles of at least one metal derivative and

at least one further organic UV light stabilizer which is different from the UV light stabilizer bound to the nanoparticles and from octyl methoxycinnamate.

4) Sunscreen-effective preparation according to one of claims 2 or 3, wherein the at least one further organic UV light stabilizer is selected from the group consisting of 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (CAS No. 6197-30-4 ), Ethylhexyl salicylate (CAS No. 1 18-60-5), homosalate

(CAS No. 1 18-56-9), dimethicodiethylbenzalmalonate (CAS No. 207574-74-1) and mixtures thereof.

5) A sunscreen effective composition according to any one of claims 1 to 4, further comprising dihydroxyacetone.

6) photoprotective composition according to any one of claims 1 to 5, wherein the metal derivative is selected from the derivatives of titanium and / or zinc.