EP1743002A2

EP1743002A2 - Polyasparaginic acid surface-modified metal oxides methods for production and use thereof in cosmetic preparations

Info

Publication number: EP1743002A2
Application number: EP05716391A
Authority: EP
Inventors: Valerie Andre; Jens Rieger; Heidrun Debus
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-03-31
Filing date: 2005-03-26
Publication date: 2007-01-17
Also published as: WO2005094156A2; JP2007537116A; KR20060133067A; BRPI0508721A; US20070218019A1; WO2005094156A3; CA2558788A1; AU2005227690A1

Abstract

The invention relates to surface-modified nanoparticulate metal oxides, methods for production and use thereof as UV filter in cosmetic preparations.

Description

Surface-modified metal oxides, processes for their production and their use in cosmetic preparations

description

The present invention relates to surface-modified nanoparticulate metal oxides, processes for their preparation and their use as UV filters in cosmetic preparations.

Metal oxides are used for a variety of purposes, e.g. as a white pigment, as a catalyst, as a component of antibacterial skin protection ointments and as an activator for rubber vulcanization. Cosmetic sunscreens contain fine-particle zinc oxide or titanium dioxide as UV-absorbing pigments.

In the context of the present application, the term “nanoparticles” refers to particles with an average diameter of 5 to 10,000 nm, determined by means of electron microscopic methods.

Zinc oxide nanoparticles with particle sizes below approx. 30 nm are potentially suitable for use as UV absorbers in transparent organic-inorganic hybrid materials, plastics, paints and coatings. It can also be used to protect UV-sensitive organic pigments.

Particles, particle aggregates or agglomerates made of zinc oxide that are larger than approx. 30 nm lead to scattered light effects and thus to an undesirable decrease in transparency in the range of visible light. Therefore, the redispersibility, that is, the convertibility of the zinc oxide nanoparticles produced into a colloidally dispersed state, is an important prerequisite for the above-mentioned applications.

Zinc oxide nanoparticles with particle sizes below approx. 5 nm show a blue shift in the absorption edge due to the size quantization effect (L. Brus, J. Phys. Chem. (1986), 90, 2555-2560) and are therefore suitable for use as UV absorbers in UV A-area less suitable.

The production of metal oxides, for example zinc oxide, by dry and wet processes is known. The classic method of burning zinc, which is known as a dry process (e.g. Gmelin Volume 32, 8th Edition, Supplementary Volume, p. 772 ff.), Produces aggregated particles with a wide size distribution. Although it is fundamentally possible to produce particle sizes in the submicrometer range by grinding processes, dispersions with average particle sizes in the lower nanometer range cannot be achieved from such powders due to the shear forces that are too low. Particularly fine-particle zinc oxide is primarily produced by wet-chemical precipitation processes. Precipitation in aqueous solution usually gives and / or carbonate-containing materials that have to be thermally converted to zinc oxide. The thermal aftertreatment has a negative effect on the fine particle size, since the particles are subjected to sintering processes that lead to the formation of micrometer-sized aggregates that can only be broken down incompletely onto the primary particles by grinding.

Nanoparticulate metal oxides can be obtained, for example, by the microemulsion process. In this method, a solution of a metal alkoxide is added dropwise to a water-in-oil microemulsion. The hydrolysis of the alkoxides to the nanoparticulate metal oxide then takes place in the inverse micelles of the microemulsion, the size of which is in the nanometer range. The disadvantages of this process are in particular that the metal alkoxides are expensive starting materials, that additional emulsifiers have to be used and that the preparation of the emulsions with droplet sizes in the nanometer range is a complex process step.

DE 199 07 704 describes a nanoparticulate zinc oxide produced by a precipitation reaction. The nanoparticulate zinc oxide is produced from a zinc acetate solution via an alkaline precipitation. The centrifuged zinc oxide can be redispersed to a sol by adding methylene chloride. The zinc oxide dispersions produced in this way have the disadvantage that they do not have good long-term stability due to the lack of surface modification.

WO 00/50503 describes zinc oxide gels which contain nanoparticulate zinc oxide particles with a particle diameter of 15 15 nm and which are redispersible to sols. The precipitates produced by basic hydrolysis of a zinc compound in alcohol or in an alcohol / water mixture are redispersed by adding dichloromethane or chloroform. The disadvantage here is that no stable dispersions are obtained in water or in aqueous dispersants.

In the publication from Chem. Mater. 2000, 12, 2268-74 "Synthesis and Characterization of Poly (vinylpyrrolidone) -Modified Zinc Oxide Nanoparticles" by Lin Guo and Shihe Yang, Wurtzit zinc oxide nanoparticles are surface-coated with polyvinylpyrrolidone. The disadvantage here is that zinc oxide particles coated with polyvinylpyrrolidone are not dispersible in water.

WO 93/21127 describes a process for producing surface-modified nanoparticulate ceramic powders. Here, a nanoparticulate ceramic powder is surface-modified by applying a low-molecular organic compound, for example propionic acid. This method cannot be used to modify the surface of zinc oxide because the modification reactions ions are carried out in aqueous solution and zinc oxide dissolves in aqueous organic acids. Therefore, this process cannot be used to produce zinc oxide dispersions; moreover, zinc oxide is not mentioned in this application as a possible starting material for nanoparticulate ceramic powders.

JP-A-04 164814 describes a process which leads to finely divided ZnO by precipitation in an aqueous medium at elevated temperature even without thermal aftertreatment. The average particle size is given without specifying the degree of agglomeration, 20-50 nm. These particles are relatively large. Even with minimal agglomeration, this leads to scattering effects which are undesirable in transparent applications.

JP-A-07 232919 describes the production of 5 to 10,000 nm ZnO particles from zinc compounds by reaction with organic acids and other organic compounds such as alcohols at elevated temperature. The hydrolysis takes place here in such a way that the by-products formed (esters of the acids used) can be distilled off. The process allows the production of ZnO powders that can be redispersed by surface modification. However, based on the disclosure of this application, it is not possible to produce particles with an average diameter <15 nm. Accordingly, in the examples listed in the application, the smallest average primary particle diameter is 15 nm.

Metal oxides which have been rendered hydrophobic with organosilicon compounds include described in DE 33 14 741 A1, DE 3642 794 A1 and EP 0 603 627 A1 and in WO 97/16156.

These metal oxides coated with silicone compounds, for example zinc oxide or titanium dioxide, have the disadvantage that oil-in-water or water-in-oil emulsions produced with them do not always have the necessary pH stability.

Furthermore, incompatibilities of various metal oxides coated with silicone compounds are frequently observed, which can lead to undesired aggregate formation and to flocculation of the different particles.

The object of the present invention was therefore to provide nanoparticulate metal oxides which allow the production of stable nanoparticulate dispersions in water or polar organic solvents and in cosmetic oils. An irreversible aggregation of the particles should be avoided as far as possible so that a complex grinding process can be avoided.

This object was achieved by surface-modified nanoparticulate metal oxides, the metal being selected from the group consisting of aluminum, cerium, Iron, titanium, zinc and zirconium, characterized in that the surface modification comprises a coating with polyaspartic acid.

In the context of the present invention, the term polyaspartic acid encompasses both the free acid and the salts of polyaspartic acid, such as e.g. Sodium, potassium, lithium, magnesium, calcium, ammonium, alkylammonium, zinc and iron salts or mixtures thereof.

The surface coating used according to the invention for the nanoparticulate metal oxides preferably contains polyaspartic acid and / or its sodium salt.

A preferred embodiment of the surface-modified metal oxides according to the invention is characterized in that the surface coating contains polyaspartic acid with a molecular weight M _w of 1000 to 100000, preferably 1000 to 20,000, particularly preferably 1000 to 7000, determined according to gel chromatography analysis.

A further advantageous embodiment of the metal oxides according to the invention is characterized in that the metal oxide particles have an average primary particle diameter of 5 to 10000 nm, preferably 10 to 200 nm, particularly preferably 10 to 50 nm, particle diameter determined by means of scanning and transmission electron microscopy.

In the context of the present invention, preferred metal oxides are titanium dioxide and zinc oxide, particularly preferably zinc oxide.

The invention is based on the knowledge that a long-term stability of dispersions of the surface-modified metal oxides, in particular in cosmetic preparations, without undesirable pH changes in the storage of these preparations, can be achieved by surface modification of nanoparticulate metal oxides with polyaspartic acid and / or their salts.

Another object of the invention is a method for producing a surface-modified nanoparticulate metal oxide, the metal being selected from the group consisting of aluminum, cerium, iron, titanium, zinc and zirconium

a. Precipitation of the metal oxide from an aqueous solution of one of its metal salts,

b. Separation of the precipitated metal oxide from the aqueous reaction mixture and c. subsequent drying of the metal oxide,

characterized in that the precipitation of the metal oxide in process step a. in the presence of polyaspartic acid.

A preferred embodiment of the process according to the invention is characterized in that the precipitation is carried out in the presence of polyaspartic acid with a molecular weight M _w of 1000 to 100000, preferably 1000 to 20,000, particularly preferably 1000 to 7000, determined by gel chromatography analysis.

For the metal salts in process step a. it can be metal halides, acetate, sulfates or nitrates. Preferred metal salts are halides, for example zinc (II) chloride or titanium tetrachloride, and nitrates, for example zinc (II) nitrate.

The precipitation of the metal oxide in process step a. can be carried out at a temperature in the range from 20 ° C. to 100 ° C., preferably in the range from 25 ° C. to 40 ° C.

Depending on the metal salt used, the precipitation can be carried out at a pH in the range from 3 to 13. In the case of zinc oxide, the pH during the precipitation is in the range from 7 to 11.

The concentration of the metal salts is generally in the range from 0.05 to 1 mol / l, preferably in the range from 0.1 to 0.5 mol / l, particularly preferably in the range from 0.2 to 0.4 mol / l ,

The precipitation time is generally 2 to 8 hours, preferably 3 to 7 hours, particularly preferably 4 to 6 hours.

The present invention relates in particular to a process for the production of surface-modified nanoparticulate zinc oxide by

a. Precipitation of the zinc oxide from an aqueous solution of zinc (II) chloride or zinc (II) nitrate at a temperature in the range from 25 to 40 ° C and a pH in the range from 7 to 11 in the presence of an alkali metal hydroxide or ammonium hydroxide

b. Separation of the precipitated zinc oxide from the aqueous reaction mixture and

c. subsequent drying, characterized in that the precipitation of the zinc oxide in process step a. in the presence of polyaspartic acid with a molecular weight M _w of 1000 to 7000.

The precipitation of the zinc oxide in process step a. can be done, for example, by metering in a mixture of polyaspartic acid and an alkali metal hydroxide or ammonium hydroxide, in particular NaOH, to the aqueous solution of zinc (II) chloride or Zn (II) nitrate or by simultaneously metering in each case an aqueous solution of zinc (II) chloride orZn ( ll) nitrate and an aqueous solution of an alkali metal hydroxide or ammonium hydroxide to an aqueous polyaspartic acid solution.

The precipitated metal oxide can be separated from the aqueous reaction mixture in a manner known per se, for example by filtration or centrifugation.

The filter cake obtained can be dried in a manner known per se, for example in a drying cabinet at temperatures between 40 and 100 ° C., preferably between 50 and 70 ° C. under normal pressure to constant weight.

Another object of the present invention is a cosmetic agent which contains a zinc oxide or a zinc oxide dispersion surface-coated according to the invention.

The present invention furthermore relates to the use of surface-modified metal oxide, in particular titanium dioxide or zinc oxide, which are produced by the process according to the invention: for UV protection as an antimicrobial active substance

According to a preferred embodiment of the present invention, the surface-modified metal oxide, in particular titanium dioxide or zinc oxide, is redispersible in a liquid medium and forms stable dispersions. This is particularly advantageous because the dispersions produced from the zinc oxide according to the invention do not have to be redispersed before further processing, but rather can be processed directly.

According to a preferred embodiment of the present invention, the surface-modified metal oxide is redispersible in polar organic solvents and forms stable dispersions. This is particularly advantageous since it enables uniform incorporation into plastics or foils, for example.

According to a further preferred embodiment of the present invention, the surface-modified metal oxide is redispersible in water and forms stable dispersions there. This is particularly advantageous, since it opens up the possibility of using the material according to the invention, for example, in cosmetic formulations, the elimination of organic solvents being a great advantage. Mixtures of water and polar organic solvents are also conceivable.

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

According to a particularly preferred embodiment of the present invention, the metal oxide nanoparticles have a diameter of 10 to 50 nm. This size range is particularly advantageous since, after redispersion of such zinc oxide nanoparticles, the resulting dispersions are transparent and therefore do not influence the color, for example when added to cosmetic formulations. In addition, this also offers the possibility of use in transparent films.

If the metal oxides, especially 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 the absorption edge is shifted into the short-wave range (L. Brus , J. Phys., Chem. (1986) 90, 2555-2560).

The present invention furthermore relates to a cosmetic agent which contains a metal oxide, in particular titanium dioxide and / or zinc oxide, which has been surface-modified according to the invention. This is particularly advantageous since, because of the fine distribution of the metal oxide particles, in particular the zinc oxide particles, they can develop their skin-calming effect more effectively.

Another advantage is that when applied to e.g. the skin does not rub due to the small particle size, but a gentle application is possible, which causes a pleasant feeling on the skin.

According to a further embodiment of the cosmetic agent, it is used for the care or protection of the skin, in particular for sun protection or for care when exposed to sunlight, 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 granulate, a powder, a stick preparation such as a lipstick, a foam, an aerosol or a spray. Such formulations are well suited for topical preparations. Suitable emulsions are oil-in-water emulsions and water-in-oil emulsions or microemulsions. This is particularly advantageous because the use in sunscreen means that the UV-absorbing and skin-calming effects of zinc oxide, for example, can be used simultaneously. In addition, the metal oxides modified according to the invention are very suitable for use in sunscreens, since the particles can be produced in a size which makes them appear transparent to the human eye. This means that there is no white veil on the skin during use.

Another advantage is the fact that zinc oxide, in particular, is a UV broadband filter, the UV absorption behavior of which makes it possible to create a sunscreen that does not require any further chemical UV filter substances. As a result, the risk of skin irritation or allergic reactions caused by decomposition products of chemical filters or by these substances themselves can be avoided, which greatly increases the general compatibility of a sunscreen designed in this way. As a rule, the cosmetic agent is used for topical application to the skin. Topical preparations are to be understood here as those preparations which are suitable for applying the active substances to the skin in a finely divided form and preferably in a form which can be absorbed by the skin. For this, 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.

According to a preferred embodiment of the cosmetic agent according to the invention, the agent contains a carrier. The preferred carrier is water, a gas, a water-based liquid, an oil, a gel, an emulsion or microemulsion, a dispersion or a mixture thereof. The carriers mentioned show good skin tolerance. Aqueous gels, emulsions or microemulsions are particularly advantageous for topical preparations.

Nonionic surfactants, zwitterionic surfactants, ampholytic surfactants or anionic emulsifiers can be used as emulsifiers. The emulsifiers can be contained in the composition according to the invention in amounts of 0.1 to 10, preferably 1 to 5,% by weight, based on the composition.

For example, a surfactant from at least one of the following groups can be used as the nonionic surfactant: Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group;

C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;

Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

Alkyl mono- and oligoglycosides with 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 hardened castor oil;

Polyol and especially polyglycerol esters such as e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds from several of these classes of substances are also suitable;

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

Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerin, polyglycerol _^ pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, Butyl glucoside, lauryl glucoside) and 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 with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and

polyalkylene glycols; Betaine.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that carry at least one quaternary ammonium group and at least one carboxylate or sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylamino-propyl-N, N dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl- 3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the coconut acylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred.

Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ₈ , i8-alkyl or acyl group, contain at least one free amino group and at least one -COOH or -S0 ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino-butyric acids, N alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamido-propylglycines, N-alkyltaurines, N alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group.

Particularly preferred ampholytic surfactants are the N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and the C _{12 /} ιa acyl sarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred. Furthermore, alkyl ether sulfates, monoglyceride sulfates, fatty acid sulfates, sulfosuccinates and / or ether carboxylic acids can be used as anionic emulsifiers.

Suitable oil components are 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 C ₆ -C ₂₂ -Fettaikohoien, esters of branched C ₆ -C ₁₃ - Carboxylic acids with linear C ₆ -C ₂₂ fatty alcohols, esters of linear Ce-C ^ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -Cι ₀ fatty acids, liquid mono- / di-, Trigly- ceridmischungen based on C ₆ -Cι ₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C ₂ -C ₁₂ dicarboxylic acids with linear or branched alcohols with 1 up to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (eg Finsolv ^® TN), dialkyl ethers, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons. Silicone compounds can also be used as oil bodies, for example dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, alkyl and / or glycoside-modified silicone compounds which can be both liquid and resinous at room temperature. The oil bodies can be present in the agents according to the invention in amounts of 1 to 90, preferably 5 to 80, and in particular 10 to 50% by weight, based on the composition.

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

Although it is possible, as already described further above, to use the zinc oxide particles according to the invention to create a sunscreen which achieves good UV absorption properties without further UV filter substances, it may be desirable in individual cases to add further UV to the cosmetic agent or the sunscreen. Add filter substances. This can e.g. be necessary if a special focus is to be placed on filter performance. One or more further UV light protection filters can be added to the composition according to the invention.

In the case of soluble compounds, UV light protection filters are to be understood as organic substances which are able to absorb ultraviolet rays and which absorb the energy in the form of longer-wave radiation, e.g. Warmth to give up again. The organic substances can be oil-soluble or water-soluble.

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 amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4 methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isamyl ester, 4 methoxycinnamic acid isopentyl ester, 2-cyano-3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene);

Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;

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-r-hexyloxy)} -1,3,5-triazine (octyl tyltriazone) and Dioctyl Butamido Triazone (Uvasorb HEB ^®).

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

Possible water-soluble substances are:

2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, 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 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

It is particularly preferred to use esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3-phenylcinnamate (octocrylene).

Furthermore, the use of derivatives of benzophenone, in particular 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4Amethylbenzophenon, 2,2'-dihydroxy-4-methoxybenzophenone and the use of propane-1,3-diones , such as 1 - (4-tert. Butylpheny!) - 3- (4-'methoxyphenyl) 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 such as e.g. N, N-diethylamino-hydroxybenzoyl-n-hexylbenzoate.

The UV-A and UV-B filters can of course also be used in mixtures.

Other insoluble pigments, e.g. finely dispersed metal oxides or salts such as titanium dioxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate can be used. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.

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

The total proportion of light stabilizers in the sunscreen according to the invention is usually 1 to 20, preferably 5 to 15% by weight. The composition according to the invention as such can contain 1 to 95, preferably 5 to 80, and in particular 10 to 60% by weight of water.

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

Skin moisturizers, antimicrobial substances and / or deodorant or antiperspirant substances are used in particular as further cosmetic active substances. This has the advantage that further desired effects can be achieved which contribute to the care or treatment of the skin or, for example, increase the well-being of the user of the cosmetic composition when using this composition. Thus, in addition to the carrier, the surface-modified zinc oxide, water and physiologically suitable solvents, the cosmetic composition can also contain, among other things, care ingredients, such as oils, waxes, fats, lipid-replenishing substances, thickeners, emulsifiers and fragrances. A high proportion of nourishing substances is particularly advantageous for topical prophylactic or cosmetic treatment of the skin.

It is particularly advantageous if, in addition to the animal and vegetable fats and oils, which in many cases also have a care effect, the composition also contains further care components. The group of nourishing active ingredients that can be used includes, for example: fatty alcohols with 8-22 carbon atoms, especially fatty alcohols from 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, especially those of vitamin groups A and B; Mono-, di- and oligosaccharides; Plant extracts; Honey extracts; ceramides; phospholipids; Petroleum jelly, paraffin and silicone oils; Fatty acid and fatty alcohol esters, especially the monoesters of fatty acids with alcohols with 3 to 24 carbon atoms. The vitamins, provitamins or vitamin precursors to be used preferably in the composition according to the invention include:

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), as well as the palmitic acid esters, glucosides or phosphates of ascorbic acid , Tocopherols, especially α-tocopherol and its esters, for example the acetate, nicotinate, phosphate, and succinate; also vitamin F, which is understood to mean essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid;

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

The vitamins, provitamins or vitamin precursors of the vitamin B group or their derivatives and the derivatives of 2-furanone which are preferably to be used in the composition according to the invention include:

Vitamin, 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 0.05 to 1% by weight, based on the total agent. Vitamin B ₂ , common name riboflavin, chemical name 7,8-dimethyl-10- (1-D-ribityl) -benzo [g] pteridine-2,4 (3H, 10H) -dione. In free form, riboflavin comes e.g. B. in whey before, other riboflavin derivatives can be isolated from bacteria and yeast. A stereoisomer of riboflavin which is also suitable according to the invention is lyxoflavin which can be isolated from fishmeal or liver and which carries a D-arabityl radical instead of D-ribityl. Riboflavin or its derivatives are preferably used in amounts of 0.05 to 1% by weight, based on the total agent.

Vitamin B ₃ . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. According to the invention, preference is given to nicotinamide, which is preferably present in the agents according to the invention in amounts of 0.05 to 1% by weight, based on the total agent.

Vitamin B ₅ (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 cationically derivatized panthenols. In a further preferred embodiment of the invention, derivatives of 2-furanone can also be used in addition to pantothenic acid or panthenol. Particularly preferred derivatives are the dihydro-3 hydroxy-4,4-dimethyl-2 (3H) -furanone substances which are also commercially available. the common name pantolactone (Merck), 4 hydroxymethyl-γ-butyrolactone (Merck), 3,3-dimethyl-2-hydroxy-γ-butyrolactone (Aldrich) and 2,5-dihydro-5-methoxy-2-furanone (Merck) , with all stereoisomers expressly included.

These compounds advantageously impart moisturizing and skin-calming properties to the cosmetic composition according to the invention.

The compounds of the vitamin B ₅ type mentioned and the 2-furanone derivatives are preferably present in the agents according to the invention in a total amount of 0.05 to 10% by weight, based on the agent as a whole. Total amounts of 0.1 to 5% by weight are particularly preferred.

Vitamin B ₆ , which does not mean a uniform substance, but rather the derivatives of 5 hydroxymethyl-2-methylpyridin-3-ol known under the trivial names pyridoxine, pyridoxamine and pyridoxal. Vitamin B ₆ is contained in the agents according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight.

Vitamin B ₇ (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 contained in the agents according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 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 that are suitable for improving the aesthetic, application technology and / or cosmetic properties, such as 6. Co-emulsifiers, organic solvents, superfatting agents, stabilizers, antioxidants, waxes or fats, consistency agents, thickeners, browning agents, vitamins, cationic polymers, biogenic agents, preservatives, hydrotopes, solubilizers, colorants and fragrances.

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

- allantoin,

- AloeVera,

Bisabolol,

Ceramides and pseudoceramides,

Antioxidants advantageously improve the stability of the compositions according to the invention. Antioxidants include amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole and imidazole derivatives (e.g. urocanic acid), peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. Anserine), carotenoids, carotenes (eg. 6-α-carotene, β-carotene, lycopene) and their derivatives, lipoic acid and their derivatives (eg dihydroliponic acid), aurothioglu- cose, propylthiouracil and other thio compounds (eg thioglycerin, thiosorbitol , Thioglycolic acid, thi redoxin, 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, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. 6th butynesulfoximines, Homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, Heptathionine sulfoximine) in very low tolerable doses (e.g. B. pmol / kg to pmol / kg), furthermore metal chelators (eg α-hydroxy fatty 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 (e.g. propyl, octyl and dodecyl gallate), flavonoids, catechins, bilirubin, biliverdin and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid re and their derivatives, hydroquinone and its derivatives (e.g. arbutin), ubiquinone and ubiquinol as well as their derivatives, vitamin C and its derivatives (e.g. ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphate, sodium and magnesium ascorbate, disodium ascorbyl phosphate and sulfate, potassium ascorbyl tocopheryl phosphate, chitosan ascorbate), isoascorbic acid and its derivatives, tocopherols and their derivatives (for example tocopheryl acetate, linoleate, oleate and succinate, tocopheretheth-5, tocophereth-5, tocopherol-5, tocopherol-5, , Tocophereth-18, tocophereth-50, tocopher solan), vitamin A and derivatives (e.g. vitamin A palmitate), the coniferyl benzoate of benzoin, rutin, rutinic acid and its derivatives, disodium rutinyl disulfate, cinnamic acid and their derivatives (e.g. Ferulic acid, ethyl ferulate, caffeic acid), kojic acid, chitosan glycolate and - salicylate, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and their derivative ate, mannose and their derivatives, zinc and zinc derivatives (e.g. B. ZnO, ZnS04), selenium and selenium derivatives (e.g. selenium methionine), stilbene and stilbene derivatives (e.g. stilbene oxide, trans-stilbene oxide).

According to the invention, suitable derivatives (salts, esters, sugars, nucleotides, nucleosides, peptides and lipids) as well as mixtures of these active substances or plant extracts (e.g. tea tree oil, rosemary extract and rosemary 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 butylated hydroxytoluene / anisole. As water-soluble antioxidants are amino acids, e.g. B. tyrosine and cysteine and their derivatives and tannins, especially those of plant origin are preferred. The total amount of the antioxidants in the cosmetic compositions 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, rosmaric acid, betulinic acid, boswellic acid and bryonolic acid,

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

Thickeners, e.g. B. gelatin, vegetable gums such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum or locust bean gum, natural and synthetic clays and layered silicates, 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, Vegetable lycosides,

Structurants such as maleic acid and lactic acid,

dimethyl isosorbide,

Alpha, beta and gamma cyclodextrins, in particular for stabilizing retinol,

Solvents, swelling and penetration substances such as ethanol, isopropanol, ethylene glycol, propylene glycol, propylene glycol monoethyl ether, glycerin and diethylene glycol, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates

Perfume oils, pigments and dyes for coloring the agent,

Substances for adjusting the pH, e.g. α- and ß-hydroxycarboxylic acids,

Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphoric acids,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers,

Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,

Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air.

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

The cosmetic composition according to the invention can contain minor amounts of further surfactants that are compatible with the other ingredients.

Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylethersulfonates, glycerolethersulfonates, methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, sulfosate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, , Mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, 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, A- cylglutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates.

If the anionic surfactants contain polyglycol ether chains, they can 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 or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or glucoronic acid derivatives, fatty acid-N-t-alkylacyl amides (especially vegetable hydrolysates), in particular hydrofluoric acid products (N-alkylactyls) Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts.

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

According to a further particularly preferred embodiment, the cosmetic composition according to the invention is used as a sunscreen. The resulting advantages have already been explained in detail.

The use of the zinc oxide dispersions according to the invention is also particularly possible in hair cosmetics such as shampoos, conditioners, conditioners, hair lotions, hair gel, hair spray etc. In particular leave-on products which remain on the hair or scalp after application are particularly suitable. The zinc oxide applied to the scalp and hair in this way can thus also act as a UV protective agent there or develop its skin-soothing effect on the scalp.

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 since it is easy to handle, so that incorrect dosing is largely excluded. Furthermore, an additional skin care effect can be achieved. If only individual parts of the body are exposed to solar radiation, the sunscreen can also only be applied specifically to these parts of the body. Another object of the present invention is the use of the metal oxides surface-modified according to the invention for UV protection. This is particularly advantageous because, due to the fine particle size, for example of the surface-modified zinc oxide and the good distribution, a particularly high UV absorption is achieved.

Another object of the present invention is the use of the metal oxides surface-modified according to the invention, in particular zinc oxide as an antimicrobial active ingredient. The use of these particles is particularly advantageous for this purpose, since due to the fine particle size and the resulting large surface area, the antimicrobial effect is greatly improved and, on the other hand, the zinc oxide is present in finely divided form due to the good dispersing properties of the material. This means that the zinc oxide can be used in various dosage forms such as creams, skin milk, lotions or tonics without any problems.

Another object of the present invention is a pharmaceutical agent which contains a surface-modified metal oxide according to the invention. This pharmaceutical agent is characterized in that the pharmaceutical effectiveness is greatly increased due to the fine particle size of the particles.

In addition, the pharmaceutical according to the invention. It has the advantage that, due to the good long-term stability already described above, the zinc oxide dispersions, for example, do not require the addition of stabilizers which prevent segregation. This additionally increases the tolerance of the pharmaceutical agent.

The invention is illustrated by the following examples.

Production of surface modified zinc oxide

Example 1:

An aqueous solution containing 8 g / l NaOH and 10 g / l polyaspartic acid, together with an aqueous solution of 15 g / l zinc (II) nitrate and a flow rate of 100 ml / min each, was continuously introduced into a mixing chamber with a volume of 0.15 mm ³ . After a reaction time of about 4 seconds, the reaction mixture was pumped continuously into a beaker and further homogenized using an Ultra Turrax. After a ripening time of 2.5 hours under magnetic stirring, a milky suspension formed, from which the zinc oxide surface-modified with polyaspartic acid was filtered off and then dried in a drying cabinet at 50 ° C. for 9 h. Example 2:

1000 ml of a 0.2 M zinc (II) nitrate solution were heated to 40 ° C. and within 4 hours, with stirring, to 1000 ml of a 0.2 M NaOH solution likewise heated to 40 ° C., which additionally contained 20 g of polyaspartic acid (Sodium salt) contained, metered. The precipitated zinc oxide surface-modified using polyaspartic acid was filtered off and dried at 50 ° C. in a drying cabinet.

Example 3:

1000 ml of a 0.2 M zinc (II) chloride solution were heated to 40 ° C. and within 4 hours, with stirring, to 1000 ml of a 0.2 M NaOH solution, likewise heated to 40 ° C., which additionally contained 20 g of polyaspartic acid (sodium salt ) contained, added. The precipitated product modified with polyaspartic acid was filtered off and dried at 50 ° C. in a drying cabinet.

Example 4:

500 ml of a 0.4 M zinc nitrate solution were heated to 40 ° C. Using a peristaltic pump, 500 ml of a 0.8 M NaOH solution, likewise heated to 40 ° C. and additionally containing 40 g / l polyaspartic acid, were metered in at 5 l / h with stirring. The precipitate was stirred at 40 ° C for 4 hours. The ZnO modified with polyaspartic acid was then filtered and dried at room temperature.

Example 5:

In 600 ml of a polyaspartic acid solution (33.34 g / l) heated to 40 ° C., 200 ml of a 0.5 M zinc nitrate solution and 200 ml of a 1 M NaOH solution were added, both to 40 Heated to ° C, metered in with stirring at a rate of approximately 1.68 l / h via a hose pump. The precipitate was stirred at 40 ° C for 2 hours. The ZnO, surface-modified with polyaspartic acid, was then centrifuged and dried at room temperature.

Example 6:

250 ml of a 0.4 M NaOH solution, which additionally contained 20 g / l of polyaspartic acid, were heated to 40 ° C. and within about 5 seconds, with stirring, to 250 ml of a 0.2 M zinc acetate solution likewise heated to 40 ° C. Solution poured. The precipitate was stirred at 40 ° C for 2 hours. The ZnO modified with polyaspartic acid was then filtered and dried at room temperature. Examples of cosmetic formulations

General instructions for the preparation of the preparations according to the invention as emulsions

The respective phases A and C were heated separately to approx. 85 ° C. Phase C and the metal oxide were then stirred into phase A with homogenization. After a brief post-homogenization, the emulsion was cooled to room temperature with stirring and filled. All quantities are based on the total weight of the preparations.

Example 7:

Emulsion A, comprising 3 wt .-% Uvinul ^® T150 and 4 wt .-% of zinc oxide prepared according to Example 5

Example 8: Emulsion B containing 3 wt .-% Uvinul ^® T150, 2 wt .-% Uvinul ^® A Plus and 4 wt .-% of zinc oxide prepared according to Example 5

Example 9:

Emulsion A, comprising 3 wt .-% Uvinul ^® T150 and 4 wt .-% of zinc oxide prepared according to Example 2

Example 10:

Emulsion B, containing 3% by weight of Uvinul ^® T150, 2% by weight of Uvinul ^® A Plus and 4% by weight of zinc oxide, prepared according to Example 2

Claims

claims

1. Surface-modified nanoparticulate metal oxides, the metal being selected from the group consisting of aluminum, cerium, iron, titanium, zinc and zirconium, characterized in that the surface modification comprises a coating with polyaspartic acid.

2. Surface modified metal oxides according to claim 1, characterized in that the metal oxide particles have an average primary particle diameter of 5 to 10000 nm.

3. Surface-modified metal oxides according to one of claims 1 or 2, characterized in that the surface is modified with polyaspartic acid with a molecular weight M _w of 1000 to 100000.

Metal oxides according to one of claims 1 to 3, characterized in that it is surface-modified zinc oxide.

5. A process for producing a surface-modified nanoparticulate metal oxide, the metal being selected from the group consisting of aluminum, cerium, iron, titanium, zinc and zirconium by a. Precipitation of the metal oxide from an aqueous solution of one of its metal salts, b. Separation of the precipitated metal oxide from the aqueous reaction mixture and c. subsequent drying of the metal oxide, characterized in that the precipitation of the metal oxide in process step a. in the presence of polyaspartic acid.

6. The method according to claim 5, characterized in that the metal salts are metal halides, acetates, sulfates or nitrates.

7. The method according to any one of claims 5 or 6, characterized in that the precipitation is carried out in the presence of polyaspartic acid with a molecular weight M _w of 1000 to 100000.

8. The method according to any one of claims 5 to 7, characterized in that the precipitation takes place at a temperature in the range from 20 ° C to 100 ° C.

9. The method according to any one of claims 5 to 8, characterized in that the precipitation takes place at a pH in the range from 3 to 12.

10. The method according to any one of claims 5 to 9 for the production of surface-modified nanoparticulate zinc oxide.

11. The method according to claim 10, characterized in that the precipitation of the zinc oxide in process step a. from an aqueous solution of zinc (II) chloride or zinc (II) nitrate at a temperature in the range from 25 to 40 ° C and a pH in the range from 7 to 11 in the presence of polyaspartic acid with a molecular weight M _w of 1000 to 7000 takes place.

12. Use of surface-modified nanoparticulate metal oxides, defined according to one of claims 1 to 4, for the production of cosmetic preparations.

13. Use according to claim 12 for the production of cosmetic sunscreen preparations.

14. Cosmotic preparations containing surface-modified nanoparticulate metal oxides, defined according to one of claims 1 to 4.