DE10007116A1 - Aqueous dispersions, dry powders and double dispersions containing difficultly water-soluble or insoluble organic UV filter substances (especially triazines) for use in plastics, lacquers, cosmetics or pharmaceuticals - Google Patents

Abstract

Aqueous dispersions of difficultly water-soluble or water-insoluble organic UV filter substances (I) contain at least one such substance as a colloidally-dispersed phase in amorphous or partly amorphous form. Also included are Independent claims for: (1) the production of the dispersions by: (a) treating a molecularly-disperse organic solvent solution of (I) with an aqueous solution of a protective colloid so as to convert the hydrophobic phase of the substance into a colloid disperse phase and then removing the organic solvent; or (b) treating a molecularly-disperse organic solvent solution containing (I) and also a water-insoluble polymer with water or with an aqueous solution of a protective colloid so as to convert the hydrophobic phase of (I) and the polymer into a colloid disperse phase and then removing the organic solvent; and (2) production of dry powders by removal of the water and drying optionally in the presence of a coating material, these powders then being optionally converted into double dispersions by emulsifying in an oil.

Description

The invention relates to aqueous dispersions heavy water soluble or water-insoluble organic UV filter substances, their production and further processing into dry powders as well their use as photostable light stabilizers.

The quality or lifetime of many organic materials, For example, plastics and paints but also pharmaceutical and cosmetic preparations can by exposure to light, especially negatively affected by UV rays. These quality losses are evident in plastics and paints often in yellowing, discoloration, cracking or embrittlement of the Material. In the case of pharmaceutical and cosmetic use Because of the influence of UV rays, it can reduce the active ingredients contained in the formulations.

The damaging effect of the ultraviolet part of the sun's rays on the skin or hair, which in the broadest sense also represent organic material is also a problem that is gaining more and more importance. While blasting with a Wavelength less than 290 nm (the so-called UVC Area) absorbed by the ozone layer in the earth's atmosphere be, cause rays in the range between 290 nm and 320 nm, the so-called UVB range, an erythema on the skin, a simple sunburn or even more or less strong Burns.

As a maximum of the erythema efficiency of sunlight, the narrower range indicated by 308 nm.

For protection against UVB radiation are numerous compounds be knows, where u. a. to derivatives the 3-Benzylidencam phers, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and 2-phenylbenzimidazole.

Also for the range between about 320 nm and about 400 nm, the so-called UVA range, it is important to filter substances for To have available because its rays reactions in light sensitive skin. It has been proven that UVA Radiation damage to the elastic and collagen Fibers of connective tissue causes what the skin ages prematurely and that they are the cause of numerous phototoxic and  photoallergic reactions can be seen. The injurious one The flow of UVB radiation can be enhanced by UVA radiation.

For protection against UVA rays are derivatives of dibenzoyl methane used, but their photostability is not in given to a large extent (Int J. Cosm. Science 10, 53 (1988)).

The UV radiation can also cause photochemical reactions lead, in which case the photochemical reaction products in the Skin metabolism intervene.

Predominantly, such photochemical reaction products to radical compounds, such as hydroxy radical. Also undefined radical photoproducts, which in The skin itself can develop due to their high reactivity uncontrolled follow-up actions. But also Singlet oxygen, a non-radical excited state of the oxygen molecule can occur on UV irradiation, as well short-lived epoxides and many others. singlet For example, is distinguished from the normally present triplets oxygen (radical ground state) by ge increased reactivity. However, there are also excited, reactive (radical) triplet states of the oxygen molecule.

Furthermore, UV radiation counts as ionizing radiation. It exists So the risk that also ionic species in UV exposure ent which then in turn oxidatively into the biochemical Pro to intervene.

An application disadvantage of many UV filters is their poor solubility in water and / or in lipids whereby their Use, for example, in cosmetic formulations often is restricted.

Another disadvantage with the application of some sunscreen tel is due to the appearance of skin irritations and allergies from too high skin permeability.

GB-A-2 303 549 discloses a milling process for the production of micronized insoluble organic UV absorbers in the presence of alkylpolyglycosides. The microni thus obtained sate can be incorporated into cosmetic sunscreen preparations be.  

GB-A-2 286 774 also describes a micromilling process nization of insoluble organic UV absorbers.

It was now an object of the present invention, UV light protection mitmit tel formulations that provide an effective Protection for organic material, especially for human Skin and / or human hair from UV rays and which work well in aqueous and lipophilic systems let it go.

This problem has been solved by aqueous dispersions difficult water-soluble or water-insoluble organic UV filterub punching, characterized in that they at least one hard water-soluble or water-insoluble organic UV filter substance as a colloid-disperse phase in amorphous or partially amorphous form contain.

Under the name aqueous dispersions are within the present invention, both aqueous suspensions and Emul understandings. Preference is given to aqueous suspensions call, in which the dispersed phase at least one hard water-soluble or water-insoluble organic UV filter substance as nanoparticulate particles. In the foreground of the creator Moreover, the compounds of the above aqueous are also available Suspensions prepared dry powder or emulsions before added to double emulsions, in particular o / w / o emulsions.

Among poorly water-soluble organic UV filter substances in this context, to understand those compounds whose Water solubility <5 wt .-%, preferably <1 wt .-%, particularly be preferably <0.5% by weight, very particularly preferably <0.1% by weight.

The new sunscreen formulations are charact that they contain at least one sparingly water-soluble or water-insoluble organic UV filter substance whose amorphous content in the range greater than 10%, preferably greater than 30%, be more preferably in the range of 50 to 100%, especially be preferably in the range of 75 to 99%. The determination of Crystallinity rate of the UV filter substances can example way done by X-ray diffraction measurements.

The content of at least one sparingly water-soluble or what serunlöslichen organic UV filter substance in the erfindungsge The light stabilizer formulations are in the range of 0.1 to 70 wt .-%, preferably in the range of 2 to 40 wt .-%, in particular It preferably ranges from 3 to 30 wt .-%, most preferably  in the range of 5 to 25 wt .-%, based on the dry mass of the formulations.

The mean particle size of the nanoparticulate particles in the aqueous dispersion is depending on the type of formulation method in Area smaller than 10 μm, preferably in the range smaller than 5 μm, especially ders preferably in the range of 0.01 to 2 microns, especially be preferably in the range of 0.05 to 1 micron.

A preferred form of the aqueous dispersions according to the invention is characterized in that the particles of the colloid-disper sen phase have a core / shell structure, the core minde at least one sparingly water-soluble or water-insoluble organic Contains UV filter substance. The shell enclosing the core contains essentially at least one protective colloid, preferably one higher molecular weight compound.

The purpose of this polymer shell is to release the particles in their colloid dalen state against heterogeneous particle growth (aggregation, Flocculation, etc.) to stabilize.

One or more polymers may be used for this purpose become. The molecular weights of the polymers used are in the range from 1000 to 10,000,000 g / mol, preferably in the range of 1,000 to 1000000 g / mol. Basically, all come for the Anwendungsbe rich pharmaceutical and cosmetic suitable polymers into consideration.

Suitable as polymeric stabilizers for the shell's shell matrix According to the invention advantageously water-soluble or what water-swellable protective colloids such as bovine, porcine or fish gelatin, in particular sour or base degraded Ge latin with Bloom numbers in the range of 0 to 250, especially preferably gelatin A 100, A 200, B 100 and B 200 and lower molecular, enzymatically degraded gelatin types with the bloom Number 0 and molecular weights from 15,000 to 25,000 D as for Example Collagel A and Gelitasol P (company Stoess, Eberbach) so such as mixtures of these types of gelatin and starch, dextrin, Pectin, gum arabic, lignosulfonates, chitosan, polystyrene sul fonate, alginates, casein, caseinate, methylcellulose, carboxy methylcellulose, hydroxypropylcellulose, milk powder, dextran, Whole milk or skimmed milk or mixtures of these protective colloids. Furthermore, homo- and copolymers are based on new tralen, cationic or anionic monomers such. B. ethylene oxide, propylene oxide, acrylic acid, maleic anhydride, lactic acid, N-vinyl pyrrolidone, vinyl acetate, α- and β-aspartic acid.  

The water solubility or water swellability of the o. polymers depends on the temperature, the pH and the Ionic strength of the solution.

Another, likewise preferred form of the invention aqueous dispersion is characterized in that the particles the colloid-disperse phase additionally a water-insoluble Polymer matrix containing, in the at least one difficult wasserlöslös Liche or water-insoluble organic UV filter substance is bedding. To improve the colloidal stability of these aqueous dispersion, it may be advantageous if the disper giert particles of one of the above. Protective colloids around are shrouded.

The matrix polymers inside the particles contribute to the To get drug in its non-crystalline state, as well the colloidal structures in terms of homogeneous particles growth (Ostwald ripening).

As polymeric constituents, which are in the core of the particles of the The preparation of active compound according to the invention are suitable basically all polymers that are in a temperature range between 0 and 240 ° C, a pressure range between 1 and 100 bar, a pH range from 0 to 14 or ionic strengths up to 10 mol / l or not only partially in water or aqueous solutions or water Solvent mixtures are soluble.

In this context, no or only partially soluble means that the second virial coefficient for the polymer or polymers in water or a mixture of water and an organic solvent can assume values below zero. (See MD Lechner, "Macro Molecular Chemistry", Birkhäuser Verlag, Basel, pp. 170-175). The second virial coefficient, which makes a statement about the behavior of a polymer in a solvent (mixture), can be determined experimentally, for example by light scattering measurement or determination of the osmotic pressure. The dimension of this coefficient is (mol.l) / g ² .

One or more polymers can be used. The moles masses of the polymers used are in the range of 1000 to 10000000 g / mol, preferably in the range of 1000 to 1,000,000 g / mol. Basically, all come for the application area Pharma and Cosmetics suitable polymers into consideration.

Of particular interest are polymers used in organic, with Water-miscible solvents are soluble, and at Tempe temperatures between 0 and 240 ° C not or only partially in water  or aqueous solutions or water-solvent mixtures are. The following polymers are exemplified, but without to be restrictive:

Poly (vinyl ethers) such as. Poly (benzyloxyethylene), poly (vinylacet tals), poly (vinyl ketones), poly (allyl alcohol), poly (vinyl esters) such as As poly (vinyl acetate), poly (oxytetramethylene), poly (glutar dialdehyde), poly (carbonates), poly (ester), poly (siloxanes), Poly (amides), poly (piperazines), poly (anhydrides) such as. B. poly (me tharyanhydride), Gutta Percha, cellulose ethers such as. B. Methylzel lulose (substitution ridge: 3 to 10%), ethyl cellulose, butylcel cellulose, cellulose esters, such as. As cellulose acetate or starches. In particular, copolymers and block copolymers of the monomers of the above mentioned polymers. Furthermore, copolymers and block copolymers of Polyesters and hydroxycarboxylic acids and linear and star poly ethylene glycol, e.g. B. AB, ABA and ABC block copolymers of a Combination of L-poly (lactide), polyglycolide and / or poly ethylene glycol, e.g. Resomer 505, Resomer RG-756 or Resomer RG-858 (Böhringer Ingelheim).

Of particular interest are also polymers disclosed by Tem temperatures between 0 and 240 ° C in water or aqueous solutions or water-solvent mixtures an upper and / or lower Have miscibility gaps, d. H. by increasing or decreasing the temperature of these polymers from appropriate solutions be precipitated. The following polymers are mentioned by way of example, without being limiting, however:

Poly (acrylamides), poly (methacrylamides) such. B. Poly (N-isopropylacrylamide), poly (N, N-dimethylacrylamide), Poly (N- (1,1-dimethyl-3-oxobutyl) acrylamide), poly (methoxyethylene), Poly (vinyl alcohols), acetylated poly (vinyl alcohols), Poly (oxyethylene), cellulose ethers such. B. methyl cellulose (Degree of substitution: 20 to 40%), isopropyl cellulose, Cellulose esters, starches, modified starches such. B. Methyl ether starch, gum arabic, as well as copolymers or Block copolymers of monomers of the above-mentioned compounds. In particular AB or ABA block copolymers on the basis Ethylene oxide and propylene oxide, e.g. Poloxamers such as poloxamer 188 and Poloxamer 407.

Of particular interest are also polymers disclosed by Tem temperatures between 0 and 240 ° C in water or aqueous solutions or water-solvent mixtures by varying the pH or the ionic strength can be precipitated from appropriate solutions  can. The following polymers are exemplified without but to be limiting:

Alginates, Chitosan, Chitin, Schellak, Polyelectrolytes, Poly (acrylic acid), poly (methacrylic acid), poly (methacrylic ester) with with secondary tertiary or quaternary amino groups, ins special copolymers or block copolymers based on different which acrylates, methacrylates, methacrylic acid, acrylic acid, z. B. a copolymer of methacrylic acid / methacrylic acid ester (weight ratio MAS / MAE 1: 1 or 1: 2) or a copolymer of dimethyl aminoethyl methacrylate and methacrylic acid ester by weight ratio 1: 1 (Eudragit® types).

The amounts of the various components are according to the invention chosen so that the preparations, in addition to the abovementioned UV Filter substances 0.1 to 80 wt .-%, preferably 5 to 70 wt .-% be more preferably 10 to 60 wt .-%, most preferably 15 to 35% by weight of one or more polymeric protective colloids (Hüll polymer) and optionally 0.1 to 80 wt .-%, preferably 0.5 to 70 wt .-%, particularly preferably 1 to 50 wt .-%, very particularly preferably 5 to 35 wt .-% of one or more matrix polymers for contain the core. The percentages by weight relate to the dry matter of the sunscreen formulation.

In addition, the preparations can still low molecular Stabi dispersants such as antioxidants and / or preservatives for Protection of UV filter substances included. Suitable anti Oxidants or preservatives are, for example, α-Toco pherol, ascorbic acid, tert-butyl-hydroxytoluene, tert-butyl hydroxyanisole, lecithin, ethoxyquin, methylparaben, propylpara ben, sorbic acid or sodium benzoate. The antioxidants or Preservatives may be in amounts of 0.01 to 50 wt .-%, be preferably from 0.1 to 30% by weight, particularly preferably from 0.5 to 20% by weight, most preferably 1 to 10 wt .-%, based on the Dry matter of sunscreen formulation.

Furthermore, the dispersions can still plasticizer to increase the mechanical stability of an optionally derived herge contained dry powder. Suitable plasticizers are for example, sugars and sugar alcohols such as sucrose, glucose, Lactose, invert sugar, sorbitol, mannitol, xylitol or glycerin. Preferably, lactose is used as the plasticizer. The soft agents may be used in amounts of from 0.1 to 70% by weight, preferably from 10 to 60% by weight, particularly preferably 20 to 50 wt .-%, based on the Dry mass of the sunscreen formulation may be included.  

Furthermore, the sunscreen formulations may be low molecular weight kular surface-active compounds (emulsifiers) in a con concentration of 0.01 to 70% by weight, preferably 0.1 to 50% by weight, particularly preferably 0.5 to 20 wt .-%, based on the dry mass of the sunscreen formulation. As such are particularly suitable amphiphilic compounds or mixtures sol cher connections. Basically, all surfactants come with a HLB value of 5 to 20 into consideration. As appropriate surfaces active substances are for example: esters long chain fatty acids with ascorbic acid, mono- and diglycerides of Fatty acids and their oxyethylation products, esters of monofatty Acid glycerides with acetic acid, citric acid, lactic acid or Diacetyltartaric, Polyglycerinfettsäureester such. For example, the mono stearate of triglycerin, sorbitan fatty acid ester, propylene glycol fatty acid esters and lecithin. Preferably, ascorbyl palmitate is included set.

Under certain circumstances, it may also be advantageous to additionally physiologically approved oil such as sesame oil, corn germ oil, cottonseed oil, soy or peanut oil, as well as kosme table oils, for example paraffin oil, glyceryl stearate, isopro pylmyristate, diisopropyl adipate, 2-ethylhexanoic acid cetylstearyl ester, hydrogenated polyisobutene, vaseline, caprylic acid / caprin acid triglycerides, microcrystalline wax, lanolin and stearin acid in a concentration of 0.1 to 500 wt .-%, preferably 10 to 300 wt .-%, particularly preferably 20 to 100 wt .-%, based on the (hardly) water-soluble or water-insoluble used to use organic UV filter substance (s).

As sparingly water-soluble or water-insoluble organic UV Filter substances are u. a. Compounds from the group of tria zine, anilides, benzophenones, triazoles, cinnamamides and the called sulfonated benzimidazoles.

As a particular embodiment of the aqueous dispersion according to the invention dispersions are to be mentioned which contain at least one 1,3,5-triazine derivative of the formula I,

in which the substituents independently of one another have the following meaning:
R is hydrogen, halogen, OH, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -alkoxy, C ₁ -C ₂₀ -alkoxyalkyl, C ₁ -C ₂₀ -hydroxyalkoxy, NR ¹ R ² ,
or a radical of the formula Ia

R ¹ and R ^{2 are} hydrogen, C ₁ -C ₂₀ -alkyl, optionally substituted by one or more C ₁ -C ₄ -alkyl-substituted C ₆ -C ₁₂ -aryl, optionally substituted by one or more C ₁ -C ₄ -alkyl C ₇ -C ₁₀ aralkyl, heteroaryl optionally substituted by one or more C ₁ -C ₄ alkyl, C ₅ -C ₈ cycloalkyl;
R ³ to R ^{5 are} hydrogen, OH, NR ⁹ R ¹⁰ , C ₁ -C ₂₀ alkoxy, optionally substituted by one or more C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₂ aryl, where appropriate with one or more C C ₁ -C ₄ -alkyl-substituted C ₇ -C ₁₀ -aralkyl, heteroaryl optionally substituted by one or more C ₁ -C ₄ -alkyl, C ₅ -C ₈ -cycloalkyl;
R ⁶ to R ^{8 are} hydrogen, C ₁ -C ₂₀ alkoxy, -C (= O) -R ¹¹ , -C (= O) -XR ¹² , SO ₂ R ¹³ , CN;
R ⁹ to R ¹¹ is hydrogen, C ₁ -C ₂₀ alkyl optionally substituted with one or meh reren C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₂ aryl, optionally substituted with one or more C ₁ -C ₄ alkyl C C ₇ -C ₁₀ aralkyl, heteroaryl optionally substituted by one or more C ₁ -C ₄ alkyl, C ₅ -C ₈ cycloalkyl;
R ^{12 is} hydrogen, C ₁ -C ₂₀ -alkyl, optionally substituted by one or more C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₂ aryl, optionally substituted by one or more C ₁ -C ₄ alkyl-substituted C ₇ -C ₁₀ aralkyl, optionally substituted by one or more C ₁ -C ₄ alkyl substituted heteroaryl, C ₅ -C ₈ cycloalkyl or a radical of the formula Sp-Sil;
R ^{13 is} C ₁ -C ₂₀ -alkyl, C ₅ -C ₈ -cycloalkyl, optionally substituted by one or more C ₁ -C ₄ -alkyl-substituted C ₆ -C ₁₂ -aryl, if appropriate with one or more C ₁ -C ₄ - Alkyl substituted C ₇ -C ₁₀ aralkyl, heteroaryl optionally substituted with one or more C ₁ -C ₄ alkyl;
XO, NR ¹⁴ ;
R ^{14 is} hydrogen, C ₁ -C ₂₀ -alkyl, optionally substituted by one or more C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₂ aryl, optionally substituted by one or more C ₁ -C ₄ alkyl-substituted C ₇ -C ₁₀ aralkyl, optionally substituted by one or more C ₁ -C ₄ alkyl substituted heteroaryl, C ₅ -C ₈ cycloalky;
Sp spacer;
Sil residue from the group consisting of silanes, oligosiloxanes and polysiloxanes.

Alkyl radicals for R, R ¹ and R ² and R ⁹ to R ¹⁴ are branched or unbranched C ₁ -C ₂₀ -alkyl chains, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2- Dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylhutyl, 3 , 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n -octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, n-nonyl, n-decyl, n-undecyl, 1-methylundecyl, n-dodecyl, 1,1, 3,3,5,5-hexa methylhexyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl called.

Halogen for R means fluorine, bromine, iodine or preferably chlorine.

As alkoxy for R and R ³ to R ⁸ are straight-chain and ver branched radicals having 1 to 20 carbon atoms, preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms into consideration.

For example:

methoxy ethoxy isopropoxy n-propoxy 1-Methylpropoxy- n-butoxy n-pentoxy 2-Methylpropoxy- 3-methylbutoxy 1,1-dimethylpropoxy 2,2-dimethylpropoxy hexoxy 1-methyl-1-ethylpropoxy heptoxy octyloxy 2-Ethylhexoxy-

Hydroxyalkoxy radicals for R are the above mentioned. Alkoxy radicals with too additional terminal Hodroxylfunktion into consideration.

As cycloalkyl radicals R ¹ to R ⁵ and R ⁹ to R ^{14 are} preferably branched or unbranched C ₃ -C ₁₀ -cycloalkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-1-butylcyclo propyl, 1,2-dimethylcyclopropyl, 1-methyl-2-ethylcyclopropyl, cyclooctyl, cyclononyl or cyclodecyl called. Preference is given to C ₅ -C ₈ -cycloalkyl such as cyclopentyl, cycloheptyl, cyclooctyl and in particular cyclohexyl.

The cycloalkyl radicals may optionally with one or more, for. B. 1 to 3 radicals such as halogen z. For example, fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or other radicals be substituted or 1 to 3 heteroatoms such as sulfur, nitrogen, whose free valencies Kings K saturated by hydrogen or C ₁ -C ₄ alkyl or contain oxygen in the ring.

Examples of C ₆ -C ₁₂ -aryl are, in particular, phenyl, naphthyl and biphenyl.

Examples of C ₇ -C ₁₀ aralkyl are benzyl, phenylethyl, α-methyl phenylethyl or α, α-dimethylbenzyl.

Heteroaryl radicals are advantageously simple or condensed based aromatic ring systems with one or more heteroaro matic 3- to 7-membered rings. As heteroatoms can be a or more nitrogen, sulfur and / or oxygen atoms in the Ring or ring system may be included.

As substituents of the abovementioned aryl, aralkyl and heteroaryl radicals, C ₁ -C ₄ -alkyl groups are, for example, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl in question.

The term spacer for Sp in this context means a bivalent branched or unbranched C ₃ -C ₁₂ -alkylene or alkenylene chain which links the silane, oligosiloxane or polysiloxane part with the triazine radical.

Examples of a C ₃ -C ₁₂ alkylene chain are propylene, 2-methylpropylene, butylene, pentylene and hexylene.

Examples of a C ₃ -C ₁₂ alkenylene chain are 2-propen-2-ylene, 2-methyl-3-propenylene, 3-buten-3-ylene and 4-penten-4-ylene.

Preferred spacers are - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - [CH (CH ₃ )] - (CH ₂ ) -, - (CH ₂ ) ₂ -CH = CH-, -C (= CH ₂ ) -CH ₂ -, -C (= CH ₂ ) - (CH ₂ ) ₂ -O- (CH ₂ ) ₄ -, - (CH ₂ ) ₄ -O- (CH ₂ ) ₂ -.

The term silanes in this context means a radical SiR ¹⁵ R ¹⁶ R ¹⁷ in which R ¹⁵ , R ¹⁶ , R ¹⁷ independently of one another are C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy or phenyl.

Examples are: Si (CH ₂ -CH ₃ ) ₃ , Si (CH ₂ -CH ₂ -CH ₃ ) ₃ , Si (isopropyl) ₃ , Si (tert-butyl) ₃ , Si (tert-butyl) ( CH _{3) 2,} Si (CH _{3) 2} (hexyl), Si (OCH _{3) 3,} Si (OEt) _3, SiPh. ₃

The term oligosiloxanes means a radical from the group of the general formula consisting of SiR ¹⁸ _m (OSiR ¹⁸ ₃ ) _n with m = 0, 1 or 2; n = 3, 2 or 1 and m + n = 3, R ¹⁸ - [Si (R ¹⁸ ) ₂ -O-] _r -Si (R ¹⁸ ) ₂ -A and R ¹⁸ - [Si (R ¹⁸ ) ₂ - O-] _r -Si (A) (R ¹⁸ ) -O-Si (R ¹⁸ ) ₃ , in which A is a chemical bond or a spacer and R ^{18 is} a C ₁ -C ₆ -alkyl radical or phenyl radical and r is values from 1 to 9 stands.

The term polysiloxanes includes, for example, a radical from the group of the general formula consisting of A- [Si (R ¹⁹ ) ₂ -O] _s -Si (R ¹⁹ ) ₂ -A or (R ¹⁹ ) ₃ -Si- [O-] Si (R ¹⁹ ) ₂ ]] _t - [O-Si (R ¹⁹ ) (A)] _q -O-Si (R ¹⁹ ) ₃ in which A is a chemical bond or a spacer and R ^{19 is} a C ₁ -C ₆ alkyl or phenyl, s and t are from 4 to 250 and q is from 1 to 30.

Examples of silanyl triazines in which R ^{12 is} a radical of the For mel Sp-Sil can be found in EP-A-0 933 376.

In the foreground are triazine compounds of the formula Ib,

wherein R ³ to R ⁵ are ortho to the phenylamino radical of the triazine.

Preference is given to aqueous dispersion comprising at least one 1,3,5-triazine derivative of the formula Ib in which the substituents un depend on one another have the following meanings:
R ³ to R ⁵
Hydrogen, OH;
R ⁶ to R ⁸
C ₁ -C ₁₂ alkoxy, -C (= O) -XR ¹² ;
XO, NR ¹⁴ ;
R ¹² and R ¹⁴
Hydrogen, C ₄ -C ₈ -alkyl.

A particularly advantageous UVB filter is 2,4,6-trianilino p- (carbo-2'-ethylhexyl-1'-oxi) -1,3,5-triazine obtained from BASF Joint-stock company under the trade name Uvinul® T 150 ver is marketed.

Uvinul® T 150 is characterized by good UV absorption properties with an exceptionally high extinction coefficient <1500 at 314 nm.

Other sparingly water-soluble or water-insoluble organic UV filter substances from the group of the triazines include the following compounds described in WO 94/05645 and EP-A-0 444 323:

Preferred anilides are compounds of the formula II in which W ¹ and W ² independently of one another are C ₁ -C ₁₈ -alkyl or C ₁ -C ₁₈ -alkoxy.

Particularly preferred is N- (2-ethoxyphenyl) -N '- (2-ethylphe nyl) -ethandiamid.

Preferred triazoles are compounds of the formula III in which, independently of one another, T ^{1 is} C ₁ -C ₁₈ -alkyl or hydrogen and T ^{2 is} C ₁ -C ₁₈ -alkyl.

Another preferred class of water-insoluble triazoles are compounds of the formula IIIa in which T ² denotes C ₁ -C ₁₈ -alkyl.

Also preferred representatives from the group of water-insoluble triazoles are compounds of the formula IIIb and IIIc in which T ^{2 is} C ₁ -C ₁₈ -alkyl, preferably tert-butyl (in the case of IIIb) and methyl (in the case of IIIc).

Preferred cinnamamides are compounds of the formula IV in which Y ¹ and Y ² independently of one another are hydrogen or C ₁ -C ₄ -alkyl, preferably methyl or ethyl, and Y ^{3 is} aryl, preferably phenyl or 4-methoxyphenyl.

Preferred sulfonated benzimidazoles are compounds of the formula V, in the M for hydrogen, an alkali metal - preferably sodium - or an alkali metal such as magnesium, calcium or zinc.

Preferred benzophenones are compounds of the formula VI in which, independently of one another, M ¹ to M ^{4 are} hydrogen or C ₁ -C ₄ -alkyl, M ¹ and M ^{4 are} preferably methyl or ethyl and M ² and M ^{3 are} preferably hydrogen.

The spherical isotropic character of the present invention Dispersions contained particles shows in contrast to ge milled anisotropic particles no pseudoplastic behavior. An incorporation of this dispersion, for example in cosmetic Formulations and the application of these formulations is so with much easier.

Furthermore, it could be shown that a sunscreen on Ba sis the dispersion of the invention by a factor of 4 height Sun protection factor has as an analog sunscreen medium preparation in which the same amount of UV filter substance mole Kular Dispers has been present.

While ground UV filter substances in training in Skin creams increasingly tend to particle size growth, that too a deterioration of the sun protection factor and a unan can lead to a pleasant feeling on the skin, show the inventive Dispersions due to their matrix and protective colloid structure of not like style.

The invention also provides a process for preparing an aqueous dispersion containing at least one sparingly water-soluble or water-insoluble organic UV filter substance as colloidally disperse phase in amorphous or partially amorphous form, characterized in that

• a) a molecular disperse solution of at least one heavy water soluble or water insoluble organic UV filterub produced in an organic solvent,
• b) this solution with an aqueous solution of at least one Protective colloid, with the hydrophobic phase of the UV Filter substance as a colloid-disperse phase is formed and  
• c) the resulting dispersion of organic solvent be freed.

As organic solvent in process step a) is before Partially, at least one water-miscible, organic Solvent or a mixture of water and at least one used with water-miscible organic solvent.

The preferred solvents are, in particular, water-miscible ble, thermally stable, volatile, only carbon, water substance and oxygen containing solvents such as alcohols, To name ethers, esters, ketones and acetals. Appropriately used such solvents, which are at least 10% water-miscible are, have a boiling point below 200 ° C and / or less than Have 10 carbons. Particularly preferred are ethanol, n-Pro panol, isopropanol, 1,2-butanediol-2-methyl ether, 1,2-propane diol-1-n-propyl ether, tetrahydrofuran or acetone.

The method is further characterized in that the Solution in step a) optionally further additives, out selects from the group consisting of emulsifiers, antioxidants, Preservatives, water-insoluble polymers and edible Adding oils and / or that in step b) the aqueous contactor colloid idlösung additionally contains at least one plasticizer. It is but also possible one or more emulsifiers of protection Add colloid solution. To describe these additives Please note the explanations given at the beginning.

In a preferred embodiment of the method is in Step a) the molecular disperse solution of at least one heavy water-soluble or water-insoluble organic UV filterub at temperatures above 15 ° C, preferably at temperatures in the Range of 50 ° C to 240 ° C, more preferably in the range of 140 ° C to 180 ° C and immediately afterwards in Step b) with the aqueous solution of the protective colloid, wherein a mixture temperature of about 35 ° C to 120 ° C, be more preferably from 55 ° C to 70 ° C sets.

The invention furthermore relates to a process for the preparation of an aqueous dispersion of at least one sparingly water-soluble or water-insoluble organic UV filter substance in which the particles of the colloidally disperse phase contain a water-insoluble polymer matrix into which at least one sparingly water-soluble or water-insoluble organic UV Embedded filter, characterized in that one

• a) a molecular disperse solution of at least one heavy water soluble or water-insoluble organic UV filter substance and at least one water-insoluble polymer in produces an organic solvent,
• b) this solution with water or an aqueous solution at least a protective colloid, wherein the hydrophobic phase of the Mixture of UV filter substance and water-insoluble polymer arises as a colloid-disperse phase and
• c) the resulting dispersion of organic solvent freed.

According to one embodiment of the method, a molecular disperse solution of UV filter substance in the chosen solution together with the polymer that is present in the sunscreen agent Preparation should be located in the core of the particles. This Polymer has the property, in a certain temperature, pH or salt portion is not or only partially soluble in water his.

The concentration of the sunscreen-polymer Solution is generally 10 to 500 g of at least one poorly water-soluble or water-insoluble UV filter substance per 1 kg of solvent and 0.01 to 400 g of polymer, the Polymer light stabilizer weight ratio between 0.01 to 1 and 5 to 1. In a preferred embodiment of Ver The low molecular weight stabilizer goes directly to the Light stabilizer-polymer solution given.

In a subsequent process step, the Light stabilizer-polymer solution with water or preferably one aqueous solution of the polymeric shell material mixed. The Concentration of the polymeric shell material is generally 0.1 to 200 g / l, preferably 1 to 100 g / l.

According to another embodiment of the method is a molecular disperse solution of UV filter substance in the selected Solvent without the polymer used in the sunscreen Preparation should be located in the core of the particles. The Concentration of the sunscreen solution thus prepared be generally carries 10 to 500 g of UV filter substance per 1 kg Solvent.

In a subsequent process step, this is Solution with an aqueous molecular solution of the polymer ge mixed in the light stabilizer preparation at the core of the  Particles should lie. The concentration of the so produced Polymer solution is generally from 0.01 to 400 g of polymer. The temperatures, pH values and salt concentrations are of the two solutions to be united so chosen that after the Association of solutions UV filter substance and polymer in the insoluble solution are insoluble. In a preferred off The method of the method is the low molecular Stabilisa tor directly to the drug solution.

In a subsequent process step is the Light stabilizer-polymer precipitate with an aqueous solution of the polymeric shell material. The concentration of polymeric shell material is 0.1 to 200 g / l, preferably 1 up to 100 g / l.

The mixing process may be discontinuous or, preferably, conti to be done wisely. As a result of the mixing process, it comes to a Precipitation.

Which conditions in the implementation of the invention Method with regard to variation of the system water / organic Solvent, the pH, the temperatures or the ions Strengths to be chosen in a specific case, the expert can with Help the 2nd Virialkoeffizienten by some simple Vorver search for the appropriate polymer.

The invention also provides a process for the preparation a dry powder containing at least one heavy water soluble or water-insoluble organic UV filter substance as nanoparticulate particles in amorphous or partially amorphous form, since characterized in that one of the o. g. invention aqueous dispersions freed of water and, optionally in Presence of a coating material, dries.

The conversion into a dry powder can be, for example by spray drying, freeze drying or drying in the vortex bed, if appropriate also in the presence of a coating material respectively. As a coating agent are u. a. Cornstarch, pebbles acid or tricalcium phosphate.

In the lyophilization of nanoparticles according to the invention can cryoprotective substances such. B. trehalose or polyvinyl pyrrolidone be added.

Dry powder can thus be obtained in accordance with the invention their properties recovered in the primary dispersion no longer to lose. That is, the amorphous character of the UV filter substance  as well as the core-shell structure is preserved. It is furthermore a property according to the invention, which this Dispersions on redissolution with a deviation of 20% preferably <15% show the same particle size distribution, the they had as primary dispersion.

Claimed are also powdered preparations, available after one of the o. g. Process containing at least one heavy water-soluble or water-insoluble organic UV filters substance as nanoparticulate particles in amorphous or part amorphous form.

The invention also relates to a process for the manufacture an oil-miscible preparation in the form of a double Dispersion containing at least one sparingly water-soluble or water-insoluble organic UV filter substance in amorphous or teilamorpher form, characterized in that the beginning emulsified aqueous emulsions in oil emulsified.

In this case, using an emulsifier, a water-in-oil Emulsion formed in the water phase Schutzkolloidstabili nano particles of at least one sparingly water-soluble or water-insoluble organic UV filter substance contains. When Emulsifiers come in known W / O emulsifiers with a HLB value less than 10, in particular from 2 to 6 into consideration (see. H. P. Fiedler, Lexicon of excipients for pharmacy, cosmetics and adjacent areas, 1996, pages 753 ff). Typical representatives This emulsifier class are partial fatty acid esters mehrwertiger Alcohols z. As glycerol monostearate or mixtures of mono-, di- and triglycerides, partial fatty acid esters of sorbitan and / or preferably fatty acid esters of polyglycerol such as Polyglycerol polyricinoleate, which in a concentration of 10 to 1000 wt .-%, preferably 100 to 900 wt .-%, especially before zugt 400 to 800 wt .-%, based on the UV filter substance (s), be used.

The dispersant may be synthetic, mineral, be of plant as well as animal origin. Typical Ver people are u. a. Sesame oil, corn oil, cottonseed oil, soy bean oil or peanut oil, ester medium-chain vegetable fat acids and paraffin oil, glyceryl stearate, isopropyl myristate, Diisopropyl adipate, 2-ethylhexanoic acid cetylstearyl ester, hydrogenated Polyisobutene, vaseline, caprylic acid / capric acid triglycerides, microcrystalline wax, lanolin and stearic acid. The amount of Dispersant is generally from 30 to 95, preferably  50 to 80 wt .-%, based on the total mass of the finished Emul sion.

You can emulsify continuously or discontinuously carry out.

The physical stability of the double dispersion system, such as the sedimentation stability is achieved by a very good fine distribution of the water phase in the oil phase, z. B. by intensive treatment with a rotor / stator disperser Temperatures of 20 to 80, preferably 40 to 70 ° C or with a High-pressure homogenizer such as an APV Gaulin or with a High pressure homogenizer such as the Microfluidizer in the pressure range from 700 to 1000 bar. The achievable mean diameter water of the aqueous-dispersed phase are less than 500 microns, preferably less than 100 microns, more preferably less than 10 microns, in particular less than 1 μm.

The invention also liquid, are miscible with oil Preparations of at least one slightly water-soluble or water insoluble organic UV filter substance, available upwards called method, characterized in that they are double Dispersion systems an aqueous-dispersed phase with a particle diameter less than 500 microns, in the protective colloid stabilized Particles of one or more poorly water soluble or water insoluble organic UV filter substances dispersed before contained in an oil as a dispersing agent.

The formulations according to the invention - dispersions and from them dry powders produced - are in an excellent way for stabilizing organic material and the like a. against the Einwir kung of light, oxygen and heat. They become too stable sizing organic material in a concentration of 0.01 to 10 wt .-%, preferably 0.01 to 5 wt .-%, particularly preferably from 0.02 to 2% by weight, based on the organic material, of added during or after its preparation.

Among organic material are, for example, photographic Recording materials, in particular photographic emulsions or precursors for plastics and paints, but in particular To understand plastics and paints themselves.

Under organic material but are also cosmetic preparations such as creams, lotions, gels, lips to understand pens.  

The subject of the present invention is also against the Ein effect of light, oxygen and heat stabilized orga containing niche material, in particular plastics and paints 0.01 to 10 wt .-%, preferably 0.01 to 5 wt .-%, especially before added to 0.02 to 2 wt .-%, based on the total amount of orga niche material, one or more poorly water soluble or water-insoluble organic UV filter substances in the form of he inventive formulations.

For mixing the formulations of the invention especially With plastics, all known devices and methods for incorporation of stabilizers or other additives be applied in polymers.

The stabilized by the formulations of the invention organic material may optionally contain other additives included, for. B. antioxidants, light stabilizers, Metal deactivators, antistatic agents, flame retardants, Pigments and fillers.

Antioxidants and light stabilizers, in addition to the invention can be added to appropriate formulations, z. B. verbin based on sterically hindered phenols or sulfur or phosphorus-containing costabilizers.

As such phenolic antioxidants are, for example Example 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-β- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-) hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6- tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionylethyl] isocyanurate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) -isocyanu rat and pentaerythritol tetrakis- [β- (3,5-di-tert-butyl-4-hydroxy phenyl) propionate].

As phosphorus-containing antioxidants, for example Tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, Tris (2,4-di-tert-butylphenyl) phosphite, tris- (2-tert-butyl-4-) methylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaeryt hrddiphosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4'-bi phenylenediphosphite into consideration.  

As sulfur-containing antioxidants are, for example dilauryl thiodipropionate, dimyristyl thiodipropionate, di stearyl thiodipropionate, pentaerythritol tetrakis (β-laurylthiopro pionate) and pentaerythritol tetrakis- (β-hexylthiopropionate).

Other antioxidants and light stabilizers that work together with can be used in the formulations according to the invention, are z. B. 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzo phenones, aryl esters of hydroxybenzoic acids, α-cyanocinnamic acid derivatives, benzimidazolecarboxylic anilides, nickel compounds or Oxanilides.

A particularly good stabilization is obtained when the inventions formulations according to the invention at least one light stabilizer from the class of sterically hindered amines in üb Licher concentration is added.

As sterically hindered amines come z. B. into consideration: Bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-penta methylpiperidyl) sebacate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and Bern tartaric acid, the condensation product of N, N'-di- (2,2,6,6-tetra methylpiperidyl) hexamethylenediamine and 4-tert-octylamino-2,6- dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethylpiperidyl) nitrile Lotiacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4- butane-tetracarboxylate, 1,1 '- (1,2-ethanediyl) bis- (3,3,5,5-tetrame thylpiperazinone), the condensation products of 4-amino-2,2,6,6- tetramethylpiperidines and tetramethylolacetylenediureas.

As plastics which can be stabilized by the compounds I according to the invention, mention may be made, for example:
Polymers of monoolefins and diolefins, such as. As low or high density polyethylene, polypropylene, linear polybutene-1, poly isoprene, polybutadiene and copolymers of mono- or diols finen or mixtures of said polymers;
Copolymers of monoolefins or diolefins with other vinyl mono mers, such as. Ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers;
Polystyrene and copolymers of styrene or α-methylstyrene with dienes and / or acrylic derivatives, such as. Styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methacrylate, acrylonitrile-butadiene-styrene (ABS) or methyl methacrylate-butadiene-styrene (MBS);
halogen-containing polymers, such as. As polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride and their copolymers;
Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates, polymethacrylates, polyacrylamides and polyacrylonitriles;
Polymers derived from unsaturated alcohols and amines or from their acyl derivatives or acetals, for. As polyvinyl alcohol and polyvinyl acetate;
Polyurethanes, polyamides, polyureas, polyesters, polycarbonates, polysulfonates, polyethersulfones and polyether ketones.

Furthermore, with the formulations according to the invention varnish coatings are stabilized, z. B. industrial coatings. Under these are baked finishes, under these turn vehicle paints, preferably two-coat paints, especially emphasized.

The formulations can be in solid or liquid form the paint be added. Their good solubility in paint systems is there of particular advantage.

Also when used as stabilizers in paints, the already listed additional additives, in particular Antioxi dants and light stabilizers.

The formulations according to the invention are characterized by a good compatibility with the usual types of plastic and by a good solubility in the conventional paint systems and in the usual cosmetic oils. They usually have no or only a very low intrinsic color, are in the usual art Fabric and lacquer processing temperatures stable and not fleeting, show a low tendency to migrate and cause Above all, a long protection period of the treated with them organic materials.

Furthermore, the sunscreen agents according to the invention are suitable Formulations also called photostable UV filters in cosmetic and pharmaceutical preparations for the protection of human Skin or human hair against the sun's rays but also against artificial light, which has high levels of UV, alone or together with for cosmetic or pharmaceutical preparations  known, absorbing compounds in the UV range. Under orga niche materials are in the widest sense thus also the to understand human skin and human hair. The kosme Tables and pharmaceutical preparations as such will become available of course also stabilized to be effective for as long as possible stay.

Accordingly, the subject of the present invention are also light containing cosmetic and pharmaceutical Zuberei protect human skin or human hair against UV light in the range of 280 to 400 nm, characterized records that they are in a cosmetically or pharmaceutically g., carriers as photostable UV filters effective amounts of a Formulation of poorly water-soluble or water-insoluble orga nischer UV filter substances in amorphous or teilamorpher form alone or together with in itself for cosmetic and pharmazeu table preparations known absorbers in the UV-A and UV-B range bender compounds - containing, wherein the Formu lierungen to the aforementioned aqueous according to the invention Dispersions or the O / W / O emulsions produced therefrom or Dry powders act.

The amount of sparingly water-soluble or water-insoluble orga nischer UV filter substance in the form of the invention Formu lations used in cosmetic and pharmaceutical preparations is used in the range of 0.05 to 20 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably in the range of 1 to 7 wt .-%, based on the total amount of the cosmetic and pharmaceutical preparation.

The sunscreen-containing cosmetic and pharma Ceutic preparations are usually based on a Carrier containing at least one oil phase. But they are too Preparations are possible only on an aqueous basis. Accordingly come Oils, oil-in-water and water-in-oil emulsions, creams and Pastes, lip balm masses or fat-free gels into consideration.

As emulsions u. a. also O / W macroemulsions, O / W micro emulsions or O / W / O emulsions in dispersed form lying amino-substituted hydroxybenzophenones of the formula I. in question, where the emulsions are prepared by phase inversion technology, are obtainable according to DE-A-197 26 121.

Usual cosmetic excipients which are considered as additives can come, for. As co-emulsifiers, fats and waxes, Stabi dispersants, thickeners, biogenic agents, film formers, Fragrances, dyes, pearlescing agents, preservatives,  Pigments, electrolytes (eg magnesium sulfate) and pH regulators. As co-emulsifiers are preferably known W / O and next also O / W emulsifiers such as polyglycerol esters, sorbitan esters or partially esterified glycerides. Typical examples of Fats are glycerides; as waxes u. a. Beeswax, paraffin wax or microwaxes, optionally in combination with hydro call philen waxing. Stabilizers may be metal salts of fatty acids such. As magnesium, aluminum and / or zinc Stearate be used. Suitable thickening agents are included For example, crosslinked polyacrylic acids and their derivatives, poly saccharides, especially xanthan gum, guar guar, agar agar, algi nate and Tylose, carboxymethylcellulose and hydroxyethylcellu loose, also fatty alcohols, monoglycerides and fatty acids, polycry late, polyvinyl alcohol and polyvinylpyrrolidone. Under biogenic Active ingredients are, for example, plant extracts, protein hydrolytes sate and vitamin complexes. Common film-maker For example, hydrocolloids such as chitosan are microcrystalline Chitosan or quaternized chitosan, polyvinylpyrrolidone, vinyl pyrrolidone-vinyl acetate copolymers, polymers of acrylic acid series, quaternary cellulose derivatives and similar compounds. Suitable preservatives are, for example, formaldehyde solution, p-hydroxybenzoate or sorbic acid. As a pearlescing agent For example, glycol distearic acid esters such as ethylene Glycol distearate, but also fatty acids and fatty acid monoglycol ester into consideration. As dyes can be used for cosmetic Used for appropriate and approved substances, as described, for example, in the publication "Cosmetic Stains tel "the dye commission of the Deutsche Forschungsgemein Society, published by Verlag Chemie, Weinheim, 1984, together are set. These dyes are commonly used in Kon concentration of 0.001 to 0.1 wt .-%, based on the total Mixture, used.

An additional level of antioxidants is generally prefers. So as favorable antioxidants can all be used for kosme tables and / or dermatological applications suitable or ge common antioxidants are used.

Advantageously, the antioxidants are selected from the group consisting of amino acids (eg, glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg, urocaninic acid) and their derivatives, peptides such as D, L-carnosine , D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenoids (eg .beta.-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg. Dihydro lipoic acid), aurothioglucose, propyl thiouracil and other thiols (eg, thiorodoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl) , and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (for example, buthionine sulfoximines, homozygous sulfoximines, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages (eg. Pmol to μmol / kg), furthermore (metal) chelators (for example α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, biliburin, biliverdin, EDTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubinquinone and ubiquinol and their derivatives, vitamin C and their derivatives Derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherol and derivatives (eg vitamin E acetate, tocanol trienol), vitamin A and derivatives (vitamin A palmitate) and coni feryl benzoate of the benzoin resin , Rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and derivatives thereof, zinc and its derivatives (e.g. B. ZnO, ZnSO ₄ ), selenium and its derivatives (z. Selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide).

The amount of the aforementioned antioxidants (one or more Ver Compounds) in the preparations is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 to 20 wt .-%, in particular 1 to 10 wt .-%, based on the total weight of the preparation.

If vitamin E and / or its derivatives, the antioxidant (s) danties, it is advantageous to their respective Konzen from the range of 0.001 to 10 wt .-%, based on the Total weight of the formulation to choose.

If vitamin A and / or its derivatives or carotenoids the or which are antioxidants, it is advantageous whose ever average concentration in the range from 0.001 to 10% by weight, based on the total weight of the formulation to choose.

Usual oil components in cosmetics, for example Paraffin oil, glyceryl stearate, isopropyl myristate, diisopropyl adipate, 2-ethylhexanoic acid cetylstearyl ester, hydrogenated polyisobutene,  Vaseline, caprylic acid / capric acid triglycerides, micro crystalline wax, lanolin and stearic acid.

The total content of auxiliaries and additives can be 1 to 80, before preferably 6 to 40 wt .-% and the non-aqueous portion ("Active Substanz ") 20 to 80, preferably 30 to 70 wt .-% - based on the means - amount. The preparation of the agent can in itself known manner, d. H. For example, by hot, cold, hot Hot / cold or PIT emulsification done. This is it a purely mechanical process, a chemical reaction does not take place.

Such sunscreen preparations can accordingly in liquid, pastö water or solid form, for example as water-in-oil Creams, oil-in-water creams and lotions, aerosol creams, Gels, oils, grease sticks, powders, sprays or alcoholic-aqueous Lotions.

Finally, further known per se in the UV range absor be used, provided that they are included in the total system of the combination according to the invention to be used Filters are stable.

Most of the sunscreen in the protection of human epidermis serving cosmetic and pharma ceutical preparations consists of compounds that produce ultraviolet light absorb in the UV-B range d. H. in the range of 280 to 320 nm. For example, the proportion of the invention is verwen UV-A absorber 10 to 90 wt .-%, preferably 20 to 50 wt .-% based on the total amount of UV-B and UV-A absorbing sub punch.

Suitable UV filter substances which are used in combination with the formulations to be used according to the invention are any UV-A and UV-B filter substances. For example:

Polymeric or polymer-bound filter substances can also be used used according to the invention.

The cosmetic and dermatological preparations according to the invention may advantageously also comprise inorganic pigments based on metal oxides and / or other sparingly soluble or insoluble metal compounds in water, in particular the oxides of titanium (TiO ₂ ), zinc (ZnO), iron (eg Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (eg MnO), aluminum (Al ₂ O ₃ ), cerium (eg Ce ₂ O ₃ ), mixed oxides of the corresponding Contain metals and mixtures of such oxides. Particularly preferred are pigments based on TiO ₂ and ZnO.

It is particularly advantageous in the context of the present invention, although not mandatory, if the inorganic pigments in hy present in a drophobic form, d. H. that they are superficially water-repellent are treated. This surface treatment may be in stand that the pigments according to known manner, as in DE-A-33 14 742, with a thin hydrophobic layer are provided.

To protect human hair from UV rays, the sunscreen formulations according to the invention in shampoos, Lotions, gels, hair sprays, aerosol creams or emulsions in concentrations of 0.1 to 10% by weight, preferably 1 to 7% by weight be incorporated. The respective formulations can thereby u. a. for washing, dyeing and hair styling ver be used.

The formulations to be used according to the invention are characterized usually by a particularly high absorption capacity in Be rich in UV-A radiation with a sharp band structure. more They are well soluble in cosmetic oils and can be absorbed easy to incorporate into cosmetic formulations. The with the Formulations prepared emulsions are particularly distinguished by their high stability, the formulations I myself by  their high photostability, and the Zube made with it preparations due to their pleasant skin feel.

The UV filter effect of the formulations according to the invention can also for the stabilization of active ingredients and excipients in kosmeti and pharmaceutical formulations are exploited.

The preparations according to the invention are characterized by a be especially high absorption capacity in the range of UV-B radiation with sharp band structure and high sun protection factors.

In particular, the high SPF of the preparations, the even at low levels of UV-absorbing activity was measured, was surprising.

The following examples are intended to illustrate the present invention without restricting it.

example 1 Preparation of a Uvinul® T 150-containing dry powder with a Active substance content of 20% by weight a) Preparation of the aqueous dispersion

10 g of Uvinul® T 150 were dissolved in 216 g of acetone at room temperature solved kular disperse. For precipitation of the Uvinul® T 150 in collo In id-disperse form, the solution was added to a mixing chamber at 240 ° C guided. There, the mixture was mixed with a 1 N NaOH adjusted to pH 9.1 aqueous solution of 16.88 g of gelatin B 100 bloom and 11.25 g lactose in 1500 ml deionized water. The whole Process was carried out under pressure limitation to 40 bar to a Ver to prevent evaporation of the solvent. After mixing was a colloidally disperse Uvinul® T 150 dispersion with a white get dull hue.

By means of Fraunhofer diffraction, the mean value of the volume ver Division to D (4,3) = 0,50 μm with a fine portion of the distribution 98.5% <1.22 microns determined.

b)

After spray-drying the dispersion, a dry powder was obtained with an active ingredient content of 20.56 wt .-% Uvinul® T 150 (Ge content determination was carried out by UV / VIS spectroscopy). The dry powder  was redissolved in deionized water to give a white redispersion of cloudy dispersion (hydrosol).

By means of Fraunhofer diffraction, the mean value of the volume ver Division in the re-dispersion determined to D (4.3) = 0.65 microns at a fine fraction of the distribution of 97.1% <1.22 μm.

Example 2 a) Preparation of a Uvinul® T 150-containing aqueous dispersion

10 g of Uvinul® T 150 were added to a solution of 2 g of ascorbyl palmitate stirred into 216 g of acetone. For precipitation of the Uvinul® T 150 in Colloidally disperse form was this molecular disperse solution at 20 ° C fed to a mixing chamber. There was the mixing aqueous solution of 16.88 g Kollidon 90F in 1500 ml deionized water. The entire process was carried out under pressure limitation to 40 bar to to prevent evaporation of the solvent. After mixing was a colloidally dispersed Uvinul® T 150 dispersion with a get white-dull hue.

By quasi-elastic light scattering became the middle particles size to 255 nm with a distribution width of ± 40%. By means of Fraunhofer diffraction, the mean value of the volume ver Division to D (4,3) = 0.62 microns with a fine fraction of the distribution Determined 99.8% <1.22 microns.

b) Preparation of a Uvinul® T 150-containing aqueous dry powder verse

Spray drying of the dispersion of 2a) resulted in a nano particulate dry powder. The drug content in the powder was UV / VIS spectroscopically determined to 21.36 wt .-% Uvinul® T 150. The dry powder dissolves in demineralized water to form a white-cloudy dispersion (hydrosol).

By quasi-elastic light scattering became the middle particles size to 350 nm with a distribution width of ± 44%. By means of Fraunhofer diffraction, the mean value of the volume ver Division determined to D (4,3) = 0.62 microns at a fine fraction of Distribution of 99.8% <1.22 μm.

Example 3 Preparation of a Uvinul® T 150-containing dry powder with a Active substance content of 20% by weight a) Preparation of the aqueous dispersion

10 g of Uvinul® T 150 were dissolved in a mixture of 166 g of water and Suspended 50 g of acetone at room temperature and at a temperature temperature of 240 ° C molecularly dissolved. For precipitation of the Uvinul® T 150 in colloidally disperse form, the solution was mixed at 240 ° C chamber supplied. There, the mixing with a means of 1N NaOH adjusted to pH 9.1, aqueous solution of 16.88 g of Ge latin B 100 Bloom and 11.25 g lactose in 1500 ml deionized water. The entire process was carried out under pressure limitation to 40 bar to a To prevent evaporation of the solvent. After mixing was a colloidally disperse Uvinul® T 150 dispersion with a white get dull hue.

By means of Fraunhofer diffraction, the mean value of the volume ver Division to D (4,3) = 0,50 μm with a fine portion of the distribution 98.5% <1.22 microns determined.

b)

After spray-drying the dispersion, a dry powder was obtained with an active ingredient content of 20.56 wt .-% Uvinul® T 150 (Ge content determination was carried out by UV / VIS spectroscopy). The dry powder ver again in demineralised water to form a white-cloudy Redisperse dispersion (hydrosol).

By means of Fraunhofer diffraction, the mean value of the volume ver Division in the re-dispersion determined to D (4.3) = 0.65 microns at a fine fraction of the distribution of 97% <1.22 μm.

Example 4 Preparation of a Uvinul® BMBM-containing dry powder with a Active substance content of 20% by weight a) Preparation of the aqueous dispersion

10 g of Uvinul® BMBM were dissolved in 216 g of acetone at room temperature solved kular disperse. For precipitation of Uvinul® BMBM in colloid disperse form, the solution was added at 20 ° C a mixing chamber leads. There, the mixture was mixed with a 1 N NaOH adjusted to pH 9.1 aqueous solution of 16.88 g of gelatin B 100 bloom and 11.25 g lactose in 1500 ml deionized water. The whole Process was carried out under pressure limitation to 40 bar to a Ver to prevent evaporation of the solvent. After mixing was  a colloidally disperse Uvinul® BMBM dispersion with a white get dull hue.

By means of Fraunhofer diffraction, the mean value of the volume ver Division to D (4,3) = 0,50 μm with a fine portion of the distribution 98.5% <1.22 microns determined.

b)

After spray-drying the dispersion, a dry powder was obtained with an active ingredient content of 20.56% by weight of Uvinul® BMBM (content determination was carried out by UV / VIS spectroscopy). The dry powder allowed to re-deionize to give a white cloudy Redisperse dispersion (hydrosol).

By means of Fraunhofer diffraction, the mean value of the volume ver Division in the re-dispersion determined to D (4.3) = 0.65 microns at a fine fraction of the distribution of 96.5% <1.20 μm.

Example 5 Precipitation of Uvinul® T 150 and shellac as hydrosol, with Ascorbyl palmitate and Na caseinate

The active ingredient suspension was initially 23 g of Uvinul® T 150 and 47 g Shellac is stirred into 343 g of isopropanol. As watery Protective colloid solution was 36 g Na-caseinate and 1.1 g ascorbyl palmitate dissolved in 10820 g of water. The pH turned out to be to pH 6.9.

The active ingredient suspension was raised to a temperature of 95.degree heats and continuously with iso at a flow rate of 1.1 kg / h propanol / water azeotrope, which is at a temperature of 218 ° C ge was mixed at a flow rate of 0.8 kg / h. there Uvinul® T 150 and leaf shellac dissolved molecularly. These Solution was with the o. G. aqueous protective colloid solution whose Flow rate 54.8 kg / h, mixed. Here were Uvinul® T 150 and leaf shellac precipitated as matrix particles by Na-caseinate stabilized as hydrosol. The hydrosol was then in a rotary evaporator to 31% solids content concentrated, dissolved with 14.6 g of gelatin B 200 Bloom and then worked up via double emulsification to a dry powder. The content of Uvinul® T 150 in the dry powder was then 15%.  

preparations Example 6 Composition for lip care

Mass content (wt.%) ad 100 Eucerinum anhydricum 10.00 glycerin 10.00 Titanium dioxide, micronized 5.00 Uvinul® T 150 dry powder from example 1 8.00 Octyl methoxycinnamate 5.00 Zinc oxide 4.00 Castor oil 4.00 Pentaerythritol stearate / caprate / caprylate adipate 3.00 Glyceryl stearate SE 2.00 beeswax 2.00 Microcrystalline wax 2.00 Quaternium-18 bentonite 1.50 PEG-45 / dodecyl glycol copolymer

Example 7 Composition for sunblocker with micropigments

Mass content (wt.%) ad 100 water 10.00 Octyl methoxycinnamate 6.00 PEG-7-Hydrogenated Castor Oil 6.00 Titanium dioxide, micronized 5.00 Uvinul® T 150 dry powder from example 1 5.00 Mineral oil 5.00 Isoamyl p-methoxycinnamate 5.00 Propylene glycol 3.00 Jojoba oil 3.00 4-methylbenzylidene camphor 2.00 PEG-45 / dodecyl glycol copolymer 1.00 dimethicone 0.50 PEG-40 Hydrogenated Castor Oil 0.50 Tocopheryl acetate 0.50 phenoxyethanol 0.20 EDTA

Example 8 Fat-free gel

Mass content (wt.%) ad 100 water 8.00 Octyl methoxycinnamate 7.00 Titanium dioxide, micronized 5.00 Uvinul® T 150 dry powder from example 1 5.00 glycerin 5.00 PEG-25 PABA 1.00 4-methylbenzylidene camphor 0.40 Acrylates C10-C30 alkyl acrylate crosspolymer 0.30 Imidazolidinyl urea 0.25 Hydroxyethyl cellulose 0.25 Sodium methylparaben 0.20 Disodium EDTA 0.15 Fragrance 0.15 Sodium Propylparaben 0.10 Sodium hydroxide

Example 9 Sunscreen (SPF 20)

Mass content (wt.%) ad 100 water 8.00 Octyl methoxycinnamate 8.00 Titanium dioxide, micronized 6.00 PEG-7-Hydrogenated Castor Oil 5.00 Uvinul® T 150 dry powder from example 1 6.00 Mineral oil 5.00 Zinc oxide 5.00 Isopropyl palmitate 0.30 Imidazolidinyl urea 3.00 Jojoba oil 2.00 PEG-45 / dodecyl glycol copolymer 1.00 4-methylbenzylidene camphor 0.60 Magnesium stearate 0.50 Tocopheryl acetate 0.25 methylparaben 0.20 Disodium EDTA 0.15 Propylparaben

Example 10 Waterproof sunscreen

Mass content (wt.%) ad 100 water 8.00 Octyl methoxycinnamate 5.00 PEG-7-Hydrogenated Castor Oil 5.00 Propylene glycol 4.00 Isopropyl palmitate 4.00 Caprylic / Capric triglyceride 5.00 Uvinul® T 150 dry powder from example 1 4.00 glycerin 3.00 Jojoba oil 2.00 4-methylbenzylidene camphor 2.00 Titanium dioxide, micronized 1.50 PEG-45 / dodecyl glycol copolymer 1.50 dimethicone 0.70 Magnesium sulfate 0.50 Magnesium stearate 0.15 Fragrance

Example 11 Sun Milk (SPF 6)

Mass content (wt.%) ad 100 water 10.00 Mineral oil 6.00 PEG-7-Hydrogenated Castor Oil 5.00 Isopropyl palmitate 3.50 Octyl methoxycinnamate 5.00 Uvinul® T 150 dry powder from example 1 3.00 Caprylic / Capric triglyceride 3.00 Jojoba oil 2.00 PEG-45 / dodecyl glycol copolymer 0.70 Magnesium sulfate 0.60 Magnesium stearate 0.50 Tocopheryl acetate 3.00 glycerin 0.25 methylparaben 0.15 Propylparaben 0.05 tocopherol

Example 12 Day lotion with UV protection

Mass content (wt.%) ad 100 water 2.00 Cetearyl alcohol 1.00 glycerol 2.00 vaseline 7.50 Octyl methoxycinnamate 4.00 Octyl salicylate 3.00 Uvinul® T 150 dry powder from example 1 1.50 4-tert-butyl-4'-methoxydibenzoylmethane 0.50 dimethicone 5.00 Propylene glycol 0.20 EDTA 0.20 Carbomer 5.00 C ₁₂ -C ₁₅ alkyl benzoate 0.27 triethanolamine 1.00 Tocopheryl acetate q. s. Fragrance

Example 13 Day cream with UV protection

Mass content (wt.%) ad 100 water 2.00 Cetearyl alcohol 2.00 Cetyl alcohol 1.00 glycerol 2.00 vaseline 7.50 Octyl methoxycinnamate 4.00 Octyl salicylate 3.00 Uvinul® T 150 dry powder from example 1 1.50 4-tert-butyl-4'-methoxydibenzoylmethane 4.00 Propylene glycol 0.20 EDTA 0.20 Carbomer 0.20 xanthan 0.20 C ₁₀ -C ₃₀ alkyl acrylate crosspolymer 5.00 C ₁₂ -C ₁₅ alkyl benzoate 0.54 triethanolamine 1.00 Tocopheryl acetate q. s. Fragrance q. s. preservative

Example 14 Liquid Make Up

Mass content (wt.%) ad 100 water 2.00 Cetearyl alcohol 2.00 Ceteareth 25 6.00 glycerol 1.00 cetyl alcohol 8.00 paraffin oil 7.00 Cetearyl octanoate 0.2 dimethicone 3.00 Propylene glycol 1.00 panthenol 3.00 Uvinul® T 150 dry powder from example 1 1.50 4-tert-butyl-4'-methoxydibenzoylmethane 3.50 Octyl methoxycinnamate 0.1 bisabolol 5.70 Titanium dioxide 1.10 iron oxide q. s. Fragrance

Example 15 Hair gel with sunscreen

Mass content (wt.%) ad 100 water 1.20 Carbomer 0.50 Hydroxyethyl cellulose 4.00 triethanolamine 0.70 PEG-40 Hydrogenated Castor oil 1.50 Uvinul® T 150 dry powder from example 1 0.70 4-tert-butyl-4'-methoxydibenzoylmethane 2.80 Octyl methoxycinnamate 5.00 Propylene glycol 0.01 EDTA q. s. Fragrance q. s. Sicovit patent blue 85 E 131

Claims (32)

1. Aqueous dispersions of poorly water-soluble or wasserunlös Licher organic UV filter substances, characterized in that they contain at least one sparingly water-soluble or water-insoluble organic UV filter substance as a colloidally disperse phase in amorphous or teilamorpher form. 2. Aqueous dispersions according to claim 1, characterized that they are suspensions containing at least one poorly water-soluble or water-insoluble organic UV Filter substance as nanoparticulate particles in amorphous or partially amorphous form. 3. Aqueous dispersions according to claim 1, characterized that the particles of colloid-disperse phase have a nucleus and have a shell, the core being at least one heavy water-soluble or water-insoluble organic UV filters substance and the shell contains at least one protective colloid. 4. Aqueous dispersions according to one of claims 1 to 3, as characterized in that the particles of the colloid-disperse Phase have an average particle size less than 10 microns. 5. Aqueous dispersions according to any one of claims 1 to 4, ent holding 0.1 to 70 wt .-% of at least one heavy water solvent or water-insoluble organic UV filter substance, 0.1 to 80% by weight of at least one polymeric protective colloid, where all percentages are based on the dry matter of aqueous dispersion. 6. Aqueous dispersions according to claim 5, containing in addition 0.1 to 70% by weight of at least one plasticizer, 0.01 to 70% by weight at least one emulsifier and / or 0.01 to 50% by weight at least one antioxidant and / or preservative means. 7. Aqueous dispersions according to claim 1, characterized that the particles of colloid-disperse phase a wasserun soluble polymer matrix, in which at least one poorly water-soluble or water-insoluble organic UV Filter substance is embedded.   8. Aqueous dispersions according to claim 7, characterized that the colloid-disperse particles additionally from a Protective colloid are sheathed. 9. Aqueous dispersions according to claim 7, containing 0.1 to 70 wt .-% at least one slightly water-soluble or wasserun Soluble organic UV filter substance, 0.1 to 80% by weight at least one water-insoluble matrix polymer and 0 to 80 wt .-% of at least one polymeric protective colloid, wherein all percentages are based on the dry mass of the aqueous Obtain dispersion. 10. Aqueous dispersions according to claim 9, containing in addition 0.1 to 70% by weight of at least one plasticizer, 0.01 to 70% by weight at least one emulsifier and / or 0.01 to 50% by weight at least one antioxidant. 11. An aqueous dispersion according to any one of claims 1 to 10, ent holding at least one 1,3,5-triazine derivative of the formula I,
in which the substituents independently of one another have the following meaning:
R is hydrogen, halogen, OH, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -alkoxy, C ₁ -C ₂₀ -alkoxyalkyl, C ₁ -C ₂₀ -hydroxyalkoxy, NR ¹ R ² ,
or a radical of the formula Ia
R ¹ and R ^{2 are} hydrogen, C ₁ -C ₂₀ -alkyl, optionally substituted by one or more C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₂ aryl, optionally substituted with one or more C ₁ -C ₄ alkyl substituted C ₇ -C ₁₀ aralkyl, heteroaryl optionally substituted by one or more C ₁ -C ₄ alkyl, C ₅ -C ₈ cycloalkyl;
R ³ to R ^{5 are} hydrogen, OH, NR ⁹ R ¹⁰ , C ₁ -C ₂₀ -alkoxy, C ₆ -C ₁₂ -aryl, optionally substituted by one or more C ₁ -C ₄ -alkyl, optionally with one or more C ₁ - C ₄ alkyl substituted C ₇ -C ₁₀ aralkyl, heteroaryl optionally substituted with one or more C ₁ -C ₄ alkyl, C ₅ -C ₈ cycloalkyl;
R ⁶ to R ^{8 are} hydrogen, C ₁ -C ₂₀ alkoxy, -C (= O) -R ¹¹ , -C (= O) -XR ¹² , SO ₂ R ¹³ , CN;
R ⁹ to R ^{11 are} hydrogen, C ₁ -C ₂₀ -alkyl, optionally substituted by one or more C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₂ aryl, optionally substituted with one or more C ₁ -C ₄ alkyl substitu- tuiertes C ₇ -C ₁₀ aralkyl, heteroaryl optionally substituted by one or more C ₁ -C ₄ alkyl, C ₅ -C ₈ cycloalkyl;
R ¹² is hydrogen, C ₁ -C ₂₀ alkyl, optionally substituted with one or more C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₂ aryl, ge optionally with one or more C ₁ -C ₄ alkyl substi tuiertes C ₇ - C ₁₀ aralkyl, optionally substituted by one or more C ₁ -C ₄ alkyl substituted heteroaryl, C ₅ -C ₈ - cycloalkyl or a radical of the formula Sp-Sil;
R ^{13 is} C ₁ -C ₂₀ -alkyl, C ₅ -C ₈ -cycloalkyl, optionally substituted by one or more C ₁ -C ₄ -alkyl-substituted C ₆ -C ₁₂ -aryl, if appropriate with one or more C ₁ -C ₄ - Alkyl substituted C ₇ -C ₁₀ aralkyl, heteroaryl optionally substituted with one or more C ₁ -C ₄ alkyl;
XO, NR ¹⁴ ;
R ¹⁴ is hydrogen, C ₁ -C ₂₀ alkyl, optionally substituted with one or more C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₂ aryl, ge optionally with one or more C ₁ -C ₄ alkyl substi tuiertes C ₇ - C ₁₀ aralkyl, heteroaryl optionally substituted by one or more C ₁ -C ₄ alkyl, C ₅ -C ₈ cycloalkyl;
Sp spacer;
Sil residue from the group consisting of silanes, oligosiloxanes and polysiloxanes. 12. Aqueous dispersions according to claim 11, comprising at least one 1,3,5-triazine derivative of the formula Ib, in which the substituents have, independently of one another, the following meanings:
R ³ to R ⁵
Hydrogen, OH;
R ⁶ to R ⁸
C ₁ -C ₁₂ alkoxy, -C (= O) -XR ¹² ;
XO, NR ¹⁴ ;
R ¹² and R ¹⁴
Hydrogen, C ₄ -C ₈ -alkyl. 13. A process for preparing an aqueous dispersion minde least one poorly water-soluble or water-insoluble organic UV filter substance, defined according to claim 1, characterized in that

• a) provides a molecular disperse solution of at least one sparingly water-soluble or water-insoluble organic UV filter substance in an organic solvent,
• b) adding this solution with an aqueous solution of at least one protective colloid, wherein the hydrophobic phase of the UV filter substance is formed as a colloidally disperse phase, and
• c) freed the dispersion thus obtained from the organic solvent.

14. The method according to claim 13, characterized in that one as organic solvent in process step a) min at least one water-miscible organic solvent or a mixture of water and at least one with water miscible organic solvent used. 15. The method according to any one of claims 13 or 14, characterized ge indicates that the molecularly dispersed solution in Step a) other additives selected from the group, consisting of emulsifiers, antioxidants, preservatives agents, water-insoluble polymers and cosmetic oils added. 16. The method according to any one of claims 13 to 15, characterized gekenn characterized in that in step b) the aqueous protective colloid solution additionally contains at least one plasticizer. 17. The method according to any one of claims 13 to 16, characterized marked characterized in that in step a) the molecular disperse solution of at least one sparingly water-soluble or water-insoluble union organic UV filter substance at temperatures greater 15 ° C and immediately afterwards in step b) with the aqueous solution of the protective colloid is added, wherein a mixing temperature of 35 ° C to 120 ° C sets.   18. A process for preparing an aqueous dispersion minde least one poorly water-soluble or water-insoluble organic UV filter substance, defined according to claim 7, characterized in that

• a) preparing a molecular disperse solution of at least one sparingly water-soluble or water-insoluble organic UV filter substance and a water-insoluble polymer in an organic solvent,
• b) admixing this solution with water or an aqueous solution minde least one protective colloid, wherein the hydrophobic phase of the mixture of UV filter substance and wasserunlös Lichem polymer is formed as a colloidally disperse phase and
• c) freed the dispersion thus obtained from the organic solvent.

19. The method according to claim 18, characterized in that one in step b) uses an aqueous protective colloid solution. 20. A process for producing a dry powder containing at least one slightly water-soluble or water-insoluble organic UV filter substance as nanoparticulate particles in amorphous or partially amorphous form, characterized in that an aqueous dispersion, defined according to claim 1, from Water freed and, if appropriate in the presence of an over zugsmaterials, dries. 21. Powdered preparations of at least one heavy water soluble or water-insoluble organic filter substance, obtainable by a method defined according to claim 20, containing at least one sparingly water-soluble or water-insoluble organic UV filter substance as nano particulate particles in amorphous or partially amorphous form. 22. A process for the preparation of an oil-miscible preparation at least one slightly water-soluble or water-insoluble organic UV filter substance in the form of a double Dispersion, characterized in that an aqueous Dispersion defined according to claim 1 in the presence of a Emulsifier emulsified in oil. 23. Liquid, oil-miscible preparations of at least one poorly water-soluble or water-insoluble organic UV filter substance, obtainable by a method according to claim 22, characterized in that it is double  Dispersion systems an aqueous-dispersed phase with a Particle diameter less than 500 μm, in the protective colloid stabilized particles of one or more heavy water solubles Licher or water-insoluble organic UV filter substances be present dispersed in an oil as a dispersant ent hold. 24. Use of the aqueous dispersions, defined according to a of claims 1 to 12 as a photostable light stabilizer for organic materials. 25. Use of the pulverulent preparations defined in accordance with Claim 21 as a photostable light stabilizer for organic Materials. 26. Use of the liquid, oil-miscible preparations, defined according to claim 23 as photostable light protection medium for organic materials. 27. Use according to any one of claims 24 to 26 as Stabili for plastics and paints. 28. Use according to one of claims 24 to 26 as a photo stable UV filter in cosmetic and pharmaceutical industry preparations for the protection of human skin or human Hair against UV rays. 29. Use according to any one of claims 24 to 26 as UV stabili sator in cosmetic and pharmaceutical preparations. 30. sunscreen containing cosmetic and pharmaceutical Preparations for the protection of human skin or human Licher hair against UV light in the range of 280 to 400 nm, characterized in that they are in a cosmetically or pharmaceutically suitable carrier as a photostable UV filter effective amounts of an aqueous dispersion defined according to An claim 1 included. 31. sunscreen containing cosmetic and pharmaceutical Preparations for the protection of human skin or human Licher hair against UV light in the range of 280 to 400 nm, characterized in that they are in a cosmetically or pharmaceutically suitable carrier as a photostable UV filter effective amounts of a powdered preparation, defined according to claim 21 included.   32. sunscreen containing cosmetic and pharmaceutical Preparations for the protection of human skin or human Licher hair against UV light in the range of 280 to 400 nm, characterized in that they are in a cosmetically or pharmaceutically suitable carrier as a photostable UV filter effective amounts of a liquid, oil-miscible preparation tions defined according to claim 23.