ES2352237T3 - WATERPROOF DISPERSION OF ORGANIC SUBSTANCES, INSOLUBLE IN WATER, UV FILTERS. - Google Patents

Abstract

Aqueous dispersions of organic substances, hardly soluble in water or insoluble in water, UV filters, characterized in that they contain at least one organic substance, hardly soluble in water or insoluble in water, UV filter as a dispersion phase colloidal in amorphous or partially amorphous form, because it can be obtained by a) the preparation of a solution in molecular dispersion of at least one organic substance, hardly soluble in water or insoluble in water, UV filter, in a solvent organic, b) the combination of this solution with an aqueous solution of at least one protective colloid, the hydrophobic phase of the UV filtering substance being constituted as a colloidal dispersion phase and c) the dispersion release obtained from this mode, of the organic solvent; 15 being the organic substance, at least unique, hardly soluble in water or insoluble in water, UV filter, a 1,3,5-triazine derivative of the formula I, ** (See formula) ** in which the substituents have, independently of each other, the following meaning: 20 R means hydrogen, halogen, OH, alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, alkoxyalkyl with 1 to 20 carbon atoms, hydroxyalkoxy with 1 to 20 carbon atoms, NR1R2, or a remainder of the formula Ia ** (See formula) ** R1 and R2 mean hydrogen, alkyl with 1 to 20 carbon atoms, aryl-51 with 6 to 12 atoms of carbon substituted, if necessary, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 10 carbon atoms substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, heteroaryl substituted, if necessary, with one or more alkyl with 1 to 4 atoms carbon, cycloalkyl with 5 to 8 carbon atoms; R3 to R5 mean hydrogen, OH, NR9R10, alkoxy with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 up to 10 carbon atoms substituted, if necessary, with one or more alkyl with 1 to 4 carbon atoms, heteroaryl substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms; R6 to R8 mean hydrogen, alkoxy with 1 to 20 carbon atoms, -C (= O) -R11, -C (= O) -X-R12, SO2R13, CN; R9 to R11 mean hydrogen, alkyl with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if any, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 10 carbon atoms carbon substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, heteroaryl substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms ; R12 means hydrogen, alkyl with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if any, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 10 carbon atoms substituted , where appropriate, with one or more alkyl with 1 to 4 carbon atoms, substituted heteroaryl, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or a rest of the Sp-Sil formula; R13 means alkyl with 1 to 20 carbon atoms, cycloalkyl with 5 organic, hardly soluble in water or insoluble in water, UV filter as a particle on a nanometric scale with an average particle size in the range between 0, 01 and 2 µm in amorphous or partially amorphous form. - 52 to 8 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if any, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 10 carbon atoms substituted, if applicable, with one or more alkyl with 1 to 4 carbon atoms, heteroaryl substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms; X means O, NR14; R14 means hydrogen, alkyl with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if any, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 10 carbon atoms substituted , where appropriate, with one or more alkyl with 1 to 4 carbon atoms, substituted heteroaryl, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms; Sp means spacer; Sil means a residue from the group consisting of silanes, oligosiloxanes and polysiloxanes.

Description

The invention relates to aqueous dispersions of organic substances hardly soluble in water or insoluble in water, UV filters, to their preparation and processing to form dry powders as well as to their use as photostable agents, protective against light.

The quality or duration of life of a large number of organic materials, for example synthetic materials and paints as well as pharmaceutical and cosmetic preparations, can be negatively influenced as a result of the action of light, especially of UV irradiation. These loss of quality is evident in the case of synthetic materials and paints frequently by means of yellowing, coloring, cracking or embrittlement of the material. In the case of pharmaceutical and cosmetic preparations, degradation of the active ingredients contained in the formulations may occur as a result of the action of UV irradiation.

The harmful effect of the ultraviolet part of the solar irradiation on the skin or on the hair, which also represents an organic material in the broad sense of the word, is also a problem that acquires increasing significance. While irradiations with a wavelength less than 290 nm (the interval called UVC), are absorbed by the ozone layer in the Earth's atmosphere, irradiations in the range between 290 nm and 320 nm, the so-called UVB interval, cause on the skin an erythema, a simple solar erythema or even more or less pronounced burners.

It has been indicated that the narrow range, which is located around 308 nm, corresponds to the maximum erythematous activity of sunlight.

A large number of UVB irradiation protective compounds are known, whose compounds are constituted, inter alia, by derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone as well as 2-phenylbenzimidazole .

- 2 In the same way, it is important to have filtering substances for the range between approximately 320 nm and approximately 400 nm, which constitutes the so-called UVA interval, since their irradiations can cause reactions in the case of a light sensitive skin . It has been shown that UVA irradiation leads to a deterioration of the elastic and collagen fibers of the connective tissue, which allows premature aging of the skin and should be considered as the origin of a large number of phototoxic and photoallergic reactions. The harmful action of UVB irradiation can be reinforced by means of UVA irradiation. In order to provide protection against UVA irradiation, dibenzoylmethane derivatives are used, whose photostability does not, however, occur to a sufficient extent (Int. J. Cosm. Science 10, 53 (1988)). However, UV irradiation can also lead to photochemical reactions, the photochemical products of the reaction acting on the skin metabolism then acting. Preferably, such photochemical products of the reaction consist of compounds in the form of radicals, for example hydroxy radicals. In the same way, undefined photoproducts formed by radicals, which are formed in the skin itself, can be the origin of successive uncontrolled reactions as a result of their high reactivity. Similarly, as a result of UV irradiation, singlet oxygen can be presented, which is an excited state not constituted by radicals of the oxygen molecule, and short-lived and many other epoxides can also occur. By way of example, singlet oxygen is characterized by an increased reactivity with respect to triplet oxygen, which normally occurs (basic state in the form of radicals). Of course there are also excited triplet states, reactive (in the form of radicals) of the oxygen molecule. On the other hand, UV irradiation belongs to ionizing irradiation. Therefore there is a danger that even ionic species are formed as a result of exposure to UV, whose species can intervene on their part, by oxidation, in biochemical processes. A drawback of the industrial application of many UV filters

it resides in its poor solubility in water and / or lipids, which often limits its use, for example in cosmetic formulations.

Another drawback in the case of the application of some protective agents against light resides in the appearance of skin irritations and allergies as a result of too high skin permeability.

GB-A-2 303 549 describes a grinding process for carrying out organic, micronized, insoluble UV absorbers in the presence of alkyl polyglycosides. The micronized products, obtained in this way, can be incorporated into cosmetic preparations for protection against light.

GB-A-2 286 774 also describes a grinding process to carry out the micronization of organic, insoluble UV absorbers.

The task of the present invention was to provide protective formulations against UV light, which entailed effective protection for the organic material, especially for human skin and / or for human hair against UV irradiation and that could be perfectly incorporated into systems aqueous and in lipophilic systems.

This task was solved by means of the aqueous dispersions of organic substances hardly soluble in water or insoluble in water, UV filters, characterized in that they contain at least one organic substance hardly soluble in water or insoluble in water, UV filter , as a phase in colloidal dispersion in amorphous or partially amorphous form, characterized in that a) a solution in molecular dispersion of at least one substance is prepared

organic, hardly soluble in water or insoluble in water, filtering

UV, in an organic solvent, b) this solution is combined with an aqueous solution of at least one colloid

protective, the water-repellent phase of the filtering substance of

the UV as a phase in colloidal dispersion and c) the dispersion, thus obtained, of the organic solvent is released; the organic substance being at least unique, hardly soluble in water or insoluble in water, a UV filter, a 1,3,5-triazine derivative of the formula,

image 1

in which the substituents have, independently of each other, the meaning next: R means hydrogen, halogen, OH, alkyl with 1 to 20 carbon atoms,

alkoxy with 1 to 20 carbon atoms, alkoxyalkyl with 1 to 20 carbon atoms, hydroxyalkoxy with 1 to 20 carbon atoms, NR1R2,

or a remainder of the formula Ia

image 1

R1 and R2 mean hydrogen, alkyl with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if any, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 10 carbon atoms carbon substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, heteroaryl substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms ;

R3 to R5 mean hydrogen, OH, NR9R10, alkoxy with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 up to 10 carbon atoms substituted, if necessary, with one or more alkyl with 1 to 4 carbon atoms, heteroaryl substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 6 carbon atoms;

R6 to R8 mean hydrogen, alkoxy with 1 to 20 carbon atoms, -C (= O) -R11, -C (= O) -X-R12, SO2R13, CN;

- 5

R9 to R11

mean hydrogen, alkyl with 1 to 20 carbon atoms, aryl

with 6 to 12 carbon atoms substituted, if necessary, with one or

with several alkyl with 1 to 4 carbon atoms, aralkyl with 7

up to 10 carbon atoms substituted, if any, with one or with

several alkyl with 1 to 4 carbon atoms, heteroaryl

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, cycloalkyl with 5 to 8 carbon atoms;

R12

means hydrogen, alkyl with 1 to 20 carbon atoms, aryl

with 6 to 12 carbon atoms substituted, if necessary, with one or

with several alkyl with 1 to 4 carbon atoms, aralkyl with 7

up to 10 carbon atoms substituted, if any, with one or with

several alkyl with 1 to 4 carbon atoms, heteroaryl

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, cycloalkyl with 5 to 8 carbon atoms or a

rest of the Sp-Sil formula;

R13

means alkyl with 1 to 20 carbon atoms, cycloalkyl with 5

up to 6 carbon atoms, aryl with 6 to 12 carbon atoms

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, aralkyl with 7 to 10 carbon atoms

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, substituted heteroaryl, if any, with one or

with several alkyl with 1 to 4 carbon atoms;

X

means O, NR14;

R14

means hydrogen, alkyl with 1 to 20 carbon atoms, aryl

with 6 to 12 carbon atoms substituted, if necessary, with one or

with several alkyl with 1 to 4 carbon atoms, aralkyl with 7

up to 10 carbon atoms substituted, if any, with one or with

several alkyl with 1 to 4 carbon atoms, heteroaryl

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, cycloalkyl with 5 to 8 carbon atoms;

Sp

means spacer;

Sil

means a remainder from the group consisting of silanes,

- 6 oligosiloxanes and polysiloxanes. Within the scope of the present invention, the designation of aqueous dispersions will be understood as both aqueous suspensions as well as aqueous emulsions. Preferably, aqueous suspensions should be mentioned, in which the dispersed phase contains at least one organic substance, hardly soluble in water or insoluble in water, UV filtering, in the form of particles on a nanometric scale. On the other hand, in the foreground of the invention there are also dry powders or emulsions, preferably double emulsions, especially oil / water / oil emulsions (o / w / o), which can be they prepare from the aqueous suspensions mentioned above. In this context, organic substances hardly soluble in water, UV filters, are those compounds whose solubility in water is <5% by weight, preferably <1% by weight, especially preferably <0.5% in weight, in a very particularly preferred manner <0.1% by weight. The new light-protective formulations are characterized in that they contain at least one organic substance, hardly soluble in water or insoluble in water, a UV filter, whose amorphous part is in the range above 10%, of preferably over 30%, especially preferably it is in the range between 50 and 100%, very particularly preferably it is in the range between 75 and 99%. The determination of the crystallinity rate of UV filter substances can be carried out in this case, for example, by means of X-ray diffraction measurements. The content of at least one organic substance, hardly soluble in water or in water-insoluble, UV filter in light-protective formulations, in accordance with the invention, is in the range between 0.1 and 70% by weight, preferably in the range between 2 and 40% by weight, especially preferably in the range between 3 and 30% by weight, very particularly preferably in the range between 5 and 25% by weight, based on the dry mass of the formulations. The average particle size corresponding to scale particles

nanometric in the aqueous dispersion is located, in accordance with the type of the method for carrying out the formulation, in the range below 10 µm, preferably in the range below 5 µm, especially preferably in the range between 0.01 and 2 µm, very particularly preferably in the range between 0.05 and 1 µm.

A preferred form of the aqueous dispersions, in accordance with the invention, is characterized in that the colloidal dispersion phase particles have a core / crust structure, the core containing at least one organic substance, hardly soluble in water or insoluble. in water, UV filter. The cortex, which surrounds the nucleus, essentially contains at least one protective colloid, preferably a high molecular weight compound.

The task of this polymeric envelope is to stabilize the particles in their colloidal state against the heterogeneous growth of the particles (aggregation, flocculation, etc.).

One or more polymers can be used for this purpose. The molecular weights of the polymers used are located in the range between 1,000 and 10,000,000 g / mol, preferably in the range between 1,000 and 1,000,000 g / mol. Basically all polymers suitable for the pharmaceutical and cosmetic application sector come into consideration.

Advantageously, the water-soluble or water-swellable protective colloids such as, for example, beef, pork jellies, are suitable as polymer stabilizers for the shell shell matrix in accordance with the invention or fish, especially acid or basic degraded gelatins with Bloom indices in the range between 0 and 250, especially gelatins A 100, A 200, B 100 and B 200 as well as low molecular weight gelatin types, enzymatically degraded, with the Bloom index 0 and with molecular weights between 15,000 and 25,000 D such as, for example, Collagel A and Gelitasol P (Stoess, Eberbach) as well as mixtures of these kinds of gelatin as well as starch, dextrin, pectin, gum arabic, lignin sulphonates, chitosan, polystyrene sulfonate, alginates, casein, caseinate, methylcellulose, carboxymethyl cell sa, hydroxypropyl cellulose, milk powder, dextran, whole milk or skim milk or mixtures of these protective colloids. On the other hand, homopolymers and copolymers based on neutral, cationic or anionic monomers such as, for example, ethylene oxide, propylene oxide, acrylic acid, maleic acid anhydride, lactic acid, are suitable. N-vinyl pyrrolidone, vinyl acetate, α-asparagine acid and β-asparagine acid.

In this case, the water solubility or the swelling capacity of the polymers, which have been mentioned above, depends on the temperature, the pH value as well as the ionic strength of the solution.

Another, equally preferred, form of the aqueous dispersion, in accordance with the invention, is characterized in that the colloidal dispersion phase particles additionally contain a water-insoluble polymer matrix, in which the organic substance is embedded, at least unique, hardly soluble in water or insoluble in water, UV filter. In order to improve the colloidal stability of this aqueous dispersion, it may be advantageous if the dispersed particles are also coated with one of the protective colloids that have been cited above.

The matrix polymers inside the particles contribute to obtaining the active substance in its non-crystalline state, as well as stabilizing colloidal structures in relation to the homogeneous growth of the particles (Oswald maturation).

As polymer components, which are in the core of the particle of the active ingredient preparation according to the invention, all polymers are suitable, in principle, that do not dissolve or only partially dissolve in water or in aqueous solutions or in mixtures of aqueous solvents in a temperature range between 0 and 240 ° C, in a pressure range between 100 bar and a pH range between 0 and 14 or an ionic strength of up to 10 mol / l .

In this context the concept of non-soluble or only partially soluble means that the second Virial coefficient can take values below zero for the polymer or for polymers in water or in a mixture consisting of water and an organic solvent (see MD Lechner publication, "Makromolekulare Chemie", Birkhäuser Verlag, Basel, pages 170-175). The second Virial coefficient, which provides a prediction on the behavior of a polymer in a solvent or in a solvent mixture, can be determined experimentally, for example by measuring the diffraction of light or by means of Osmotic pressure determination. The dimension of this coefficient is (mol·l) / g2.

One or more polymers can be used. The molecular weights of the polymers used are located in the range between 1,000 and 10,000,000 g / mol, preferably in the range between 1,000 and

1,000,000 g / mol. Basically, all polymers suitable for the pharmaceutical and cosmetic application field come into consideration.

Especially interesting are polymers, which are soluble in organic solvents, miscible with water, and which are not soluble or only partially soluble in water or in aqueous solutions or in mixtures of aqueous solvents at temperatures between 0 and 240 ° C. Polymers are cited below by way of example without, however, this being limiting:

poly (vinyl ethers) such as for example poly (benzyloxyethylene), poly (vinyl acetals), poly (vinyl ketones), poly (allyl alcohol), poly (vinyl esters) such as for example poly ( vinyl acetate), poly (oxytetramethylene), poly (glutarodialdehyde), poly (carbonates), poly (esters), poly (siloxanes), poly (amides), poly (piperazines), poly ( anhydrides) such as, for example, poly- (methyl anhydride), Gutta Percha, cellulose ethers such as, for example, methyl cellulose (degree of substitution: from 3 to 10%), ethyl cellulose, butyl cellulose, cellulose esters, such as for example cellulose acetate, or starches. Especially the copolymers and block copolymers of the monomers of the polymers that have been mentioned above. On the other hand, the copolymers and block copolymers of the polyesters and of the hydroxycarboxylic acids and of the linear polyethylene glycol and of the star polyethylene glycol, for example the AB, ABA and ABC block copolymers constituted by a combination formed by L-poly (lactide ), polyglycolide and / or polyethylene glycol, for example Resomer 505, Resomer RG756 or Resomer RG-858 (Böhringer Ingelheim).

- 10

On the other hand, polymers have a special interest, which have a higher and / or lower miscibility window at temperatures between 0 and 240 ° C in water or in aqueous solutions or in mixtures of aqueous solvents, that is, by increasing or by decreasing the temperature, these polymers can be precipitated from the corresponding solutions. The following polymers should be cited by way of example, without this being limiting:

poly (acrylamides), poly (methacrylamides) such as, for example, poly (N-isopropylacrylamide), poly (N, N-dimethylacrylamide), poly (N- (1,1-dimethyl-3-oxobutyl) acrylamide ), poly (methoxyethylene), polyvinyl alcohols, acetylated polyvinyl alcohols, poly (oxyethylene), cellulose ethers such as, for example, methylcellulose (degree of substitution: from 20 to 40%), isopropyl cellulose, cellulose esters, starches, modified starches such as, for example, methyl ethyl starch, gum arabic, as well as copolymers or block copolymers consisting of the monomers of the compounds which have been cited above. In particular, the AB or ABA block copolymers based on ethylene oxide and propylene oxide, for example poloxamers such as Poloxamer 188 and Poloxamer 407. On the other hand, polymers that may be of particular interest are polymers which may be

precipitates at temperatures between 0 and 240 ° C in water or in aqueous solutions or in mixtures of aqueous solvents by means of varying the pH value or ionic strength from the corresponding solutions. The following polymers should be cited by way of example without this being limiting:

alginates, chitosan, chitin, shellac, polyelectrolytes, poly (acrylic) acid, poly (methacrylic acid), poly (methacrylate) esters with secondary, tertiary or quaternary amino groups, especially copolymers or copolymers block based on various acrylates, methacrylates, methacrylic acid, acrylic acid, for example a copolymer consisting of methacrylic acid / esters of methacrylic acid (weight ratio MAS / MAE

1: 1 or 1: 2) or a copolymer consisting of dimethylaminoethyl methacrylate and esters of methacrylic acid in the weight ratio of 1: 1 (Eudragit® types).

- 11 In accordance with the invention, the quantities of the various components will be chosen in such a way that the preparations contain, in addition to the UV filtering substances, which have been mentioned above, from 0.1 to 80% by weight, preferably from 5 to 70% by weight, especially preferably from 10 to 60% by weight, most preferably from 15 to 35% by weight of one or more colloids polymeric protectors (shell polymer) and, where appropriate, from 0.1 to 80% by weight, preferably from 0.5 to 70% by weight, especially preferably from 1 to 50 % by weight, very particularly preferably from 5 to 35% by weight of one or more matrix polymers for the core. The indications of percentage by weight refer to the dry mass of the formulation for protection against light. Additionally, the preparations may also contain low molecular weight stabilizers such as antioxidants and / or preservatives intended for the protection of UV filter substances. Suitable antioxidants or preservatives are, for example, αtocopherol, ascorbic acid, tert.-butyl hydroxytoluene, tert.-butylhydroxyanisole, lecithin, ethoxyquin, methylparaben, propylparaben, sorbic acid or sodium benzoate. The antioxidants or the preservatives can be used in amounts between 0.01 and 50% by weight, preferably between 0.1 and 30% by weight, especially preferably between 0, 5 and 20% by weight, very particularly preferably between 1 and 10% by weight, based on the dry mass of the light-protective agent formulation. On the other hand, the dispersions may also contain plasticizers in order to increase the mechanical stability of a dry powder prepared, if necessary, therefrom. Suitable plasticizers are, for example, sugars and saccharic alcohols such as sucrose, glucose, lactose, invert sugar, sorbitol, handyman, xylite or glycerin. Preferably, lactose is used as a plasticizer. The plasticizers may be contained in amounts between 0.1 and 70% by weight, preferably between 10 and 60% by weight, especially preferably between 20 and 50%

- 12

by weight, based on the dry mass of the formulation of the protective agent against light.

On the other hand, the light-protective agent formulations may contain low molecular weight compounds surfactants (emulsifiers) in a concentration between 0.01 and 70% by weight, preferably between 0.1 and 1 50% by weight, especially preferably between 0.5 and 20% by weight, based on the dry mass of the light-protective agent formulation. As such, first of all, amphiphilic compounds or mixtures of such compounds are suitable. Basically, all surfactants with an HLB value between 5 and 20 are considered. Corresponding surfactants include, for example: esters of long chain fatty acids with ascorbic acid, monoglycerides and diglycerides of fatty acids and its oxyethylation products, the glyceride esters of mono fatty acids with acetic acid, citric acid, lactic acid or diacetyltartaric acid, polyglycerin esters of fatty acids such as, for example, triglycerin monostearate, esters of sorbitan of fatty acids, propylene glycol esters of fatty acids and lecithin. Preferably, ascorbyl palmitate is used.

Under certain circumstances it may also be advantageous to additionally use a physiologically acceptable oil such as, for example, sesame oil, corn seed oil, cottonseed oil, soy bean oil or peanut oil as well as cosmetic oils, for example paraffin oil, glyceryl stearate, isopropyl myristate, diisopropyl adipate, 2-ethylhexanoic acid cetyl stearyl ester, hydrogenated polyisobutene, petrolatum, triglycerides of caprylic acid / caprinic acid, microcrystalline wax, lanolin and stearic acid in a concentration between 0.1 and 500% by weight, preferably between 10 and 300% by weight, especially preferably between 20 and 100% by weight, based on the organic substance (s) used, hardly soluble in water or insoluble in water, filtering agents. UV

The aqueous dispersion, according to the invention, contains at least one 1,3,5-triazine derivative of the formula I,

image2

in which the substituents have, independently of each other, the following meaning: R means hydrogen, halogen, OH, alkyl with 1 to 20 atoms of

carbon, alkoxy with 1 to 20 carbon atoms, alkoxyalkyl with 1 to 20 carbon atoms, hydroxyalkoxy with 1 to 20 carbon atoms, NR1R2,

or a remainder of the formula Ia

image 1

10

R1 and R2 mean hydrogen, alkyl with 1 to 20 carbon atoms, aryl

with 6 to 12 carbon atoms substituted, if necessary, with one or

with several alkyl with 1 to 4 carbon atoms, aralkyl with 7

up to 10 carbon atoms substituted, if any, with one or with

various

I rent with one until 4 atoms from carbon, heteroaryl

fifteen

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, cycloalkyl with 5 to 8 carbon atoms;

R3 to R5

mean hydrogen, OH, NR9R10, alkoxy with 1 to 20 atoms of

carbon, aryl with 6 to 12 carbon atoms substituted, in case

given, with one or several alkyl with 1 to 4 carbon atoms,

twenty

aralkyl with 7 to 10 carbon atoms substituted, if necessary,

with

one or with several rent  with 1 to 4 carbon atoms,

heteroaryl substituted, if appropriate, with one or more alkyl with

1 to 4 carbon atoms, cycloalkyl with 5 to 8 atoms of

carbon;

- 14

R6 to R8

they mean hydrogen, alkoxy with 1 to 20 carbon atoms,

-C (= O) -R11, -C (= O) -X-R12, SO2R13, CN;

R9 to R11

mean hydrogen, alkyl with 1 to 20 carbon atoms, aryl

with 6 to 12 carbon atoms substituted, if necessary, with one or

with several alkyl with 1 to 4 carbon atoms, aralkyl with 7

up to 10 carbon atoms substituted, if any, with one or with

several alkyl with 1 to 4 carbon atoms, heteroaryl

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, cycloalkyl with 5 to 8 carbon atoms;

R12

means hydrogen, alkyl with 1 to 20 carbon atoms, aryl

with 6 to 12 carbon atoms substituted, if necessary, with one or

with several alkyl with 1 to 4 carbon atoms, aralkyl with 7

up to 10 carbon atoms substituted, if any, with one or with

several alkyl with 1 to 4 carbon atoms, heteroaryl

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, cycloalkyl with 5 to 8 carbon atoms or a

rest of the Sp-Sil formula;

R13

means alkyl with 1 to 20 carbon atoms, cycloalkyl with 5

up to 8 carbon atoms, aryl with 6 to 12 carbon atoms

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, aralkyl with 7 to 10 carbon atoms

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, substituted heteroaryl, if any, with one or

with several alkyl with 1 to 4 carbon atoms;

X

means O, NR14;

R14

means hydrogen, alkyl with 1 to 20 carbon atoms, aryl

with 6 to 12 carbon atoms substituted, if necessary, with one or

with several alkyl with 1 to 4 carbon atoms, aralkyl with 7

up to 10 carbon atoms substituted, if any, with one or with

several alkyl with 1 to 4 carbon atoms, heteroaryl

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, cycloalkyl with 5 to 8 carbon atoms;

- fifteen -

Sp means spacer; Sil means a remainder of the group consisting of silanes, oligosiloxanes and polysiloxanes. As alkyl moieties for R, R1 and R2 as well as for R9 to R14 they can

Cited alkyl chains with 1 to 20 branched or unbranched carbon atoms, preferably methyl, ethyl, n-propyl, 1-methyl ethyl, n-butyl, 1 methylpropyl, 2-methylpropyl, 1,1-dimethyl ethyl, 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

10-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 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, nundecyl, 1-methylundecyl, n-dodecyl, 1,1,3,3,5,5-hexamethylhexyl, n-tridecyl, n

Tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl. In the case of R, halogen means fluorine, bromine, iodine or, preferably, it means chlorine. As alkoxy moieties for R as well as for R3 to R8, straight chain or branched chain moieties with 1 to

20 20 carbon atoms, preferably with 1 to 12 carbon atoms, especially preferably with 1 to 8 carbon atoms. As an example, we can mention:

Methoxy

Ethoxy

Isopropoxy

n-Propoxy

1-Methylpropoxy

n-Butoxi

n-Pentoxi

2-Methylpropoxy

3-Methylbutoxy

1,1-Dimethylpropoxy

2,2-Dimethylpropoxy-

Hexoxy

1-Methyl-1-ethylpropoxy-

Heptoxy

Octoxy

2-ethylhexoxy

- 16

As the hydroxyalkoxy moiety for R, alkoxy moieties, which have been mentioned above, with an additional hydroxyl function, located at the end, are considered.

By way of cycloalkyl moieties for R1 to R5 as well as for R9 to R14, cycloalkyl moieties with 3 to 10 branched or unbranched carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1pentylcyclopropyl, 1-methyl-1-butylcyclopropyl, 1,2-dimethylcyclopropyl, 1-methyl-2-ethyl, cyclopropyl cyclononyl or cyclodecyl. Cycloalkyl with 5 to 8 carbon atoms such as cyclopentyl, cycloheptyl, cyclooctyl and, especially, cyclohexyl are preferred.

The cycloalkyl moieties can be substituted, if necessary, with one or more moieties, for example with 1 to 3 moieties such as halogen, for example fluorine, chlorine or bromine, cyano, nitro, amino, alkylamino with 1 to 4 atoms carbon, dialkylamino with 1 to 4 carbon atoms, hydroxy, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or with other moieties or contain from 1 to 3 heteroatoms such as sulfur, nitrogen, whose free valences can be saturated with hydrogen or with alkyl with 1 to 4 carbon atoms or contain oxygen in the ring.

Examples of aryl having 6 to 12 carbon atoms may be mentioned, in particular, phenyl, naphthyl and biphenyl.

Examples of aralkyl with 7 to 10 carbon atoms are benzyl, phenylethyl, α-methylphenylethyl or α, α-dimethylbenzyl.

The heteroaryl moieties are advantageously simple aromatic ring systems or condensed with one or several heteroaromatic rings with 3 to 7 members. As heteroatoms, one or more nitrogen, sulfur and / or oxygen atoms may be contained in the ring or in the annular system.

As substituents of the aryl, aralkyl and heteroaryl moieties, which have been cited above, alkyl groups having 1 to 4 carbon atoms, for example methyl, ethyl, n-propyl, 1-methyl ethyl, n- butyl, 1

- 17

methylpropyl, 2-methylpropyl, 1,1-dimethylethyl.

In this context, the concept of spacer for Sp means an alkylene chain or an alkenylene chain with 3 to 12 carbon atoms bivalent, branched or unbranched, linking the silane part, the oligosiloxane part or the polysiloxane part with the rest of triazine.

Examples of an alkylene chain with 3 to 12 carbon atoms are propylene, 2-methylpropylene, butylene, pentylene and hexylene.

Examples of an alkenylene chain with 3 to 12 carbon atoms are 2-propene-2-ylene, 2-methyl-3-propenylene, 3-buten-3-ylene and 4-pentene-4-ylene.

Preferred spacers are - (CH2) 3-, - (CH2) 4-, - (CH2) 5-, - [CH (CH3)] (CH2) -, - (CH2) 2-CH = CH-, -C (= CH2) -CH2-, -C (= CH2) - (CH2) 2-O- (CH2) 4 -, - (CH2) 4-O (CH2) 2-.

The concept of silane means in this context a SiR15R16R17 moiety, in which R15, R16, R17 means, independently of one another, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms or phenyl.

How

examples they can meet up with: If (CH2-CH3) 3, If (CH2-CH2-CH3) 3,

If (isopropyl) 3,

Si (tert-butyl) 3, Si (tert-butyl) (CH3) 2, If (CH3) 2- (hexyl),

Yes (OCH3) 3, Yes (OEt) 3, SiPh3.

The concept of oligosiloxane means a remainder of the group of the general formula, consisting of SiR18 m (OSiR18 3) n with m = 0, 1 or 2; n = 3, 2 or 1 and m + n = 3, R18- [Si (R18) 2-O-] r-Si (R18) 2-A and R18- [Si (R18) 2-O-] r-Si (A) (R18) -O-Si (R18) 3, in which A means a chemical bond or a spacer and R18 means an alkyl moiety with 1 to 6 carbon atoms or a phenyl moiety and r takes values between 1 and 9.

The concept of polysiloxane comprises, for example, a remainder of the group of the general formula, consisting of A- [Si (R19) 2-O] s-Si (R19) 2-A or (R19) 3-Si- [OSi (R19) 2]] t- [O-Si (R19) (A)] qO-Si (R19) 3, in which A means a chemical bond or a spacer and R19 means an alkyl moiety with 1 to 6 atoms of carbon or a phenyl moiety, syt take values between 4 and 250 and q take values between 1 and 30.

Examples of silanyl-triazines, in which R12 means a remainder of the Sp-Sil formula, are found in EP-A-0 933 376.

image 1

in which R3 to R5 are in ortho position with respect to the rest of triazine phenylamino.

5 Aqueous dispersions containing at least one 1,3,5-triazine derivative of the formula Ib are preferred, in which the substituents have, independently of each other, the following meaning: R3 to R5 mean hydrogen, OH; R6 to R8 means alkoxy with 1 to 12 carbon atoms, -C (= O) -X-R12;

10 X means O, NR14; R12 and R14 mean hydrogen, alkyl with 4 to 8 carbon atoms. An especially advantageous UVB filter is constituted by 2,4,6trianylino-p- (carbo-2'-ethyl-hexyl-1'-oxy) -1,3,5-triazine, which is marketed by the firm BASF Aktiengesellschaft under the name Uvinul® T150.

image3

Uvinul® T150 is characterized by good UV absorption properties with an extraordinarily high extinction coefficient> 1,500 at 314 nm. The spherical isotropic character of the particles, which are contained in the dispersions according to the invention, does not exhibit a behavior of

Intrinsic viscosity, contrary to what happens in the case of ground anisotropic particles. Therefore, an incorporation of this dispersion is clearly facilitated for example in cosmetic formulations as well as the use of these

- 19

formulations

On the other hand, it could be observed that a sun protection cream based on the dispersion, according to the invention, has a factor for sun protection by a factor 4 times greater than that of an analogous agent preparation light shield, in which the same amount of the UV filtering substance has been arranged in a dispersed molecular state.

While the filtering substances of the ground UV have an increased tendency to increase the size of the particles on the occasion of the incorporation into skin creams, which can lead to a worsening of the sun protection factor and an unpleasant sensation on the skin , the dispersions according to the invention do not exhibit such tendencies as a consequence of their matrix and their protective colloid structure.

In the same way, the object of the invention is constituted by a method for carrying out the obtaining of an aqueous dispersion containing at least one organic substance, hardly soluble in water or insoluble in water, filtering the UV in form phase in colloidal dispersion in amorphous or partially amorphous form, characterized in that a) a solution in molecular dispersion of at least one substance is prepared

organic, hardly soluble in water or insoluble in water, filtering

UV, in an organic solvent, b) this solution is combined with an aqueous solution of at least one colloid

protective, forming the water-repellent phase of the UV filter substance

as the phase in colloidal dispersion and c) the dispersion, thus obtained, of the organic solvent is released.

The organic solvent in step a) of the process is advantageously used at least one water-miscible organic solvent, or a mixture formed by water and at least one water-miscible organic solvent.

Preferred solvents should be mentioned, above all, those water miscible solvents, thermally stable, volatile, containing only carbon, hydrogen and oxygen such as alcohols, ethers, esters, ketones and acetals. Conveniently, those solvents that are miscible with water at least 10% are used, which have a

- twenty

boiling point below 200 ° C and / or having less than 10 carbon atoms. Ethanol, npropanol, isopropanol, 1,2-butanediol-l-methyl ether, 1,2-propanediol-1-n-propyl ether, tetrahydrofuran or acetone are especially preferred.

The process is also characterized in that it provides the solution in step a), if necessary, another additive, chosen from the group consisting of emulsifiers, antioxidants, preservatives, water-insoluble polymers or edible oils and / or because in step b) the aqueous solution of the protective colloid additionally contains at least one plasticizer. However, it is also possible to provide one or more emulsifiers to the solution of the protective colloid. With regard to the description of these additives, reference is made to the explanations that have already been given at the beginning.

In a preferred embodiment of the process, in step a) the solution in molecular dispersion of at least one organic substance, hardly soluble in water or insoluble in water, UV filter, at temperatures above 15 ° C is prepared , preferably at temperatures in the range between 50 ° C and 240 ° C, especially preferably in the range between 140 ° C and 180 ° C and immediately thereafter combined in step b) with the aqueous solution of the protective colloid, whereby a temperature of the mixture situated from about 35 ° C to 120 ° C is established, especially preferably from 55 ° C to 70 ° C.

On the other hand, the object of the invention is constituted by a process for carrying out an aqueous dispersion of at least one organic substance, hardly soluble in water or insoluble in water, UV filter, in which The particles of the colloidal dispersion phase contain a polymer matrix insoluble in water, in which at least one organic substance, hardly soluble in water or insoluble in water, UV filter, is embedded, characterized in that a) a solution is prepared in molecular dispersion of at least one substance

organic, hardly soluble in water or insoluble in water, filtering

UV, and at least one water insoluble polymer in an organic solvent, b) this solution is combined with an aqueous solution of at least one colloid

- 21, the hydrophobic phase of the mixture consisting of the UV filtering substance and the water-insoluble polymer is formed, as a colloidal dispersion phase and c) the dispersion, thus obtained, of the organic solvent is released. In accordance with an embodiment of the process, a solution in molecular dispersion of the UV filtering substance in the solvent chosen together with the polymer is prepared, which must be found in the core of the particle in the preparation of the protective agent against light. This polymer has the property of not being soluble in water or of being only partially soluble in water at a certain temperature, pH or salt range. The concentration of the solution of the light-protective agent -polymer, prepared in this way, is generally comprised between 10 and 500 g of at least one substance hardly soluble in water or insoluble in water, UV filtering , per 1 kg of solvent and from 0.01 to 400 g of polymer, the weight ratio between the polymer and the lightning agent being between 0.01 to 1 and 5 to 1. In a preferred embodiment of the The low molecular weight stabilizer procedure is contributed directly to the light-polymer protective agent solution. In a subsequent stage of the process, the solution of light-protecting agent -polymer is mixed with water or, preferably, with an aqueous solution of polymer coating material. The concentration of the polymeric coating material is, as a rule, between 0.1 and 200 g / l, preferably between 1 and 100 g / l. In accordance with another embodiment of the process, a solution in molecular dispersion of the UV filtering substance in the solvent chosen without the polymer is prepared, which must be found in the core of the particle in the preparation of the lightning agent. The concentration of the light-protecting agent solution, prepared in this way, is generally comprised between 10 and 500 g of UV filtering substance per 1 kg of solvent. In a subsequent stage of the process, this solution is mixed with an aqueous molecular solution of the polymer, which must be found in the core of the

- 22

particle in the preparation of the lightning protection agent. The concentration of the polymer solution, prepared in this way, is generally between 0.01 and 400 g of polymer. In this case, the temperatures, pH values and salt concentrations of the two solutions that must be combined are chosen so that after the combination of the solutions the UV filtering substance and the polymer are insoluble in the solution combined. In a preferred embodiment of the process, the low molecular weight stabilizer is provided directly to the active ingredient solution.

In a subsequent stage of the process, the precipitate of the light-protective agent -polymer is mixed with an aqueous solution of the polymeric coating material. The concentration of the polymeric coating material is between 0.1 and 200 g / l, preferably between 1 and 100 g / l.

The mixing process can be carried out discontinuously or, preferably, continuously. As a consequence of the mixing process, precipitation occurs.

The conditions, under which the performance of the process according to the invention is carried out, as regards the variation of the organic water / solvent system, the pH value, the temperatures or the ionic forces that must be chosen in each case, they can be determined by the person skilled in the art with the help of the second Virial coefficient by means of a simple previous test for the corresponding polymer.

In the same way, the object of the invention is constituted by a method for carrying out the obtaining of a dry powder, which contains at least one organic substance, hardly soluble in water or insoluble in water, filtering the UV as particles on a nanometric scale in amorphous or partially amorphous form, characterized in that one of the aqueous dispersions according to the invention, which have been mentioned above, is released from the water and, if necessary, dried in the presence of a coating material .

The transformation into a dry powder can be carried out in this case, for example, by means of a spray drying, by means of a lyophilization drying or by means of a fluidized bed drying, if necessary also in the presence of a coating material. As coating agents are

- 2. 3

suitable, among others, corn starch, silicic acid or even tricalcium phosphate.

In the case of lyophilization of the nanoparticles according to the invention, cryoprotective substances such as trehalose or polyvinylpyrrolidone can be provided.

In this way, dry powders can be obtained in accordance with the invention, which no longer lose their acquired properties in the primary dispersion. That is, the amorphous character of the UV filtering substance and the core-cortex structure remain constant. On the other hand, it is a property according to the invention that these dispersions show the same particle size distribution, which were in the form of a primary dispersion, when they are dissolved again with a deviation of 20%, preferably with a deviation <15 %.

In the same way, preparations in powder form are claimed, which can be obtained according to one of the processes mentioned above, which contain at least one organic substance hardly soluble in water.

or insoluble in water, UV filter, according to claim 1 in the form of particles on a nanometric scale in amorphous form or in partially amorphous form.

The object of the invention is also constituted by a method for carrying out an oil-miscible preparation in the form of a double dispersion, which contains at least one organic substance, hardly soluble in water or insoluble in water. , UV filter, according to claim 1 in amorphous or partially amorphous form, characterized in that the aqueous dispersions that have been described at the beginning are emulsified in oil.

In this case, a water-in-oil emulsion was formed through the use of an emulsifier, in which the aqueous phase contains stabilizing nanoparticles of the protective colloid of at least one organic substance, hardly soluble in water or insoluble in water. , UV filter. Emulsifiers include water / oil emulsifiers known per se with an HLB value of less than 10, especially between 2 and 6 (see H.P. Fiedler, Lexikon der Hilfsstoffe für Pharmazie,

- 24 -

Kosmetik und angrenzende Gebiete, 1996, page 753 and following). Typical representatives of this class of emulsifiers are the partial esters of the fatty acids of polyvalent alcohols, for example glycerol monostearate or mixtures consisting of monoglycerides, diglycerides and triglycerides, partial esters of sorbitan fatty acids and / or preferably esters of polyglycerol fatty acids such as, for example, polyglycerol polyhydricinoleate, which are used in a concentration between 10 and 1,000% by weight, preferably between 100 and 900% by weight, especially preferably between 400 and 800% by weight, based on the UV filter substance or substances.

The dispersing agent can be both of synthetic, mineral, vegetable origin as well as, of animal origin. Typical representatives are, among others, sesame oil, corn seed oil, cottonseed oil, soybean oil or peanut oil, esters of vegetable fatty acids with a length of middle chain as well as paraffin oil, glyceryl stearate, isopropyl myristate, diisopropyl adipate, cetyl stearyl ester of 2-ethylhexanoic acid, hydrogenated polyisobutene, petrolatum, caprylic acid / caprinic acid triglycerides, microcrystalline wax, lanolin and stearic acid. The amount of the dispersing agent is generally between 30 and 95, preferably between 50 and 80% by weight, based on the total mass of the emulsion ready for use.

The emulsion can be carried out continuously or discontinuously.

The physical stability of the double dispersion system, such as for example sedimentation stability, is achieved by a very good fine distribution of the aqueous phase in the oil phase, for example by means of an intense treatment with a peptizer device rotor / stator at temperatures between 20 and 80, preferably between 40 and 70 ° C or with a high pressure homogenizer such as a Gaulin APV device or with a high pressure homogenizer such as a microfluidizer in the range of pressures between 700 and 1,000 bars. The average diameters of the aqueous-dispersed phase, which can be achieved in this way, are less than 500

- 25

µm, preferably they are smaller than 100 µm, especially preferably they are smaller than 10 µm, in particular they are smaller than 1 µm.

In the same way, the object of the invention is constituted by liquid preparations, miscible with oil, of at least one organic substance, hardly soluble in water or insoluble in water, UV filter, which can be obtained according to the procedures which have been cited above, characterized in that as a double dispersion system they contain an aqueous-dispersed phase with a particle diameter of less than 500 µm, in which stabilized particles with a protective colloid of one or more organic substances are presented in a dispersed state , hardly soluble in water or insoluble in water, UV filters, in an oil as a dispersing agent.

The formulations according to the invention - the dispersions and the dry powder, which is prepared therefrom - are excellently suitable for carrying out the stabilization of organic material, among other things against the action of light, of the Oxygen and heat. These formulations are contributed to the organic material, which must be stabilized, in a concentration between 0.01 and 10% by weight, preferably between 0.01 and 5% by weight, especially preferably comprised between 0.02 and 2% by weight, based on the organic material, before, during or after obtaining it.

By organic material, for example, photographic printing materials, especially photographic emulsions or starting products for synthetic materials and paints, will be understood, however, especially synthetic materials and paints themselves.

However, organic material will also mean cosmetic preparations such as, for example, creams, lotions, gels, lipsticks.

On the other hand, the object of the present invention is constituted by an organic material stabilized against the action of light, oxygen and heat, especially synthetic materials and paints, containing from 0.01 to 10 % by weight, preferably from 0.01 to 5% by weight, especially preferably from 0.02 to 2% by weight, based on the total amount of the organic material, of one or more substances organic

- 26

hardly soluble in water or insoluble in water, UV filters, in the form of the formulations according to the invention.

To carry out the mixing of the formulations according to the invention, first of all, with synthetic materials, all known devices and methods can be employed to carry out the incorporation by mixing of stabilizing agents or other additives in polymers.

The organic material, stabilized by means of the formulations according to the invention, may also contain other additives, for example antioxidants, light stabilizing agents, metal deactivators, antistatic agents, flame inhibiting agents, pigments and cargo materials.

Antioxidants and light stabilizers, which may be provided in addition to formulations according to the invention, are, for example, compounds based on sterically hindered phenols or are stabilizers containing sulfur or phosphorus.

By way of such phenolic antioxidant agents there may be mentioned, for example, 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-β- propionate (3,5-di-tert-butyl- 4-hydroxyphenyl), 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-isocyanurate, 5-tris- [β- (3,5-diterc.-butyl-4-hydroxyphenyl) -propionylethyl], 1,3,5-tris- (2,6-dimethyl-3-hydroxy-4-tert) isocyanurate. butylbenzyl) and pentaerythrite tetrakis [β- (3,5-di-tert.-butyl-4-hydroxy-phenyl) propionate].

Phosphorus antioxidants include, for example, tris- (nonylphenyl) phosphite, distearylpentaerythritite diphosphite, tris phosphite (2,4-di-tert-butyl-phenyl), tris- phosphite (2-tert-butyl-4-methylphenyl), bis- (2,4-di-tert-butylphenyl) -pentaerythritite diphosphite and tetrakis- (2,4-di-tert-butylphenyl) diphosphite - 4,4'-biphenylene.

As sulfur-containing antioxidant agents, there may be mentioned, for example, dilauryl thiodipropionate, myristyl thiodipropionate, distearyl thiodipropionate, tetrakis- (β-laurylthiopropionate) of pentaerythrite and tetrakis- (β-hexylthiopropionate) of pentaerythrite

- 27 Other antioxidants and light stabilizers, which can be used together with the formulations according to the invention, are, for example, 2- (2'-hydroxyphenyl) -benzotriazoles, 2-hydroxybenzophenone, esters of Aryl of hydroxybenzoic acids, α-cyanocinamic acid derivatives, benzimidazole carboxylic acid anilides, nickel compounds or oxalic acid dianilides. Especially good stabilization is obtained when the formulations, in accordance with the invention, are also provided with at least one light stabilizer of the class of compounds consisting of sterically hindered amines, in usual concentration. As sterically hindered amines, for example: bis- (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, the product of condensation of 1-hydroxyethyl2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N'-di- (2,2,6,6-tetramethylpiperidyl) -hexamethylenediamine and 4terc.-octylamino-2,6-dichloro-1,3,5-triazine, tris- nitrilotriacetate (2,2,6,6-tetramethylpiperidyl), tetrakis- 1,2,3,4-butanetetracarboxylate ( 2,2,6,6-tetramethyl-4-piperidyl), 1,1 '- (1,2-ethanediyl) -bis- (3,3,5,5-tetramethylpiperazinone), the condensation products of 4-amino -2,2,6,6-tetramethylpiperidines and tetramethyllacetylenediureas. As synthetic materials, which can be stabilized by means of the compounds I according to the invention, there may be mentioned, for example: polymers of monoolefins and diolefins such as, for example, low density or high density polyethylene , polypropylene, linear polybutene-1, polyisoprene, polybutadiene as well as copolymers of monoolefins or diolefins or mixtures of the aforementioned polymers; the copolymers of the monoolefins or diolefins with other vinyl monomers, such as, for example, the ethylene-alkyl acrylate copolymers, the ethylene-alkyl methacrylate copolymers, the ethylene-vinyl acetate copolymers or the copolymers of ethylene acrylic acid; polystyrene and copolymers of styrene or α-methylstyrene with dienes

- 28 and / or with acrylic derivatives such as, for example, styrene butadiene, styrene acrylonitrile (SAN), ethyl styrene methacrylate, ethyl styrene butadiene acrylate, styrene acrylonitrile methacrylate, acrylonitrile -butadiene-styrene (ABS) or methyl methacrylate-butadiene-styrene (MBS); halogenated polymers such as, for example, polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride as well as their copolymers; polymers, which are derived from α, β-unsaturated acids and their derivatives such as polyacrylates, polymethacrylates, polyacrylamides and polyacrylonitriles; polymers, which are derived from unsaturated alcohols and amines or their acyl or acetal derivatives, for example polyvinyl alcohol and polyvinyl acetate; polyurethanes, polyamides, polyureas, polyesters, polycarbonates, polysulfonates, polyether sulfones and polyether ketones. In the same way paint coatings can be stabilized with the formulations according to the invention, for example industrial paint coatings. Among these, coatings with baked paint should be specially described, and among these, in turn, coatings with paint for motor vehicles, preferably coatings with two-layer paint. The formulations can be contributed to the paint in solid form or in liquid form. Its good solubility in paint systems is especially advantageous in this case. In the same way, when the formulations are used as stabilizers in paints, additional additives that have already been indicated can be used concomitantly, especially antioxidants and light stabilizers. The formulations, in accordance with the invention, are characterized by good compatibility with the usual types of synthetic materials and are characterized by good solubility in the usual paint systems and oils

- 29

Usual cosmetics As a rule, these formulations do not have their own color

or they only have a very faint color of their own, they are stable at the usual temperatures necessary to carry out the transformation of synthetic materials and paints and are not volatile, they have a reduced migration tendency and, first of all, they cause durable protection of organic materials treated with them.

On the other hand, the formulations of the protective agents against light, according to the invention, are also suitable as photostable filters of the UV in cosmetic and pharmaceutical preparations to carry out the protection of the skin of human beings or hair of human beings against solar irradiation as well as against artificial light, which has high proportions of UV, alone or together with absorbing compounds in the UV range, known for cosmetic or pharmaceutical preparations. Organic materials shall be understood in the broadest sense of the word including the skin of human beings and the hair of human beings. Naturally, cosmetic and pharmaceutical preparations as such are also stabilized so that they remain active for as long as possible.

Therefore, the object of the present invention is also made up of cosmetic and pharmaceutical preparations, which contain protective agents against light, in order to carry out the protection of human beings or the hair of human beings against UV light. in the range between 280 and 400 nm, characterized in that they contain in a suitable excipient from the cosmetic or pharmaceutical point of view, by way of photostable UV filters, active amounts of a formulation of organic substances, hardly soluble in water or insoluble in water, UV filters in amorphous form or partially amorphous form - alone or together with absorbing compounds in the UVA range and in the UVB range, known per se for cosmetic and pharmaceutical preparations -, the formulations being constituted by the dispersions aqueous in accordance with the invention, which have been mentioned at the beginning, or by the emulsions acei tea / water / oil or by dry powders prepared therefrom.

The amount of organic substance, hardly soluble in water or insoluble in water, UV filter, in the form of formulations in accordance with the

- 30

The invention, which is used in cosmetic and pharmaceutical preparations, is in the range of 0.05 to 20% by weight, preferably 0.1 to 10% by weight, especially preferably in the range between 1 and 7% by weight, based on the total amount of the cosmetic and pharmaceutical preparation.

Cosmetic and pharmaceutical preparations, which contain protective agents against light, are generally made of an excipient, which contains at least one oil phase. However, only water-based preparations are also possible. Therefore, oil emulsions, oil-in-water emulsions and water-in-oil emulsions, creams and pastes, lipstick masses or fat-free gels come into consideration.

Emulsions include, among others, oil-in-water (O / W) macroemulsions, oil-in-water (O / W) microemulsions or oil-in-water-in-oil emulsions (O / W / O) with aminosubstituted hydroxybenzophenones of the formula I, which are presented in dispersed form, and emulsions can be obtained by means of phase inversion technology, according to DE-A-197 26 121.

The usual cosmetic auxiliary products that can be considered as additives are, for example, coemulsifiers, fats and waxes, stabilizers, thickeners, biogenic active products, film formers, odorizing products, colorants, pearl luster agents, agents for conservation, pigments, electrolytes (for example magnesium sulfate) and pH regulators. Preferably, the known W / O emulsifiers and, in addition, also the O / W emulsifiers, such as, for example, polyglycerin esters, sorbitan esters or partially esterified glycerides, are used as co-emulsifiers. Typical examples of fats are glycerides; as waxes, among others, beeswax, paraffin wax or microceres should be mentioned, if necessary in combination with hydrophilic waxes. As stabilizers, metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate can be used. Suitable thickening agents are, for example, cross-linked polyacrylic acids and their derivatives,

- 31

polysaccharides, especially xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, in addition, fatty alcohols, monoglycerides and fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone. Biogenic active products will be understood as, for example, plant extracts, albumin hydrolysates and vitamin complexes. The film formers, which can be used, are, for example, hydrocolloids such as chitosan, microcrystalline chitosan or quaternized chitosan, polyvinylpyrrolidone, vinyl vinyl pyrrolidoneacetate copolymers, acrylic acid series polymers, Quaternary cellulose derivatives and similar compounds. Suitable agents for preservation are, for example, formaldehyde solution, phydroxybenzoate or sorbic acid. As pearl luster agents, for example, glycerol esters of diestearic acid such as ethylene glycol distearate, as well as fatty acids and monoglycol esters of fatty acids are considered. Suitable and accepted substances for cosmetic purposes can be used as dyes, such as those that have been collected, for example, in the publication "Kosmetische Färbemittel" der Farbstoffkoimmission der Deutschen Forschungsgemeinschaft, published in Verlag Chemie, Weinheim, 1984. These dyes will usually be used in concentrations from 0.001 to 0.1% by weight, based on the mixture as a whole.

In general, an additional antioxidant content is preferred. In this way, all suitable antioxidants or which can be used for cosmetic and / or dermatological applications can be used as favorable antioxidants.

Advantageously, the antioxidants will be chosen from the group consisting of amino acids (for example glycine, histidine, tyrosine, tryptophan) and their derivatives, for imidazoles (for example urocaninic acid) and their derivatives, for peptides such as D, L-carnosine, D-carnosine, L-carnosine and its derivatives (for example anserine), by carotinoids, by carotins (for example, β-carotine, licopine) and their derivatives, by chlorogenic acid and its derivatives, for liponic acid and its derivatives (for example dihydroliponic acid), for aurothioglucose, for propylthiouracil and for other thiols (for

- 32

example thiorodoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl esters, of γ-linoleyl, of cholesteryl and of glyceryl) as well as their salts, for dilauryl thiodipropionate, for distearyl thiodipropionate, for thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides , nucleosides and salts) as well as sulfoximin compounds (for example, butioninsulfoximin, homocysteinsulfoximin, butioninsulfone, pentathioninsulfoximin, hexa-thioninsulfoximin, heptathinsulfoximin) in very small compatible dosages (for example pmol to µmol / kg), in addition, chelating agents (metal) (for example α-hydroxygrases acids, palmitic acid, phytinic acid, lactoferrin), α-hydroxy acids (for example citric acid co, lactic acid, malic acid), humic acid, gallic acid, bile extracts, biliburin, biliverdin, EDTA and its derivatives, unsaturated fatty acids and their derivatives (for example γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and its derivatives, vitamin C and its derivatives (for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherol and its derivatives (for example vitamin E acetate, tocotrienol), vitamin A and its derivatives (vitamin A palmitate) as well as the coniferyl benzoate of the benzoic resin, rutinic acid and its derivatives, α- glycosylrutin, ferulic acid, furfurylidenglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroacid from guaiac resin, nordihydroguayretic acid, trihydroxybutyrophenone, uric acid and its derivatives, muric acid Anose and its derivatives, zinc and its derivatives (for example ZnO, ZnSO4), selenium and its derivatives (for example seleniomethionine), stilbene and its derivatives (for example stilbene oxide, trans-stilbene oxide) .

The amount of the antioxidants mentioned above (one or more compounds) in the preparations is preferably between 0.001 and 30% by weight, particularly preferably between 0.05 and 20% by weight, especially from 1 to 10% by weight, based on the total weight of the composition.

When vitamin E and / or its derivatives constitute the antioxidant (s),

- 33

it will be advantageous to choose its corresponding concentration in the range between 0.001 and 10% by weight, based on the total weight of the formulation.

When vitamin A and / or its derivatives or carotinoids constitute the antioxidant (s), it will be advantageous to choose its corresponding concentration in the range between 0.001 and 10% by weight, based on the total weight of the formulation.

The usual oleaginous components in cosmetics are, for example, paraffin oil, glyceryl stearate, isopropyl myristate, diisopropyl adipate, cetyl stearyl ethylhexanoate, hydrogenated polyisobutene, petrolatum, triglycerides of caprylic acid / acid goat, microcrystalline wax, lanolin and stearic acid.

The total percentage of auxiliary products and additives may be between 1 and 80, preferably between 6 and 40% by weight and the non-aqueous percentage ("active substance") may be between 20 and 80, preferably between 30 and 70% by weight -referred to the agent-. Obtaining the agents can be carried out in a manner known per se, that is, for example, by hot, cold, hot-hot / cold emulsion or by means of an emulsion at the inversion temperature of the PIT phases. In this case, it is a purely mechanical procedure, without a chemical reaction taking place.

Such preparations for sun protection can therefore be presented in liquid, pasty or solid form, for example in the form of water-in-oil creams, creams and oil-in-water lotions, creams spray foaming, gels, oils, fat bars, powders, aerosols or aqueous alcoholic solutions.

Finally, other substances, known per se, absorbing in the UV range can be used concomitantly, as long as they are stable in the whole system of the combination formed by the UV filters, to be used in accordance with the invention.

Most of the light-protecting agents in cosmetic and pharmaceutical preparations, which serve to protect the epidermis of human beings, consist of compounds that absorb UV light in the UV-B range, that is, in the range from 280 to 320 nm. As an example, the

- 34% of the UV-A absorbers, to be used in accordance with the invention, is between 10 and 90% by weight, preferably between 20 and 50% by weight, based on the total amount of the absorbing substances of UV-B and UV-A. As UV filter substances, which are used in combination with the formulations, to be used in accordance with the invention, all UV-A and UV-B filter substances are considered. As an example we can mention:

Nr.

Product CAS-Nr.

 image 1

 image 1

(= acid)

one

4-aminobenzoic acid 150-13-0

2

3- (4'trimethylammonium) -benzylidenbornan-2-one methylsulfate 52793-97-2

3

3,3,5-trimethyl-cyclohexyl salicylate (Homosalatum) 118-56-9

4

2-hydroxy-4-methoxy-benzophenone (Oxybenzonum) 131-57-7

5

2-phenylbenzimidazol-5-sulfonic acid and its potassium, sodium and triethanolamine salts 27503-81-7

6

3,3 '- (1,4-phenylenedimetin) -bis (7,7-dimethyl-2-oxobicyclo [2.2.1] heptan-1-methanesulfonic acid) and salts thereof 90457-82-2

7

Polyethoxy ethyl 4-bis (polyethoxy) amino benzoate 113010-52-9

8

2-ethylhexyl 4-dimethylamino-benzoate 21245-02-3

9

2-ethylhexyl salicylate 118-60-5

10

2-isoamyl 4-methoxy-cinnamate 71617-10-2

eleven

2-ethylhexyl 4-methoxy-cinnamate 5466-77-3

12

2-hydroxy-4-methoxy-benzophenone-5-sulfone- (Sulisobenzonum) and sodium salt 4065-45-6

13

3- (4'-sulfo) benzylidene-bornan-2-one and salts 58030-58-6

14

3-benzylidenebornan-2-one 16087-24-8

- 35 -

Nr.

Product CAS-Nr.

 image 1

 image 1

(= acid)

fifteen

1- (4'-Isopropylphenyl) -3-phenylpropan-1,3-dione 63260-25-9

16

4-Isopropylbenzyl Salicylate 94134-93-7

17

2,4,6-Trianilin- (o-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine 88122-99-0

18

3-imidazol-4-yl-acrylic acid and its ethyl ester 104-98-3

19

Ethyl 2-cyano-3,3-diphenylacrylate 5232-99-5

twenty

2'-ethylhexyl 2-cyano-3,3-diphenylacrylate 6197-30-4

twenty-one

mentyl o-aminobenzoate or: 5-methyl 2- (1-methyl ethyl) -2-aminobenzoate 134-09-8

22

glyceryl p-aminobenzoate or: 1-glyceryl 4-aminobenzoate 136-44-7

2. 3

2,2'-dihydroxy-4-methoxybenzophenone (Dioxy-benzone) 131-53-3

24

2-hydroxy-4-methoxy-4-methylbenzophenone (Mexonon) 1641-17-4

25

triethanolamine salicylate 2174-16-5

26

dimethoxyphenylglyoxalic acid or: 3,4-dimethoxy-phenyl-glyoxal sodium acid 4732-70-1

27

3- (4'-sulfo) benzylidene-bornan-2-one and its salts 56039-58-8

28

4-tert-butyl-4'-methoxy-dibenzoylmethane 70356-09-1

29

2,2 ', 4,4'-tetrahydroxybenzophenone 131-55-5

30

2,2`-methylene-bis- [6 (2H-benzotriazol-2-yl) -4- (1,1,3,3, -tetramethylbutyl) phenol] 103597-45-1

31

2,2 '- (1,4-phenylene) -bis-1H-benzimidazol-4,6-disulfonic acid, Na salt 180898-37-7

32

2,4-bis- [4- (2-ethylhexyloxy) -2-hydroxy] phenyl-6- (4-methoxyphenyl) (1,3,5) -triazine 187393-00-6

33

3- (4-methylbenzylidene) -camphor 36861-47-9

- 36 -

Nr.

Product CAS-Nr.

 image 1

 image 1

(= acid)

3. 4

Polyethoxyethyl 4-bis (polyethoxy) para-aminobenzoate 113010-52-9

35

2,4-dihydroxybenzophenone 131-56-6

36

2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5.5-sodium sulfonate 3121-60-6

Polymeric or polymer bound substances can also be used in accordance with the invention. Advantageously, the cosmetic and dermatological preparations of

In accordance with the invention, they may also contain inorganic pigments based on metal oxides and / or other metal compounds that are hardly soluble or insoluble in water, especially based on titanium (TiO2), zinc (ZnO) oxides, of iron (for example Fe2O3), zirconium (ZrO2), silicon (SiO2), manganese (for example MnO), aluminum (Al2O3), cerium (for example Ce2O3),

10 of mixed oxides of the corresponding metals as well as mixtures formed by such oxides. Especially preferably, the pigments are constituted based on TiO2 and ZnO. It is especially advantageous, in the sense of the present invention, that, even if not necessary, inorganic pigments are present in the form

15 water repellent, that is to say that they have been treated superficially in a water repellent manner. This surface treatment may consist of the pigments being provided with a thin water-repellent layer, in a manner known per se, as described in DE-A-33 14 742. For the protection of human hair against UV irradiation, the

20 formulations of the protective agents against light, according to the invention, can be incorporated in shampoos, lotions, gels, hair sprays, foaming creams in aerosol form or emulsions in concentrations from 0.1 up to 10% by weight, preferably from 1 to 7% by weight. The corresponding formulations can be used in this

25 case, among other things, for washing, for dyeing as well as for styling

- 37

hair.

The formulations, to be used in accordance with the invention, are generally characterized by an especially high absorption capacity in the range of irradiation of the UV-A with a clear band structure. They are also perfectly soluble in cosmetic oils and can easily be incorporated into cosmetic formulations. The emulsions, prepared with the formulations, are especially characterized by their high stability, the formulations themselves being characterized by their high photostability, and the preparations made therewith are characterized by a pleasant touch on the skin.

The UV filtering effect of the formulations, in accordance with the invention, can also be used for the stabilization of the active products and auxiliary products in cosmetic and pharmaceutical preparations.

The preparations, in accordance with the invention, are characterized by an especially high absorption capacity in the UV-B irradiation range with a clear band structure and high light protection factors. Especially, the high light protection factor of the preparations, which was already measured with low concentrations of UV-absorbing active products, was surprising.

The following examples will explain the present invention without limiting it. Example 1 Obtaining a dry powder containing Uvinul® T 150 with an active ingredient content of 20% by weight a) Obtaining the aqueous dispersion

10 g of Uvinul® T 150 were dissolved in 216 g of acetone at room temperature in a molecularly dispersed state. To carry out the precipitation of Uvinul® T 150 in the form of a colloidal dispersion, the solution was fed to a mixing chamber at 240 ° C. In said chamber, the mixture was formed with an aqueous solution, adjusted to pH 9.1 by means of 1 N NaOH, consisting of 16.88 g of B 100 Bloom gelatin and 11.25 g of lactose in 1,500 ml of completely deionized water. The whole process was carried out under limitation of pressure at 40 bar in order to prevent evaporation of the

- 38

solvent After the formation of the mixture, a dispersion of Uvinul® T 150 was obtained in colloidal dispersion with a white-turbid hue.

The average value of the volume distribution was determined by means of Fraunhofer diffraction with a D value (4.3) = 0.50 µm with a fine proportion of the distribution of 98.5% <1.22 µm. b) Obtaining an aqueous dry powder containing Uvinul® T 150

After spray drying the dispersion, a dry powder with an active ingredient content of 20.56% by weight of Uvinul® T 150 was obtained (content determination was carried out by means of UV / VIS spectroscopy). The dried powder could be redispersed again in completely deionized water with the formation of a white-cloudy dispersion (hydrosol).

The average value of the volume distribution in the redispersion was determined by means of Fraunhofer diffraction with a D value (4.3) = 0.65 µm with a fine proportion of the distribution of 97.1% <1, 22 µm Example 2 a) Obtaining an aqueous dispersion containing Uvinul® T 150

10 g of Uvinul® T 150 in a solution of 2 g of ascorbyl palmitate in 216 g of acetone were introduced under stirring. To carry out the precipitation of Uvinul® T 150 in the form of a colloidal dispersion, this solution was fed in molecular dispersion to a mixing chamber at 20 ° C. In said chamber the formation of the mixture of the 16.88 g aqueous solution of Kollidon 90 F was carried out in

1,500 ml of completely deionized water. The whole process was carried out under pressure limitation at 40 bar in order to prevent evaporation of the solvent. After the formation of the mixture, a dispersion of Uvinul® T 150 was obtained in colloidal dispersion with a white-cloudy hue.

The average particle size with a value of 255 nm with a distribution width of ± 40% was determined by diffraction of the quasi-elastic light. The average value of the volume distribution was determined by means of Fraunhofer diffraction with a D value (4.3) = 0.62 µm with a fine proportion of the distribution of 99.8% <1.22 µm. b) Obtaining an aqueous dry powder of Uvinul® T 150

Spray drying of the dispersion in accordance with 2a) led

- 39

to a dry powder on a nanometric scale. The active substance content in the powder was determined by means of a UV / VIS spectroscopy with a value of 21.36% by weight of Uvinul® T 150. The dried powder was dissolved in completely deionized water forming a white dispersion -turbia (hydrosol).

The average particle size with a value of 350 nm with a distribution width of ± 44% was determined by means of diffraction of the quasi-elastic light.

The average value of the volume distribution was determined by means of Fraunhofer diffraction with a D value (4.3) = 0.62 µm with a fine proportion of the distribution of 99.8% <1.22 µm. Example 3 Obtaining a dry powder containing Uvinul® T 150 with an active ingredient content of 20% by weight a) Obtaining the aqueous dispersion

10 g of Uvinul® T 150 were suspended in a mixture consisting of 166 g of water and 50 g of acetone at room temperature and molecularly dissolved at a temperature of 240 ° C. To carry out the precipitation of Uvinul® T 150 in the form of a colloidal dispersion, the solution was fed to a mixing chamber at 240 ° C. In said chamber, the mixture was formed with an aqueous solution, adjusted to pH 9.1 by means of 1 N NaOH, consisting of 16.88 g of B 100 Bloom gelatin and 11.25 g of lactose in 1,500 ml of completely deionized water. The whole process was carried out under pressure limitation at 40 bar in order to prevent evaporation of the solvent. After the formation of the mixture, a dispersion of Uvinul® T 150 was obtained in colloidal dispersion with a white-turbid hue.

The average value of the volume distribution was determined by means of Fraunhofer diffraction with a D value (4.3) = 0.50 µm with a fine proportion of the distribution of 98.5% <1.22 µm. b) Obtaining an aqueous dry powder containing Uvinul® T 150

After spray drying the dispersion, a dry powder with an active ingredient content of 20.56% by weight of Uvinul® T 150 was obtained (content determination was carried out by means of UV / VIS spectroscopy).

- 40

The dried powder could be redispersed again in completely deionized water with the formation of a white-cloudy dispersion (hydrosol).

The average value of the volume distribution in the redispersion was determined by means of Fraunhofer diffraction with a D value (4.3) = 0.65 µm with a fine proportion of the distribution of 97% <1.22 µm . Example 4 (comparative example) Obtaining a dry powder containing Uvinul® BMBM with an active ingredient content of 20% by weight a) Obtaining the aqueous dispersion

10 g of Uvinul® BMBM was dissolved in 216 g of acetone at room temperature in a molecularly dispersed state. To carry out the precipitation of Uvinul® BMBM in the form of a colloidal dispersion, the solution was fed to a mixing chamber at 20 ° C. In said chamber, the mixture was formed with an aqueous solution, adjusted to pH 9.1 by means of 1 N NaOH, consisting of 16.88 g of B 100 Bloom gelatin and 11.25 g of lactose in 1,500 ml of completely deionized water. The whole process was carried out under pressure limitation at 40 bar in order to prevent evaporation of the solvent. After the formation of the mixture, a dispersion of Uvinul® BMBM was obtained in colloidal dispersion with a white-turbid hue.

The average value of the volume distribution was determined by means of Fraunhofer diffraction with a D value (4.3) = 0.50 µm with a fine proportion of the distribution of 98.5% <1.22 µm. b) Obtaining a dry powder containing Uvinul® BMBM

After spray drying the dispersion, a dry powder with an active ingredient content of 20.56% by weight of Uvinul® BMBM was obtained (content determination was carried out by means of UV / VIS spectroscopy). The dried powder could be redispersed again in completely deionized water with the formation of a white-cloudy dispersion (hydrosol).

The average value of the volume distribution in the redispersion was determined by means of Fraunhofer diffraction with a D value (4.3) = 0.65 µm with a fine proportion of the distribution of 96.5% <1, 20 µm Example 5

- 41

Precipitation of Uvinul® T 150 and shellac in leaves in the form of hydrosol, with ascorbyl palmitate and Na caseinate

In the first place, 23 g of Uvinul® T 150 and 47 g of shellac in sheets were placed under stirring, as a suspension of the active substance, in 343 g of

5 isopropanol. As an aqueous solution of protective colloid, 36 g of Na caseinate and 1.1 g of ascorbyl palmitate were dissolved in 10,820 g of water. The pH value was adjusted in this case to pH 6.9.

The suspension of the active ingredient was heated to a temperature of 95 ° C and mixed with a flow rate of 1.1 kg / h continuously with isopropanol / water azeotrope that had been brought to a temperature of 218 ° C, at a flow rate of 0, 8 kg / h In this case the Uvinul® T 150 and the shellac in sheets were molecularly dissolved. This solution was mixed with the aqueous solution of the protective colloid, which has been cited above, whose flow rate was 54.8 kg / h. In this case the Uvinul® T 150 and the shellac on sheets in the form of matrix particles precipitated, which stabilized in

15 form of hydrosol by means of Na caseinate. The hydrosol was then concentrated by evaporation in a rotary evaporator to a solid content of 31%, superficially painted with 14 g of B 200 Bloom jelly and then made by means of a double emulsion to give a dry powder. The Uvinul® T 150 content in the dry powder was then 15%.

20 Preparations Example 6 Composition for lip care Mass content (% by weight) Example 7 Composition for sunscreen with micropigments Mass content (% by weight) Example 8 Fat-free gel Mass content (% by weight)

up to 100

of Eucerinum anhydricum

10.00

of glycerin

10.00

of titanium dioxide, micronized

5.00

of Uvinul® T 150 dry powder from example 1

8.00

Octyl Methoxycinnamate

5.00

zinc oxide

4.00

castor oil

- 42

4.00

of stearate / caprate / caprylate pentaerythrityl adipate

3.00

of glyceryl stearate SE

2.00

beeswax

2.00

microcrystalline wax

2.00

of bentonite Quaternium-18

1.50

of PEG-45 / dodecyl glycol copolymer

up to 100

of water

10.00

Octyl Methoxycinnamate

6.00

PEG-7 Hydrogenated Castor Oil

6.00

of titanium dioxide, micronized

5.00

of Uvinul® T 150 dry powder from example 1

5.00

of mineral oil

5.00

of isoamyl p-methoxycinnamate

5.00

propylene glycol

3.00

jojoba oil

3.00

4-methylbenzylidenal camphor

2.00

of PEG-45 / dodecyl glycol copolymer

1.00

dimethicone

0.50

castor oil PEG-40 hydrogenated

0.50

tocopheryl acetate

0.50

phenoxyethanol

- 43

0.20

from EDTA

up to 100

of water

8.00

Octyl Methoxycinnamate

7.00

of titanium dioxide, micronized

5.00

of Uvinul® T 150 dry powder from example 1

5.00

of glycerin

5.00

from PABA PEG-25

1.00

4-methylbenzylidenal camphor

0.40

cross-linked alkyl acrylate polymer with 10 to 30 carbon atoms

0.30

of imidazolidinylurea

0.25

hydroxyethyl cellulose

0.25

of Sodium Methylparaben

0.20

of disodium EDTA

0.15

of fragrance

0.15

from Sodium Propylparaben

0.10

of sodium hydroxide

Example 9 Sunscreen (LSF 20) Mass content (% by weight)

up to 100

of water

8.00

Octyl Methoxycinnamate

- 44

8.00

of titanium dioxide, micronized

6.00

castor oil PEG-7 hydrogenated

5.00

of Uvinul® T 150 dry powder from example 1

6.00

of mineral oil

5.00

zinc oxide

5.00

isopropyl palmitate

0.30

of imidazolidinylurea

3.00

jojoba oil

2.00

of PEG-45 / dodecyl glycol copolymer

1.00

4-methylbenzylidenal camphor

0.60

magnesium stearate

0.50

tocopheryl acetate

0.25

from methylparaben

0.20

of disodium EDTA

0.15

from propilparaben

Example 10 Water resistant sun cream. Mass content (% by weight)

up to 100

of water

8.00

Octyl Methoxycinnamate

5.00

castor oil PEG-7 hydrogenated

5.00

propylene glycol

4.00

isopropyl palmitate

4.00

caprylic / capric triglyceric

- Four. Five

5.00

of Uvinul® T 150 dry powder from example 1

4.00

of glycerin

3.00

jojoba oil

2.00

4-methylbenzylidenal camphor

2.00

of titanium dioxide, micronized

1.50

of PEG-45 / dodecyl glycol copolymer

1.50

dimethicone

0.70

magnesium sulfate

0.50

magnesium stearate

0.15

of fragrance

Example 11 Sun milk (LSF 6) Mass content (% by weight)

up to 100

of water

10.00

of mineral oil

6.00

castor oil PEG-7 hydrogenated

5.00

isopropyl palmitate

3.50

Octyl Methoxycinnamate

5.00

of Uvinul® T 150 dry powder from example 1

3.00

Caprylic triglyceride / caprice

3.00

jojoba oil

2.00

of PEG-45 / dodecyl glycol copolymer

0.70

magnesium sulfate

0.60

magnesium stearate

- 46

0.50

tocopheryl acetate

3.00

of glycerin

0.25

from methylparaben

0.15

from propilparaben

0.05

tocopherol

Example 12 Day lotion with UV protection Mass content (% by weight)

up to 100

of water

2.00

stearyl alcohol

1.00

of glycerin monostearate

2.00

Vaseline

7.50

Octyl Methoxycinnamate

4.00

octyl salicylate

3.00

of Uvinul® T 150 dry powder from example 1

1.50

of 4-tert-butyl-4'-methoxy-dibenzoylmethane

0.50

dimethicone

5.00

propylene glycol

0.20

from EDTA

0.20

of carcomer

5.00

of alkyl benzoate with 12 to 15 carbon atoms

0.27

of triethanolamine

1.00

tocopheryl acetate

q.s.

of fragrance

- 47

Example 13 Day cream with UV protection Mass content (% by weight)

up to 100

of water

2.00

of cetearyl alcohol

2.00

cetyl alcohol

1.00

of glycerin monostearate

2.00

Vaseline

7.50

Octyl Methoxycinnamate

4.00

octyl salicylate

3.00

of Uvinul® T 150 dry powder from example 1

1.50

of 4-tert-butyl-4'-methoxy-dibenzoylmethane

4.00

propylene glycol

0.20

from EDTA

0.20

from carbomer

0.20

xanthan

0.20

cross-linked alkyl acrylate polymer with 10 to 30 carbon atoms

5.00

of alkyl benzoate with 12 to 15 carbon atoms

0.54

of triethanolamine

1.00

tocopheryl acetate

q.s.

of fragrance

q.s.

of conservation agent

Example 14 Liquid Makeup

Mass content (% by weight)

- 48

up to 100

of water

2.00

of cetearyl alcohol

2.00

from Ceteareth 25

6.00

of glycerin monostearate

1.00

cetyl alcohol

8.00

paraffin oil

7.00

cetearyl octanoate

0.2

dimethicone

3.00

propylene glycol

1.00

of panthenol

3.00

of Uvinul® T 150 dry powder from example 1

1.50

of 4-tert-butyl-4'-methoxy-dibenzoylmethane

3.50

Octyl Methoxycinnamate

0.1

from bisabolol

5.70

titanium dioxide

1.10

iron oxide

q.s.

of fragrance

Example 15 Hair gel with sun protection Mass content (% by weight)

up to 100

of water

1.20

from carbomer

0.50

hydroxyethyl cellulose

4.00

of triethanolamine

- 49

0.70

castor oil PEG-40 hydrogenated

1.50

of Uvinul® T 150 dry powder from example 1

0.70

of 4-tert-butyl-4'-methoxy-dibenzoylmethane

2.80

Octyl Methoxycinnamate

5.00

propylene glycol

0.01

from EDTA

q.s.

of fragrance

q.s.

of Sicovit Patentblau 85 E 131

Claims (22)

1.-Aqueous dispersions of organic substances, hardly soluble in water or insoluble in water, UV filters, characterized in that they contain at least one organic substance, hardly soluble in water or insoluble in water, 5 UV filter as a phase in colloidal dispersion in amorphous or partially amorphous form, because it can be obtained by a) the preparation of a solution in molecular dispersion of at least one organic substance, hardly soluble in water or insoluble in water, 10 UV filter, in an organic solvent, b) the combination of this solution with an aqueous solution of at least one protective colloid, the hydrophobic phase of the UV filtering substance being constituted as a colloidal dispersion phase and c) the release of the dispersion, thus obtained, from the organic solvent; 15 being the organic substance, at least unique, hardly soluble in water or insoluble in water, UV filter, a 1,3,5-triazine derivative of the formula I, image 1 in which the substituents have, independently of each other, the following meaning: 20 R means hydrogen, halogen, OH, alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, alkoxyalkyl with 1 to 20 carbon atoms, hydroxyalkoxy with 1 to 20 carbon atoms, NR1R2, or a remainder of the formula Ia image 1 R1 and R2 mean hydrogen, alkyl with 1 to 20 carbon atoms, aryl - 51 with 6 to 12 carbon atoms substituted, if any, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 10 carbon atoms substituted, if necessary, with one or more alkyl with 1 to 4 carbon atoms, substituted heteroaryl, if any, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms; R3 to R5 mean hydrogen, OH, NR9R10, alkoxy with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 up to 10 carbon atoms substituted, if necessary, with one or more alkyl with 1 to 4 carbon atoms, heteroaryl substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms; R6 to R8 mean hydrogen, alkoxy with 1 to 20 carbon atoms, -C (= O) -R11, -C (= O) -X-R12, SO2R13, CN; R9 to R11 mean hydrogen, alkyl with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if any, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 10 carbon atoms carbon substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, heteroaryl substituted, if appropriate, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms ; R12 means hydrogen, alkyl with 1 to 20 carbon atoms, aryl with 6 to 12 carbon atoms substituted, if any, with one or more alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 10 carbon atoms substituted, if necessary, with one or more alkyl with 1 to 4 carbon atoms, substituted heteroaryl, if necessary, with one or more alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or a residue of the formula Sp-Sil; R13 means alkyl with 1 to 20 carbon atoms, cycloalkyl with 5 organic, hardly soluble in water or insoluble in water, UV filter as particles on a nanometric scale with an average particle size in the range between 0.01 and 2 µm in amorphous or partially amorphous form.
- 52

up to 8 carbon atoms, aryl with 6 to 12 carbon atoms

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, aralkyl

with 7 to 10 carbon atoms

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, substituted heteroaryl, if any, with one or

with several alkyl with 1 to 4 carbon atoms;

X

means O, NR14;

R14

means hydrogen, alkyl with 1 to 20 carbon atoms, aryl

with 6 to 12 carbon atoms substituted, if necessary, with one or

with several alkyl with 1 to 4 carbon atoms, aralkyl with 7

up to 10 carbon atoms substituted, if any, with one or with

various

I rent with one until 4 atoms from carbon, heteroaryl

substituted, if necessary, with one or more alkyl with 1 to 4

carbon atoms, cycloalkyl with 5 to 8 carbon atoms;

Sp

means spacer;

Sil

it means a rest coming of the group constituted by silanes,

oligosiloxanes and polysiloxanes.

2.-Aqueous dispersions according to claim 1, characterized in that

is it so

constituted by suspensions that they contain, to the less, a substance

3. Aqueous dispersions according to claim 1, characterized in that the particles of the colloidal dispersion phase have a core and a crust, the core containing at least one organic substance, hardly soluble in water or insoluble in water, filtering of the UV and containing the cortex, at least one protective colloid. 4.-Aqueous dispersions according to one of claims 1 to 3, containing from 0.1 to 70% by weight of at least one organic substance, hardly soluble in water or insoluble in water, UV filter, from 0.1 to 80% by weight of at least one polymeric protective colloid, all referring to - 53 indications in percentage of the dry mass of the aqueous dispersion. 5.-Aqueous dispersions according to claim 4, further containing from 0.1 to 70% by weight of at least one plasticizer, from 0.1 to 70% by weight of at least an emulsifier and / or from 0.01 to 50% in 5 weight of at least one antioxidant and / or a preservative. 6. Aqueous dispersions according to claim 1, characterized in that the particles of the colloidal dispersion phase contain a polymer matrix insoluble in water, in which the organic substance is embedded, at least unique, hardly soluble in water or insoluble in water, UV filter. 7. Aqueous dispersions according to claim 6, characterized in that the colloidal dispersion particles are additionally coated by a protective colloid. 8. Aqueous dispersions according to claim 6, containing from 0.1 to 70% by weight of at least one organic substance, hardly soluble in water or insoluble in water, UV filter, from 0 , 1 to 80% by weight of at least one water-insoluble matrix polymer and from 0 to 80% by weight of at least one polymeric protective colloid, all indications referring in percentage to the dry mass of the aqueous dispersion 9. Aqueous dispersions according to claim 8, further containing 20 from 0.1 to 70% by weight of at least one plasticizer, from 0.01 to 70% by weight of at least , an emulsifier and / or from 0.01 to 50% by weight of at least one antioxidant. 10.-Aqueous dispersions according to claim 1 to 9, which contain at least one 1,3,5-triazine derivative of the formula Ib, wherein the substituents 25 have, independently of each other, the following meaning : image 1 R3 to R5 mean hydrogen, OH; R6 to R8 means alkoxy with 1 to 12 carbon atoms, -C (= O) -X-R12; - 54 X means O, NR14; R12 and R14 mean hydrogen, alkyl with 4 to 8 carbon atoms. 11. Process for obtaining an aqueous dispersion of at least one organic substance, hardly soluble in water or insoluble in water, UV filter, defined according to claim 1, characterized in that a) a dispersion solution is prepared molecular of at least one substance organic, hardly soluble in water or insoluble in water, filtering UV, in an organic solvent, b) this solution is combined with an aqueous solution of at least one colloid protective, forming the water-repellent phase of the UV filter substance as the phase in colloidal dispersion and c) the dispersion, thus obtained, of the organic solvent is released. 12. Method according to claim 11, characterized in that as an organic solvent in step a) of the process, at least one organic solvent, miscible with water, or a mixture formed by water and at least one miscible organic solvent is used with water. 13. Method according to one of claims 11 or 12, characterized in that in step a) other additives, chosen from the group consisting of emulsifiers, antioxidants, preservatives, preservatives, are added to the molecular dispersion solution. Water insoluble polymers and cosmetic oils. 14. Method according to one of claims 11 to 13, characterized in that in step b) the aqueous solution of the protective colloid additionally contains at least one plasticizer. 15. Process according to one of claims 11 to 14, characterized in that in step a) the solution in molecular dispersion of at least one organic substance, hardly soluble in water or insoluble in water, UV filter is prepared to temperatures above 15 ° C and immediately thereafter combined in step b) with the aqueous solution of the protective colloid, a temperature of the mixture between 35 ° C and 120 ° C being adjusted. 16.-Procedure for obtaining an aqueous dispersion of at least one organic substance, hardly soluble in water or insoluble in water, filtering - 55 UV, defined according to claim 6, characterized in that a) a solution in molecular dispersion of at least one substance is prepared organic, hardly soluble in water or insoluble in water, filtering UV, and a water insoluble polymer in an organic solvent, b) this solution is combined with an aqueous solution of at least one colloid protective, forming the water repellent phase of the mixture constituted by the UV filter substance and water-insoluble polymer, as a phase in colloidal dispersion and c) the dispersion, thus obtained, is released from the organic solvent. 17.-Procedure for obtaining a dry powder, which contains at least one organic substance, hardly soluble in water or insoluble in water, UV filter in the form of particles on a nanometric scale in amorphous or partially amorphous form, characterized in that It releases an aqueous dispersion from water, defined according to claim 1, and, if necessary, dries in the presence of a coating material. 18.-Powder preparations of at least one organic filter substance, hardly soluble in water or insoluble in water, containing at least one organic substance, hardly soluble in water or insoluble in water, UV filter of the formula I according to claim 1 in the form of particles on a nanometric scale with an average particle size in the range between 0.01 and 2 µm in amorphous or partially amorphous form. 19.-Procedure for obtaining an oil-miscible preparation of at least one organic substance, hardly soluble in water or insoluble in water, UV filter in the form of a double dispersion, characterized in that the emulsion is carried out in oil of an aqueous dispersion, defined according to claim 1, in the presence of an emulsifier. 20. Liquid preparations, miscible with oil of at least one organic substance, hardly soluble in water or insoluble in water, UV filter of the formula I according to claim 1, characterized in that as a double dispersion system they contain a phase aqueous dispersed with a particle diameter of less than 500 µm, in which stabilized particles are present in the dispersed state with a protective colloid of one or more organic substances, - 56 Hardly soluble in water or insoluble in water, UV filters as nano-scale particles with an average particle size in the range between 0.01 and 2 µm in amorphous or partially amorphous form, in an oil as a dispersing agent. 21.-Use of the aqueous dispersions, defined according to one of claims 1 to 10 as light-protecting photostable agents of organic materials. 22.-Use of the powder preparations, defined according to claim 18 as light-protecting photostable agents of organic materials. 23.-Use of liquid preparations, miscible with oil, defined according to claim 20 as light-protecting photostable agents of organic materials. 24. Use according to one of claims 21 to 23 as a stabilizer for synthetic materials and paints. 25. Use according to one of claims 21 to 23 as photostable filters of the UV in cosmetic and pharmaceutical preparations for carrying out the protection of the skin of human beings or of the hair of human beings against UV irradiation. 26. Use according to one of claims 21 to 23 as a stabilizer against UV in cosmetic and pharmaceutical preparations. 27.-Cosmetic and pharmaceutical preparations, containing protective agents against light, intended to carry out the protection of the skin of human beings or the hair of human beings against UV light in the range between 280 and 400 nm, characterized in that they contain active amounts of an aqueous dispersion, defined according to claim 1, in a cosmetic or pharmaceutical suitable excipient as photostable UV filters. 28.-Cosmetic and pharmaceutical preparations, containing protective agents against light, intended to carry out the protection of the skin of human beings or the hair of human beings against UV light in the range between 280 and 400 nm, characterized in that they contain quantities - 57 active ingredients of a powder preparation, defined according to claim 18, in a cosmetic or pharmaceutical suitable excipient as photostable UV filters. 29.-Cosmetic and pharmaceutical preparations containing protective agents against light, intended to carry out the protection of the skin of human beings or the hair of human beings against UV light in the range between 280 and 400 nm, characterized in that they contain active amounts of an oil-miscible liquid preparation, defined according to claim 20, in a cosmetic or pharmaceutical suitable excipient as photostable UV filters.