EP1663133A2

EP1663133A2 - Powdered preparations containing a mixture of 2,4,6-trianilino-p-(carbo-2'-ethylhexyl-1'-oxi)-1,3,5-triazine and diethylamino-hydroxybenzoyl-hexyl-benzoate

Info

Publication number: EP1663133A2
Application number: EP04786919A
Authority: EP
Inventors: Werner Goedel; Birgit Blanz; Helmut Auweter; Valerie Andre; Michael Schaper; Andreas Habich
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2003-09-15
Filing date: 2004-09-08
Publication date: 2006-06-07
Also published as: DE10342861A1; JP2007505820A; CA2537712A1; US20070028401A1; KR20060054462A; CN100459968C; WO2005025521A3; WO2005025521A2; CN1852699A

Abstract

The invention relates to a method for the production of powdered preparations containing 2,4,6-trianilino-p-(carbo-2'-ethylhexyl-1'-oxi)-1,3,5-triazine of formula I and diethylamino-hydroxybenzoyl-hexyl-benzoate of formula II by a) jointly dispersing compounds I and II in an aqueous molecularly disperse or colloidally disperse solution of a protective colloid, and b) converting the obtained dispersion into a dry powder by eliminating the water and additionally used solvents, if applicable, and drying. The inventive method is characterized in that modified starch is used as a protective colloid in step a).

Description

Powdery preparations containing a mixture of 2,4,6-trianilino-p- (carbc ~ 2'-ethylhexyl-1-oxi) -1, 3,5-triazine and diethylamino-hydroxybenzoyl-hexyl benzoate

description

The invention relates to powdered preparations containing a mixture of 2,4,6-trianilino-p- (carbo-2'-ethylhexyl-1 '-oxi) -1, 3,5-triazine and diethylamino-hydroxybenzoyl-hexyl-benzoate, their production and their use as photostable light stabilizers.

The quality or service life of many organic materials, for example plastics and lacquers, but also pharmaceutical and cosmetic preparations, can be adversely affected by the action of light, in particular UV rays. This loss of quality often manifests itself in plastics and paints in yellowing, discoloration, cracking or embrittlement of the material. In the case of pharmaceutical and cosmetic preparations, the influence of UV rays can degrade the active ingredients contained in the formulations.

The harmful effect of the ultraviolet part of the sun's radiation on the skin or hair, which in the broadest sense is also an organic material, is also a problem that is becoming increasingly important. While rays with a wavelength shorter than 290 nm (the so-called UVC range) are absorbed by the ozone layer in the earth's atmosphere, rays in the range between 290 nm and 320 nm, the so-called UVB range, cause radiation Skin erythema, a simple sunburn or even more or less severe burns.

The narrower range around 308 nm is specified as a maximum of the effectiveness of sunlight.

Numerous compounds are known for protection against UVB radiation, which include are triazine derivatives, derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and 2-phenylbenzimidazole.

For the range between about 320 nm and about 400 nm, the so-called UVA range, it is important to have filter substances available, since their rays can cause reactions in light-sensitive skin. It has been proven that UVA radiation leads to damage to the elastic and collagen fibers of the connective tissue, which causes the skin to age prematurely, and that it can be seen as the cause of numerous phototoxic and photoallergic reactions. The damaging influence of UVB radiation can be intensified by UVA radiation. Derivatives of dibenzoylmethane are used to protect against UVA rays, but their photostability is not sufficient (Int. J. Cosm. Science 10, 53 (1988)).

EP-A-1 046391 describes the use of amino-substituted hydroxybenzophenones as photostable UVA filters in cosmetic preparations.

However, UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products interfere with the skin's metabolism.

Such photochemical reaction products are predominantly free radical compounds, for example hydroxy radicals. Undefined radical photo products, which are created in the skin itself, can also display uncontrolled subsequent reactions due to their high reactivity. But also singlet oxygen, a non-radical excited state of the oxygen molecule can occur with UV radiation, just as short-lived epoxies and many others. Singlet oxygen, for example, is characterized by increased reactivity compared to the triplet oxygen that is normally present (radical ground state). However, there are also excited, reactive (radical) triplet states of the oxygen molecule.

UV radiation also belongs to ionizing radiation. There is therefore a risk that ionic species can also be formed when exposed to UV, which in turn can then have an oxidative effect on the biochemical processes.

A technical disadvantage of many UV filters is their poor solubility in water and / or in natural and synthetic oils, e.g. in silicone oils and in fatty acid triglycerides, which often limits their use, for example, in cosmetic formulations.

Another disadvantage when applying some light stabilizers is the occurrence of skin irritation and allergies due to excessive skin permeability.

Numerous processes have already been published to improve the formulability of insoluble or only sparingly soluble UV absorbers.

GB-A-2303549 describes a grinding process for the production of micronized insoluble organic UV absorbers in the presence of alkyl polyglycosides. The micronisates obtained in this way can be incorporated into cosmetic sunscreen preparations. GB-A-2286774 also includes a milling process for micronizing insoluble organic UV absorbers.

EP-A-1 127567 describes aqueous dispersions of sparingly water-soluble or water-insoluble organic UV filter substances and dry powders produced therefrom, characterized in that they contain at least one sparingly water-soluble or water-insoluble organic UV filter substance as a colloidally disperse phase in amorphous or partially amorphous form , The use of the protective colloids mentioned in this document - in particular gelatin or casein or caseinate - leads to powdery products whose solubility in cold water is unsatisfactory. Furthermore, gelatin and casein in cosmetic formulations can cause skin allergies.

It was an object of the present invention to provide a process for the preparation of light stabilizer formulations which provide effective protection for organic material, in particular for human skin and / or human hair, from UVA and UVB rays which are well tolerated by the skin and which can be easily incorporated into both lipophilic and, in particular, aqueous systems.

This object has been achieved by a process for the preparation of powdered preparations containing 2,4,6-trianilino-p- (carbo-2'-ethylhexyl-1 '-oxy) - 1,3,5-triazine of the formula I.

and diethylamino-hydroxybenzoyl-hexyl-benzoate of the formula

by

a) jointly dispersing the compounds I and II in an aqueous molecularly disperse or colloidally disperse solution of a protective colloid and

b) converting the dispersion formed into a dry powder by separating off the water and, if appropriate, additionally used solvents and drying,

characterized in that modified protective starch is used in process step a).

2,4 ₎ 6-Trianilino-p- (carbc-2'-ethyl-hexyl-1 ^, -oxy) -1,3,5-triazine of the formula I is sold by BASF Aktiengesellschaft under the trade name Uvinul ⁰ T150 as UVB- Filters marketed. Uvinul ⁰ T150 is characterized by good UV absorption properties with an exceptionally high extinction coefficient> 1500 at 314 nm.

Diethylamino-hydroxybenzoyi-hexyl-benzoate of the formula II is marketed by the BASF Aktiengesellschaft under the trade name Uvinul ^® A Plus as a UVA filter. Uvinul ^® A Plus is characterized by high photostability and good UV absorption properties with a high extinction coefficient of 940 at 354 nm.

In the context of the present invention, the term aqueous dispersions means both aqueous suspensions and emulsions. Aqueous suspensions in which the dispersed phase contains the triazine I and the benzoyl benzoate II as nanoparticulate particles are preferred.

In the context of the present invention, the term modified starch preferably includes esters of starch with organic acids, for example with acetic acid and higher fatty acids (C ₆ -C ₂ 6), and also with succinic acid, adipic acid and citric acid. The starch can be obtained from corn, potatoes or wheat, among others. A particularly preferred modified starch is octenyl succinate starch, which is marketed under the trademark HiCap ^® by National Starch or EmCap ^® by Cerestar.

A preferred variant of the method according to the invention is characterized in that the dispersion in stage a) comprises the following steps:

ai) dissolving the compounds I and II in one or more water-miscible organic solvents or in a mixture of water and one or more water-miscible organic solvents or a ₂ ) dissolving the compounds I and II in one or more water-immiscible, organic solvents and

a ₃ ) Mixing the solution obtained according to ai) or a ₂ ) with an aqueous molecularly disperse or colloidally disperse solution of modified starch, the hydrophobic phase of triazine I being formed as a nanodisperse phase.

Depending on the type of solvent used, the nanodisperse phase in step a ₃ ) can be solid nanoparticles [suspension; obtainable by combining ai) and a ₃ )] or nanodroplets (emulsion; obtainable by combining a ₂ ) and a ₃ )].

The water-miscible solvents used in stage a-i) are, above all, water-miscible, thermally stable, volatile solvents containing only carbon, hydrogen and oxygen, such as alcohols, ethers, esters, ketones and acetals. Such solvents are expediently used which are at least 10% water-miscible, have a boiling point below 200 ° C., preferably below 100 ° C. and / or have less than 10 carbons. Methanol, ethanol, n-propanol, isopropanol, 1,2-butanedioM-methyl ether, 1, 2-propanediol-1-n-propyl ether, tetrahydrofuran or acetone or mixtures thereof are particularly preferred, isopropanol or acetone being very particularly preferred used.

In the context of the present invention, the term “a water-immiscible organic solvent” stands for an organic solvent with a water solubility at normal pressure of less than 10%. Possible solvents include halogenated aliphatic hydrocarbons, e.g. Methylene chloride, chloroform and carbon tetrachloride, carboxylic acid esters such as diethyl carbonate, ethyl formate, methyl, ethyl or isopropyl acetate and ethers such as methyl tert. butyl ether in question. Preferred water-immiscible organic solvents are the following compounds from the group consisting of dimethyl carbonate, propylene carbonate, ethyl formate, ethyl acetate, isopropyl acetate and methyl tert. butyl ether.

The production of the dry powder in process step b) can include by spray drying, spray cooling, freeze drying and by drying in a fluidized bed, conventional drying or contact drying, the drying also being able to be carried out in the presence of a coating material (powdering agent). Suitable coating agents include: Corn starch, silica or tricalcium phosphate.

When the nanoparticles according to the invention are lyophilized, cryoprotective substances such as trehalose or polyvinylpyrrolidones can be added. An embodiment of the method according to the invention is particularly preferred in which

ai) the compounds I and II are dissolved in acetone or isopropanol or a mixture of water and acetone or water and isopropanol at temperatures in the range from 50 to 240 ° C.,

a ₃ ) the solution obtained is mixed with an aqueous molecularly disperse or colloidally disperse solution of modified starch, in particular octenyl succinate starch at temperatures in the range from 25 to 120 ° C. and

b) the suspension formed is spray-dried after removal of the organic solvent.

The production of the above Dry powder is advantageously carried out by mixing the compounds I and II together in acetone or isopropanol or a mixture of water and acetone or water and isopropanol at temperatures in the range from 50 ° C. to 240 ° C., in particular 100 ° C. to 200 ° C. - particularly preferably in the range from 105 ° C to 180 ° C.

For the rapid preparation of the molecularly disperse solution, the application of increased pressure, e.g. in the range from 20 bar to 200 bar, preferably 30 to 100 bar.

The molecularly disperse solution thus obtained is then mixed directly with the optionally cooled aqueous molecularly disperse or colloidally disperse solution of the modified starch, in particular octenyl succinate starch, in such a way that a mixture temperature of about 25 ° C. to 120 ° C., preferably 40 ° C. to 80 ° C, particularly preferably 45 ° C to 70 ° C.

The solvent component is converted into the aqueous phase and the hydrophobic phase of triazine I and benzoyl benzoate II is formed as a nanodisperse phase.

Mixing in step a ₃ ) can be carried out by introducing the solution containing triazine and benzoyl benzoate and metering in the aqueous solution of modified starch or vice versa, or by preferably metering both solutions simultaneously and continuously into a mixing chamber.

With regard to a more detailed description of the process and apparatus for the above-mentioned dispersion, reference is made to EP-B-0065 193 at this point. In order to increase the mechanical stability of the end product, it may be expedient in some cases to add a further plasticizer to the colloid, such as sugar or sugar alcohols, for example sucrose, glucose, glucose syrup, dextrin, invert sugar, sorbitol, mannitol or glycerol.

To increase the stability of the active ingredient against oxidative degradation, it may also be expedient to add stabilizers such as .alpha.-tocopherol, t-butyl-hydroxy-toluene, t-butyl-hydroxyanisole, ascorbic acid or ethoxyquin. They can be added to either the aqueous or the solvent phase, but they are preferably dissolved together with the triazine I in the solvent phase.

Furthermore, the light stabilizer formulations can be based on low molecular weight surface-active compounds (emulsifiers) in a concentration of 0.01 to 70% by weight, preferably 0.1 to 50% by weight, particularly preferably 0.5 to 20% by weight on the dry matter of the sunscreen formulation. As such, amphiphilic compounds or mixtures of such compounds are particularly suitable. Basically, all surfactants with an HLB value of 5 to 20 can be used. Examples of suitable surface-active substances are: esters of long-chain fatty acids with ascorbic acid, mono- and diglycerides of fatty acids and their oxymethylation products, esters of monofatty acid glycerides with acetic acid, citric acid, lactic acid or diacetyltartaric acid, polyglycerol fatty acid esters such as e.g. the monostearate of triglycerol, sorbitan fatty acid ester, propylene glycol fatty acid ester and lecithin. Ascorbyl palmitate is preferably used.

To increase the stability of the active ingredient against microbial degradation, it may be appropriate to add preservatives such as e.g. Add methyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, sorbic acid or benzoic acid or their salts.

According to the invention, dry powders can be obtained which no longer lose their properties obtained in the primary dispersion. This means that the amorphous or partially crystalline character of the UV filter substances I and II is retained. It is also a property of the invention that these powders, when redispersed again, with a deviation of 20%, preferably <15%, have the same particle size distribution that they had as the primary dispersion. It is also advantageous that the dry powders according to the invention absorb both in the UVA and in the UVB range.

Another preferred embodiment of the above-mentioned process is characterized in that the suspension produced in process step a) is ground into a dry powder before it is transferred. The grinding process is preferably carried out in such a way that the triazine I and the benzoyl benzoate II are suspended in crystalline form together in an aqueous, molecularly disperse or colloidally disperse solution of modified starch and comminuted to the desired particle size by grinding.

The grinding can be carried out in a manner known per se, e.g. be carried out with a ball mill. Depending on the type of mill used, grinding is carried out until the particles have an average particle size D [4.3], determined via Fraunhofer diffraction, of 0.01 to 100 μm, preferably 0.02 to 50 μm, particularly preferably 0.05 to 20 μm , very particularly preferably 0.05 to 5 μm, in particular 0.1 to 1 μm. The term D [4,3] denotes the volume-weighted mean diameter (see manual for Malvern Mastersizer S, Malvern Instruments Ltd., UK).

By heating the aqueous suspension after the grinding process to a temperature above the melting point of triazine I and benzoyl benzoate II and then spray drying the "melt emulsion", it is possible to increase the amorphous content of active ingredients I and II in the resulting dry powder. Details on the grinding of active substances in aqueous protective colloid solutions can be found in EP-B-0498824 and EP-B-0684973.

The invention also relates to powdered preparations of a mixture of 2,4,6-trianilino-p- (carbo-2'-ethylhexyl-1 '-oxy) -1,3,5-triazine of the formula I and diethylamino-hydroxybenzoyl -hexyl benzoate of the formula II, obtainable by the processes mentioned above.

The new light stabilizer formulations are characterized in that they contain the compounds I and II, the amorphous content of which is in the range greater than 10%, preferably greater than 30%, particularly preferably in the range from 50 to 100%, very particularly preferably in the range from 75 to 99% lies. The crystallinity rate of active ingredients I and II can be determined, for example, by X-ray diffraction measurements.

The UV absorber content of the formulas I and II in the light stabilizer formulations according to the invention is in the range from 0.1 to 70% by weight, preferably in the range from 2 to 40% by weight, particularly preferably in the range from 3 to 30% by weight, very particularly preferably in the range from 5 to 25% by weight, based on the dry mass of the formulations.

The light stabilizer formulations according to the invention contain, per part by weight of triazine of the formula I, 0.1 to 10 parts by weight of benzoyl benzoate of the formula II, preferably 0.5 to 2 parts by weight, particularly preferably 0.8 to 1.2 parts by weight of benzoyl benzoate of the formula II. The average particle size D [4,3] of the nanoparticulate particles in the aqueous dispersion is, depending on the type of formulation method, in the range from 0.01 to 100 μm, preferably in the range from 0.02 to 50 μm, particularly preferably in the range from 0, 05 to 20 μm, very particularly preferably in the range from 0.05 to 5 μm, in particular 0.1 to 1 μm.

While ground UV filter substances tend to increase particle size when incorporated into skin creams, which can lead to a deterioration in the sun protection factor and an unpleasant feeling on the skin, the dry powders according to the invention do not show such tendencies due to their matrix and protective colloid structure.

The formulations according to the invention - dispersions and dry powder produced therefrom - are outstandingly suitable for stabilizing organic material, among other things. against the effects of light, oxygen and heat. They are added to the organic material to be stabilized in a concentration of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably 0.02 to 2% by weight, based on the organic material , ir, added during or after its manufacture.

Organic material includes, for example, photographic recording materials, e.g. B. photographic emulsions or precursors for plastics and paints, but especially plastics and paints themselves.

Organic material also means cosmetic preparations such as creams, lotions, gels, lipsticks.

The present invention also relates to an organic material stabilized against the action of light, oxygen and heat, in particular plastics and lacquers, containing 0.01 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably from 0.02 to 2% by weight, based on the total amount of the organic material, of the compounds I and II in the form of the formulations according to the invention.

To mix the formulations according to the invention, above all with plastics, all known devices and methods for mixing stabilizing agents or other additives into polymers can be used.

The organic material stabilized by the formulations according to the invention can optionally contain further additives, for example antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, pigments and fillers. Antioxidants and light stabilizers which can be added in addition to the formulations according to the invention are, for example, compounds based on sterically hindered phenols or costabilizers containing sulfur or phosphorus.

Examples of such phenolic antioxidants are 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- [ß- (3,5- di-tert-butyl-4-hydroxyphenyl) propionylethyl] isocyanurate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate and pentaerythritol tetrakis [B- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] mentioned.

Examples of phosphorus-containing antioxidants are tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butyl-phenyl) phosphite, tris (2-tert-butyl-4-methylphenyl) phosphite , Bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphite.

Examples of sulfur-containing antioxidants are dilauryl thiodopropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (β-lauryl thiopropionate) and pentaerythritol tetrakis (β-hexylthiopropionate).

Other antioxidants and light stabilizers that can be used together with the formulations according to the invention are e.g. 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, aryl esters of hydroxybenzoic acids, α-cyanocinnamic acid derivatives, benzimidazolecarboxylic acid anilides, nickel compounds or oxalic acid dianiiides.

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

Examples of suitable sterically hindered amines are: bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, the condensation product of 1- Hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N'-di (2,2,6,6-tetramethylpiperidyl) hexamethylene diamine and 4-tert-octylamino -2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethylpiperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, 1, 1 '- (1, 2-ethanediyl) -bis- (3,3,5,5-tetramethylpiperazinone), the condensation products of 4-amino-2,2 , 6,6-tetramethylpiperidines and tetra-methylol-acetylene diureas. Examples of plastics which can be stabilized by the compounds I according to the invention are:

Polymers of mono- and diolefins, e.g. Low or high density polyethylene, polypropylene, linear polybutene-1, polyisoprene, polybutadiene and copolymers of mono- or diolefins or mixtures of the polymers mentioned;

Copolymers of mono- or diolefins with other vinyl monomers, e.g. Ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers;

Polystyrene and copolymers of styrene or α-methylstyrene with dienes and / or acrylic derivatives, such as e.g. Styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methacrylate, acrylonitrile-butadiene-styrene (ABS) or methyl methacrylate-butadiene-styrene (MBS);

halogen-containing ^polymers,> \ for example, polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof; tir

Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates, polymethacrylates, polyacrylamides and polyacrylonitriles;

Polymers derived from unsaturated alcohols and amines or from their acyl derivatives or acetals, e.g. Polyvinyl alcohol and polyvinyl acetate;

Polyurethanes, polyamides, polyureas, polyesters, polycarbonates, polysulfonates, polyether sulfones and polyether ketones.

Furthermore, aqueous formulations and varnish coatings can be stabilized with the formulations according to the invention, e.g. Industrial coatings. Among these, stove enamels, among them vehicle paints, preferably two-coat paints, are particularly noteworthy.

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

The additional additives already listed, in particular antioxidants and light stabilizers, can also be used when used as stabilizers in paints. The light stabilizer formulations according to the invention are very particularly preferably also suitable as photostable UV filters in cosmetic and dermatological preparations for protecting human skin or human hair against sun rays, but also against artificial light which has high UV components, alone or together with for cosmetic or pharmaceutical preparations known, absorbing compounds in the UV range. In the broadest sense, organic materials also include human skin and hair. The cosmetic and pharmaceutical preparations as such are of course also stabilized in order to remain effective for as long as possible.

Accordingly, the present invention also relates to cosmetic and pharmaceutical preparations containing light stabilizers for protecting human skin or hair against UV light in the range from 280 to 400 nm, characterized in that they are in a cosmetically or pharmaceutically suitable carrier as photostable UV Filter effective amounts of a formulation of the compounds I and II in amorphous or partially amorphous form - alone or together with UV-A and C known per se for cosmetic and pharmaceutical preparations

Compounds absorbing the UV-B region - contain, the formulations being the aqueous dispersions according to the invention mentioned at the beginning or the dry powders produced therefrom.

The amount of triazine I and benzoyl benzoate II in the form of the formulations according to the invention, which is used in the cosmetic and pharmaceutical preparations, is in the range from 0.05 to 20% by weight, preferably 0.1 to 10% by weight - Another preferred in the range of 1 to 7 wt .-%, based on the total amount of the cosmetic and pharmaceutical preparation.

The cosmetic and pharmaceutical preparations containing light stabilizers are generally based on a carrier which contains at least one oil phase. However, preparations based on water alone are also possible. Accordingly, oils, oil-in-water and water-in-oil emulsions, creams and pastes, lip protection stick compositions or grease-free gels are suitable.

The emulsions include O / W macroemulsions, O / W microemulsions or O / W / O emulsions with compounds of the formula I and II present in dispersed form are also possible, the emulsions being obtainable by phase inversion technology in accordance with DE-A-19726 121.

Typical cosmetic auxiliaries which can be considered as additives are, for example, co-emulsifiers, fats and waxes, stabilizers, thickeners, biogenic active ingredients, film formers, fragrances, dyes, pearlizing agents, preservatives, pigments, electrolytes (e.g. magnesium sulfate) and pH regulators , As co-emulsifiers Known W / O and also O / W emulsifiers such as polyglycerol esters, sorbitan esters or partially esterified glycerides are preferred. Typical examples of fats are glycerides; beeswax, paraffin wax or microwaxes may be mentioned as waxes, if appropriate in combination with hydrophilic waxes. Metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate can be used as stabilizers. Suitable thickeners are, for example, crosslinked polyacrylic acids and their derivatives, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also fatty alcohols, monoglycerides and fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone. Biogenic active substances are understood to mean, for example, plant extracts, protein hydrolyzates and vitamin complexes. Common film formers are, for example, hydrocolloids such as chitosan, microcrystalline chitosan or quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives and similar compounds. Suitable preservatives are, for example, formaldehyde solution, p-hydroxybenzoate or sorbic acid. Suitable pearlizing agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acids and fatty acid monoglycol esters. The dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, published by Verlag Chemie, Weinheim, 1984. These dyes are usually used in a concentration of 0.001 to 0.1% by weight, based on the mixture as a whole.

An additional level of antioxidants is generally preferred. All of the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.

The antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. ß-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thiorodoxine, glutathione, cysteine , Cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, and lauryl, palmitoyl, oleyl, v-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (eg buthioninsulfoximines, homocysteine sulfoximines, buthioninsulfones, penta-, hexa-, hea- p-tathionine sulfoximine) in very low tolerable doses (eg pmol to μmol / kg), also (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-oleolenic acid, lininoic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and their derivatives (e.g. ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbyl acetate) , Tocopherol and derivatives (e.g. vitamin E acetate, tocotrienol), vitamin A and derivatives (vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, Butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and un d its derivatives (eg selenomethionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide).

The amount of the aforementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 2G:% by weight, in particular 1 to 10% by weight, based on the total weight the accessory.

If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentration from the range from 0.001 to 10% by weight, based on the total weight of the formulation.

If vitamin A and / or its derivatives or carotenoids represent the antioxidant (s), it is advantageous to choose their respective concentration from the range from 0.001 to 10% by weight, based on the total weight of the formulation.

Typical oil components in cosmetics are, for example, silicone oils, paraffin oil, glyceryl stearate, isopropyl myristate, diisopropyl adipate, 2-ethylhexanoic acid cetyl stearyl ester, hydrogenated polyisobutene, petrolatum, caprylic acid / capric acid triglycerides, microcrystalline wax, lanolin and stearic acid.

The total proportion of auxiliaries and additives can be 1 to 80, preferably 6 to 40% by weight and the non-aqueous proportion ("active substance") 20 to 80, preferably 30 to 70% by weight, based on the composition. The preparation of the agents can be carried out in a manner known per se, i.e. for example by hot, cold, hot-hot / cold or PIT emulsification take place. This is a purely mechanical process, there is no chemical reaction.

Such sunscreen preparations can accordingly be in liquid, pasty or solid form, for example as water-in-oil creams, oil-in-water creams and lotions, aerosol foam creams, gels, oils, grease pencils, powders, sprays or alcoholic-aqueous lotions.

Finally, other substances known to be absorbing in the UV range can also be used, provided they are stable in the overall system of the combination of UV filters to be used according to the invention.

Most of the light stabilizers in the cosmetic and pharmaceutical preparations used to protect the human epidermis consist of compounds which absorb UV light in the UV-B range, i.e. in the range of 280 to

320 nm. For example, the proportion of UV-A absorbers to be used according to the invention is 10 to 90% by weight, preferably 20 to 50% by weight, based on the total amount of UV-B and UV-A absorbing substances.

Any UV-A and UV-B filter substances are suitable as UV filter substances which are used in combination with the formulations to be used according to the invention. Examples include:

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

The cosmetic and dermatological preparations according to the invention can advantageously also contain inorganic pigments based on metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular the oxides of titanium (TiO ₂ ), zinc (ZnO), iron (eg Fe ₂ O ₃ ), Contain zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (eg MnO), aluminum (Al ₂ O ₃ ), cerium (eg Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides. Pigments based on TiO ₂ and ZnO are particularly preferred. The inorganic pigments can be present in hydrophobic form, ie they are treated to be water-repellent on the surface. This surface treatment can consist in that the pigments are provided with a thin hydrophobic layer in a manner known per se, as described in DE-A-33 14742.

To protect human hair from UV rays, the light stabilizer formulations according to the invention can be used in shampoos, lotions, gels, hair sprays, hair colorants, aerosol foam creams or emulsions in concentrations of 0.1 to 10% by weight, preferably 1 to 7% by weight. % are incorporated. The respective formulations can include can be used for washing, dyeing and styling the hair.

The formulations to be used according to the invention are generally distinguished by a particularly high absorption capacity in the UV-A radiation range with a sharp band structure. Furthermore, they are readily soluble in cosmetic oils and can be easily incorporated into cosmetic formulations. The emulsions produced with the formulations are particularly notable for their high stability, the formulations themselves for their high photostability, and the preparations thus produced are characterized by their pleasant feeling on the skin.

The UV filter effect of the formulations according to the invention can also be used to stabilize active ingredients and auxiliaries in cosmetic and pharmaceutical formulations.

The preparations according to the invention are distinguished by a particularly high absorption capacity in the area of UV-A and UV-B radiation with a sharp band structure and high sun protection factors.

In particular, the high sun protection factor of the preparations, which was already measured at low concentrations of the UV-absorbing active ingredients I and II, was surprising.

Furthermore, the preparations according to the invention have the advantage of improved cold water dispersibility over other formulations containing triazine and benzoyl benzoate.

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

example 1 Production of a Uvinul ^® T 150- / Uvinul ^® A Plus-containing dry powder with an active ingredient content of approx. 20% by weight

a) Preparation of the aqueous dispersion

12.5 g of Uvinul ^® T 150 and 12.5 g of Uvinul ^® A Plus were dissolved in 216 g of an azeotropic mixture of acetone and water (88/12, v / v) at 70 ° C in a molecularly disperse manner. The solution was fed to a mixing chamber at 240 ° C. to precipitate the active substances in colloidally disperse form. There they were mixed with an aqueous solution of 45 g HiCap in 1455 ml demineralized water. The entire process was carried out under a pressure limit of 40 bar to prevent evaporation of the solvent. After mixing, a colloidally Uvinul ^® T150 / Uvinul ^® A Plus was - get dispersion with a pale yellow cloudy color. The mean value of the volume distribution was determined by means of Fraunhofer diffraction to be D (4.3) = 0.52 μm with a fine fraction of the distribution 87.5% <1.22 μm.

b) Preparation of Uvinul ^® T 150 / Uvinul A Plus ^{®-containing} aqueous Troekenpul- vers After spray drying the dispersion obtained is a dry powder having an active ingredient content of 10.5 wt .-% Uvinul ^® T 150, and 10.5 wt .-% Uvinul ^® A Plus (content was determined using UV / VIS spectroscopy). The dry powder could be redispersed again in demineralized water to form a white, cloudy dispersion (hydrosol).

The mean value of the volume distribution in the re-dispersion was determined by means of Fraunhofer diffraction to D (4.3) = 0.9 μm with a fine fraction of the distribution of 74% <1.22 μm.

preparations

Example 2: Composition for lip care

Mass content (% by weight)

ad 100 Eucerinum anhydricum

10.00 glycerin

10.00 titanium dioxide, micronized

5.00 Uvinul ^® T150 / Uvinul A Plus ^® dry powder from Example 1 8.00 Octyl methoxycinnamate

5.00 zinc oxide

4.00 castor oil , 00 pentaerythritol stearate / caprate / caprylate adipate, 00 glyceryl stearate SE, 00 beeswax, 00 microcrystalline wax, 00 quaternium-18 bentonite, 50 PEG-45 / dodecyl glycol copolymer

Example 3: Composition for sunblock with micropigments

Mass content (% by weight)

ad 100 water

10.00 octyl methoxcinnamate

6.00 PEG-7 Hydrogenated Castor Oil

6.00 Titanium dioxide, micronized

5.00 Uvinul ^® T150 / Uvinul ^® A Plus dry powder from Example 1 5.00 mineral oil

5.00 isoamyl p-methoxycinnamate

5.00 propylene glycol

3.00 jojoba oil

3.00 4-methylbenzylidene camphor 2.00 PEG-45 / dodecyl glycol copolymer

1,00 dimethicone

0.50 PEG-40 Hydrogenated Castor Oil

0.50 tocopheryl acetate

0.50 phenoxyethanol 0.20 EDTA

Example 4: Fat Free Gel

Mass content (% by weight)

ad 100 water

8.00 octyl methoxycinnamate

7.00 Titanium dioxide, micronized

5.00 Uvinul ^® T150 / Uvinul ^® A Plus dry powder from Example 1 5.00 glycerin

5.00 PEG-25 PABA

1, 00 4-methylbenzylidene camphor

0.40 Acrylate C ₁ 0-C30 alkyl acrylate cross polymer

0.30 imidazolidinyl urea 0.25 hydroxyethyl cellulose

0.25 sodium methylparaben

0.20 disodium EDTA

0.15 fragrance

0.15 sodium propylparaben 0.10 sodium hydroxide Example 5: Sunscreen (SPF 20)

Mass content (% by weight)

ad 100 water

8.00 octyl methoxycinnamate

8.00 Titanium dioxide, micronized

6.00 PEG-7 Hydrogenated Castor Oil

5.00 Uvinul ^® T150 / Uvinul ^® A Plus dry powder from Example 1 6.00 mineral oil

5.00 isopropyl palmitate

0.30 imidazolidinyl urea

3.00 jojoba oil

2.00 PEG-45 / dodecyl glycol copolymer 1.00 4-methylbenzylidene camphor

0.60 magnesium stearate

0.50 tocopheryl acetate

0.25 methyl paraben

0.20 disodium EDTA 0.15 propylparaben

Example 6: Sunscreen waterproof

Mass content (% by weight)

ad 100 water

8.00 octyl methoxycinnamate

5.00 PEG-7 Hydrogenated Castor Oil

5.00 propylene glycol 4.00 isopropyl palmitate

4.00 Caprylic / Capric triglyceride

5.00 Uvinul ^® T150 / Uvinul ^® A Plus dry powder from Example 1

4.00 glycerin

3.00 jojoba oil 2.00 4-methylbenzylidene camphor

2.00 titanium dioxide, micronized

1, 50 PEG-45 / dodecyl glycol copolymer

1, 50 dimethicone

0.70 magnesium sulfate 0.50 magnesium stearate, 15 fragments Example 7: Sun milk (SPF 6)

Mass content (% by weight)

ad 100 water 10.00 mineral oil

6.00 PEG-7 Hydrogenated Castor Oil

5.00 isopropyl palmitate

3.50 octyl methoxycinnamate 5.00 Uvinul ^® T150 / Uvinul ^® A Plus dry powder from Example 1

3.00 Caprylic / Capric triglyceride

3.00 jojoba oil

2.00 PEG-45 / dodecyl glycol copolymer

0.70 magnesium sulfate 0.60 magnesium stearate

0.50 tocopheryl acetate

3.00 glycerin

0.25 methyl paraben

0.15 propylparaben 0.05 tocopherol

Example 8: Day lotion with UV protection

Mass content (% by weight)

ad 100 water

2.00 cetearyl alcohol

1.00 glycerol monostearate

2.00 Vaseline

7.50 octyl methoxycinnamate

4.00 octyl salicylate

3.00 Uvinul ^® T150 / Uvinul ^® A Plus dry powder from Example 1

1, 50 4-tert-butyl-4'-methoxy-dibenzoylmethane

0.50 propylene glycol

0.20 EDTA

0.20 carbomer

5.00 C ₁₂ -C ₁₅ alkyl benzoate

0.27 triethanolamine

1.00 tocopheryl acetate qS Fragrance Example 9: Day cream with UV protection

Mass content (% by weight)

ad 100 water

2.00 cetearyl alcohol

2.00 cetyl alcohol

1.00 glycerol monostearate

2.00 petroleum jelly 7.50 octyl methoxycinnamate

4.00 octyl salicylate

3.00 Uvinul ^® T150 / Uvinul ^® A Plus dry powder from Example 1

1, 50 4-tert-butyl-4'-methoxy-dibenzoylmethane

4.00 propylene glycol 0.20 EDTA

0.20 carbomer

0.20 xanthan

0.20 Cιo-C ₃₀ alkyl acrylate cross polymer.

5.00 C ₁₂ -C ₁₅ alkyl benzoate 0.54 triethanolamine

1.00 tocopheryl acetate q.s. Fragrance q.s. preservative

Example 10: Liquid Make Up

Mass content (% by weight)

ad 100 water 2.00 Cetearyl alcohol

2.00 Ceteareth 25

6.00 glycerol monostearate

1.00 cetyl alcohol

8.00 paraffin oil 7.00 cetearyl octanoate

0.2 dimethicone

3.00 propylene glycol

1.00 panthenol

3.00 Uvinul ^® T150 / Uvinul A Plus ^® dry powder from Example 1 1 50 4-tert-butyl-4'-methoxydibenzoylmethane

3.50 octyl methoxycinnamate

0.1 bisabolol 5.70 titanium dioxide 1.10 iron oxide qs fragrance

Example 11: Hair gel with sun protection

Mass content (% by weight)

ad 100 water 1, 20 carbomer

0.50 hydroxyethyl cellulose

4.00 triethanolamine

0.70 PEG-40 Hydrogenated Castor oil

1, 50 Uvinul ^® Tl50 / Uvinul ^® A Plus dry powder from Example 1 0.70 4-tert-butyl-4'-methoxy-dibenzoylmethane

2.80 octyl methoxycinnamate

5.00 propylene glycol

0.01 EDTA q.s. Fragrance q.s. Sicovit patent blue 85 E 131

Claims

claims

1. Process for the preparation of powdered preparations containing 2,4,6-trianilino-p- (carbo-2-ethylhexyl-1'-oxi) - 1, 3,5-triazine of the formula I.

and diethylamino-hydroxybenzoyl-hexyl-benzoate of the formula II

by a) dispersing the compounds I and II together in an aqueous molecularly disperse or colloidally disperse solution of a protective colloid and b) converting the dispersion formed into a dry powder by separating off the water and, if appropriate, additionally used solvents and drying, characterized in that the protective colloid in the process step a) modified starch used.

2. The method according to claim 1, characterized in that the dispersion in step a) comprises the following steps: a- _t ) dissolving the compounds I and II in one or more water-miscible organic solvents (n) or in a mixture of water and one or more water-miscible organic solvents (n) or a ₂ ) dissolving the compounds I and II in one or more water-immiscible organic solvents (a) and a ₃ ) mixing the solution obtained according to ai) or a ₂ ) with an aqueous molecular-disperse or colloid-disperse solution of modified starch, the hydrophobic phase of the compounds I and II arise as a nanodisperse phase.

3. The method according to any one of claims 1 or 2, characterized in that the drying in process step b) is carried out in the presence of a coating material.

4. The method according to any one of claims 1 to 3, characterized in that it is in Disρergierschrf # a) to prepare a suspension of the compounds I and II in an aqueous molecularly disperse or colloidally disperse solution of modified starch.

5. The method according to claim 4, characterized in that the suspension produced in process step a) is ground before being transferred to a dry powder.

6. The method according to claim 4, characterized in that a ^ the compounds I and II in acetone or isopropanol or a mixture of water and acetone or water and isopropanol at temperatures in the range from 50 to 240 ° C, a ₃ ) the the solution obtained is mixed with an aqueous molecularly disperse or colloidally disperse solution of modified starch at temperatures in the range from 25 to 120 ° C. and b) the suspension formed is spray-dried after removal of the organic solvent.

7. The method according to any one of claims 1 to 3, characterized in that the dispersing step a) is the preparation of an emulsion of the compounds gen I and II acts in an aqueous molecularly disperse or colloidally disperse solution of modified starch.

8. The method according to any one of claims 1 to 7, characterized in that octenyl succinate starch is used as the protective colloid.

9. Powdery preparations of a mixture of 2,4,6-trianilinc-p- (carbo-2'-ethylhexyl-1 '-oxy) -1,3,5-triazine of the formula I and diethylamino-hydroxybenzoyl-hexyl-benzoate Formula II, obtainable by a process defined according to one of claims 1 to 8.

10. Preparations according to claim 9 with a content of triazine I and benzoyl benzoate II from 0.1 to 70 wt .-%.

11. Preparations according to one of claims 9 or 10 containing per part by weight of triazine I 0.1 to 10 parts by weight of benzoyl benzoate II.

12. Use of the powdered preparations, defined according to one of claims 9 or 10, a,> photostable UV filters in cosmetic and dermatological preparations.