DE10254335A1 - Sunscreen concentrate with water-soluble polymers - Google Patents

Abstract

A process for producing an O / W emulsion, characterized in that it contains an O / W emulsion
a) a lipid phase in a concentration of 20 to 95% by weight,
b) one or more water-soluble polymers in a total concentration of 1 to 80% by weight,
in each case based on the total weight of the preparation, and
c) one or more UV light protection filters and
d) an aqueous phase,
in addition to optionally further cosmetic and / or dermatological active ingredients, auxiliaries and additives, is dried by spray drying and / or freeze drying.

Description

• a) eine Lipidphase in einer Konzentration von 20 bis 95 Gewichts-%,
• b) ein oder mehrere wasserlösliche Polymere in einer Gesamtkonzentration von 1 bis 80 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung, sowie
• c) ein oder mehrere UV-Lichtschutzfilter und
• d) eine wässrige Phase, neben gegebenenfalls weiteren kosmetischen und/oder dermatologischen Wirk-, Hilfsund Zusatzstoffen, durch Sprühtrocknung und/oder Gefriertrocknung getrocknet wird.

The present invention relates to a method for producing an O / W emulsion, characterized in that it contains an O / W emulsion

• a) a lipid phase in a concentration of 20 to 95% by weight,
• b) one or more water-soluble polymers in a total concentration of 1 to 80% by weight, in each case based on the total weight of the preparation, and
• c) one or more UV light protection filters and
• d) an aqueous phase, in addition to any other cosmetic and / or dermatological active ingredients, auxiliaries and additives, is dried by spray drying and / or freeze drying.

The desire to look beautiful and attractive is inherently rooted in humans. Even if the ideal of beauty has undergone changes over time, so is the pursuit a flawless appearance, always been the goal of people. A substantial part of one beautiful and has an attractive exterior the condition and appearance of the skin and skin appendages, i.e. of hair and nails.

The skin is the largest organ of the human. Among its many functions (e.g. for heat control and as a sensory organ) is the barrier function, which is drying out the skin (and ultimately the entire organism), probably the most important. At the same time, the skin acts as a protective device the penetration and absorption of substances coming from outside and the UV radiation. This barrier function is caused by the epidermis, which as the outermost layer the actual protective cover towards the Environment forms. With about a tenth of the total thickness, it is simultaneous the thinnest Layer of skin.

So that the skin's biological Fully perform functions can, it needs regular cleaning and care. The cleaning of the skin serves to remove Dirt, sweat and leftovers dead skin particles, which are an ideal breeding ground for pathogens and parasites of all kinds. Skin care products, usually creams, ointments or lotions, are mostly used for moisturizing and regreasing of the skin. Frequently they have added active ingredients that regenerate the skin and For example, their premature aging (e.g. the emergence of Pucker, Prevent and reduce wrinkles).

Skin care products exist in the Usually from emulsions. Emulsions are generally understood heterogeneous systems consisting of two not or only to a limited extent miscible liquids consist of the usual are called phases and in which one of the two liquids in the form of the finest droplets in the other liquid is dispersed. externally and with sheer When viewed by eye, emulsions appear homogeneous.

Are the two liquids Water and oil and lie oil droplets fine distributed in water before, it is an oil-in-water emulsion (O / W emulsion, e.g. milk). The basic character of an O / W emulsion is shaped by the water. With a water-in-oil emulsion (W / O emulsion, e.g. butter) is the opposite principle, the basic character is determined here by the oil.

The trend away from the paleness for "healthy, athletic brown skin "is unbroken for years. To achieve this, people bet their skin from the sun's rays, as this causes pigment formation in the sense of melanin formation. The ultraviolet radiation However, sunlight also has a damaging effect on the skin. In addition to the acute damage (Sunburn) long-term damage occur like an elevated one Risk of skin cancer from excessive exposure to light from the UVB range (wavelength: 280-320 nm). The excessive exposure UVB and UVA radiation (wavelength: 320-400 nm) also leads to a weakening the elastic and collagen fibers of the connective tissue. This leads to numerous phototoxic and photoallergic reactions and has a premature Skin aging.

To protect the skin were therefore developed a range of light protection filters used in cosmetic preparations can be used. These UVA and UVB filters are in shape in most industrialized countries summarized by positive lists such as Appendix 7 of the Cosmetics Ordinance.

• – Sie besitzen ein hohes Gewicht, was beim Transport zu höherem Energieverbrauch und höheren Kosten führt.
• – Sie besitzen ein größeres Volumen, was beim Transport zu geringeren Transportkapazitäten führt.
• – Insbesondere dünnflüssige Emulsionen sind wesentlich aufwendiger zu lagern und transportieren, da die Zubereitungen „auslaufen" können.
• – Die Anwendungskonzentrationen der Inhaltsstoffe (z.B. UV-Filterkonzentration und damit UV-Filterleistung) sind dem Verbraucher bereits vorgegeben. Eine individuelle Anpassung an die Gegebenheiten am Anwendungsort sind nicht mehr möglich.

Conventional cosmetic and / or dermatological emulsions, for example sunscreen creams or lotions, have a number of disadvantages due to their water content:

• - They are heavy, which leads to higher energy consumption and higher costs during transport.
• - They have a larger volume, which leads to lower transport capacities during transport.
• - Particularly thin-bodied emulsions are much more difficult to store and transport, since the preparations can "leak".
• - The application concentrations of the ingredients (e.g. UV filter concentration and thus UV filter performance) are already predetermined for the consumer. An individual adaptation to the conditions at the application site is no longer possible.

It was therefore the task of the present one Invention to eliminate the disadvantages of the prior art and a "dry" emulsion and a To develop processes for producing the same.

• a) eine Lipidphase in einer Konzentration von 20 bis 95 Gewichts-%,
• b) ein oder mehrere wasserlösliche Polymere in einer Gesamtkonzentration von 1 bis 80 Gewichts-%, jeweils bezogen auf das Gesamtgewicht der Zubereitung, sowie
• c) ein oder mehrere UV-Lichtschutzfilter und
• d) eine wässrige Phase, neben gegebenenfalls weiteren kosmetischen und/oder dermatologischen Wirk-, Hilfsund Zusatzstoffen, durch Sprühtrocknung und/oder Gefriertrocknung getrocknet wird.

The object is surprisingly achieved by a process for producing an O / W emulsion, characterized in that it contains an O / W emulsion

• a) a lipid phase in a concentration of 20 to 95% by weight,
• b) one or more water-soluble polymers in a total concentration of 1 to 80% by weight, in each case based on the total weight of the preparation, and
• c) one or more UV light protection filters and
• d) an aqueous phase, in addition to any other cosmetic and / or dermatological active ingredients, auxiliaries and additives, is dried by spray drying and / or freeze drying.

It is preferred according to the invention if the lipid phase in a concentration of 25 to 90% by weight and particularly preferably in a concentration of 35 to 80% by weight, each based on the total weight of the preparation in the emulsion according to the invention is included.

It is further preferred according to the invention if one or more water soluble Polymers in a total concentration of 5 to 70% by weight and particularly preferably in a concentration of 10 to 60% by weight, each based on the total weight of the emulsion are included.

It is further preferred according to the invention if the water content in the preparation after spraying and / or Freeze drying less than 8% by weight and particularly preferred less than 5% by weight, based on the total weight of the dried emulsion.

Also are following such a procedure O / W emulsions produced according to the invention.

Surprised is in particular that the dry emulsions by simple Let the addition of water "re-emulsify", which means that again an O / W emulsion is formed, which is usually not the case with "dried" emulsions the case is.

Although Y. Kawashima et al [Int. J. Pharmaceut., 86 (1992) 25-33, Drug Development and Industrial Pharmacy, 18 (9), 919-937 (1992) and Chem. Pharm. Bull. 39 (6) 1528-1531 (1991)] and H.G. Kristensen et al. [Euro. J. Pharmaceutis and Biopharmaceutics 53 (2002) 147-153 and Int. J. Pharmaceutics 212 (2001) 187-194, 195-202] dried, redispersible emulsions. These emulsions too are stabilized with the help of hydroxypropylmethyl cellulose. However, the emulsions described there are far from being so complex structure like cosmetic and / or dermatological emulsions. Therefore, these writings were unable to achieve the present invention point. The emulsions according to the invention point towards the previously known, redispersible emulsions a special pleasant feeling on the skin and can be used with a variety of cosmetic active, auxiliary and additives. So contain the emulsions according to the invention UV light protection filters, which so far could not be incorporated into re-emulsifiable emulsions.

The oil phase of the emulsion according to the invention, i.e. the lipophilic organic components become advantageous chosen from the group of polar oils, for example from the group of lecithins and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, especially 12 to 18 carbon atoms. The fatty acid triglycerides can for example, advantageously chosen are from the group of synthetic, semi-synthetic and natural oils, such as z. B. cocoglyceride, olive oil, Sunflower oil, Soybean oil, Peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, safflower oil, evening primrose oil, macadamia nut oil and the like more.

According to the invention, z. B. natural Waxes of animal and vegetable origin, such as Beeswax and other insect waxes as well as berry wax, shea butter and / or Lanolin (wool wax).

For the purposes of the present invention, further advantageous polar oil components can also be selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms and from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms. Such ester oils can then advantageously be selected from the group octyl palmitate, octyl cocoate, octyl isostearate, octyl dodeceyl myristate, octyl dodecanol, cetearyl isononanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethyl hexyl laurate, 2-hexyl decyl stearate, 2-octyl dodecyl palmitate, stearylheolate ether, stearylheolate trucate, stearylheolate ether, stearylheolate trucate , semi-synthetic and natural mixtures of such esters, such as. B. Jojoba oil.

Furthermore, the oil phase can advantageously be chosen from the group of dialkyl ethers and dialkyl carbonates, advantageous are z. B. dicaprylyl ether (Cetiol OE) and / or dicaprylyl carbonate, for example that under the trade name Cetiol CC at Cognis available.

It is further preferred that the oil component from the group consisting of isoeicosane, neopentyl glycol, propylene glycol dicaprylate / dicaprate, caprylic / capric / diglyceryl succinate, butylene glycol dicaprylate / dicaprate, cocoglycerides (z. B. Myritol ^® 331 from Henkel), C _12-13 alkyl lactate , Di-C _12-13 alkyl tartrate, trüsostearin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tricaprylin, dimethyl isosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention has a content of C _12-15 alkyl benzoate or consists entirely of this.

Advantageous oil components are also e.g. B. butyloctyl salicylate (for example that available under the trade designation Hallbrite BHB Fa. CP Hall), hexadecyl and butyloctyl benzoate and mixtures thereof (Hall AB) and / or diethylhexyl (Corapan ^® TQ by Haarmann & Reimer).

Any mix of such oil and wax components are to be used advantageously for the purposes of the present invention.

The lipid phase can contain the polar oil components according to the definition in one Concentration of up to 80% by weight based on the total weight the lipid phase. The weight specification refers on the composition of the preparation before drying by means of Freeze and / or spray drying.

Furthermore, the oil phase can also be advantageous also non-polar oils contain, for example those which are selected from the group of branched and unbranched hydrocarbons and waxes, in particular Mineral oil, Vaseline (petrolatum), paraffin oil, Squalane and squalene, polyolefins, hydrogenated polyisobutenes and Isohexadecane. Among the polyolefins are polydecenes and hydrogenated ones Polyisobutenes are the preferred substances.

The non-polar oil components can be beneficial in a concentration of up to 80% by weight based on that Total weight of the lipid phase in the emulsions according to the invention be included. The weight given relates to the composition preparation before drying by freeze and / or spray drying.

The oil phase can also be advantageous have a content of cyclic or linear silicone oils or completely such oils exist, although it is preferred, except for the silicone sleeve or silicone oils additional Content of other oil phase components to use.

werden auch als Polydimethylsiloxan bzw. Dimethicon (INCI) bezeichnet. Dimethicone gibt es in verschiedenen Kettenlängen bzw. mit verschiedenen Molekulargewichten.Silicone oils are high-molecular synthetic polymeric compounds in which silicon atoms are linked in a chain and / or network-like manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups, etc.) are saturated. The silicone oils are systematically referred to as polyorganosiloxanes. The methyl-substituted polyorganosiloxanes, which are the most important compounds of this group in terms of quantity and are characterized by the following structural formula

are also known as polydimethylsiloxane or dimethicone (INCI). Dimethicone is available in different chain lengths or with different molecular weights.

Particularly advantageous polyorganosiloxanes for the purposes of the present invention are, for example, dimethylpolysiloxanes [Poly (dimethylsiloxane)], which, for example, under the trade names Abil 10 to 10,000 are available from Th. Goldschmidt. Also advantageous are phenylmethylpolysiloxanes (INCI: Phenyl Dimethicone, Phenyl Trimethicones), cyclic silicones (octamethylcyclotetrasiloxane or Decamethylcyclopentasiloxane), which according to INCI also as Cyclomethicone amino modified silicones (INCI: Amodimethicone) and silicone waxes, e.g. B. Polysiloxane-polyalkylene copolymers (INCI: Stearyl Dimethicone and Cetyl Dimethicone) and Dialkoxydimethylpolysiloxane (Stearoxy Dimethicone and Behenoxy Stearyl Dimethicone), which as different Abil wax types are available from Th. Goldschmidt. But other silicone oils are also to be used advantageously for the purposes of the present invention, for example cetyldimethicone, hexamethylcyclotrisiloxane, Polydimethylsiloxane, poly (methylphenylsiloxane).

Silicones particularly preferred according to the invention are dimethicone and cyclomethicone.

The silicone oil portion of the lipid phase can advantageously 20 to 100% by weight and particularly preferably 30 up to 60% by weight, based in each case on the total weight of the lipid phase be.

Water-soluble polymers advantageous according to the invention can advantageous according to the invention from the group of water-soluble or dispersible film formers (e.g.

Polyurethanes, Dimethicone Copolyol Polyacrylates, polyvinylpyrrolidone-vinyl acetates PVPNA, polyvinylpyrrolidones (PVP), see below) and from the group of hydrocolloids (e.g. agar-agar, Carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, Guar flour, locust bean gum, starch, dextrins, polysaccharide nalkyl urethanes, Inulin carbamate, gelatin, casein, cellulose ether, hydroxyethyl and - propyl cellulose derivatives, Polysaccharides, polyacrylic and polymethacrylic compounds, ammonium acryloyldimethyl taurates / vinyl pyrrolidone copolymers and ammonium polyacryldimethyl tauramides, vinyl polymers, polycarboxylic acids, polyethers, Polyimines, polyamides, polysilicic acids, clay minerals, zeolites, silicas, see below) become.

in der R ein Wasserstoff oder eine Methylgruppe darstellen kann.Hydrocolloids preferred according to the invention are, for example, methyl celluloses, as the methyl ethers of cellulose are referred to. They are characterized by the following structural formula

in which R can represent a hydrogen or a methyl group.

Particularly advantageous for the purposes of the present invention are the cellulose mixed ethers, which are generally also referred to as methyl celluloses and which, in addition to a dominant content of methyl, also contain 2-hydroxoxyethyl, 2-hydroxypropyl or 2-hydroxy-butyl groups. Particularly preferred hydroxypropylmethyl celluloses (HPMC) have an average molar mass M _m <50,000 g mol ⁻¹ and are, for example, under the name Pharmacoat 603, Pharmacoat 606 and Pharmacoat 645 or under the name Metolose 65 SH 50 or Metolose 60 SH 50 from FA Shin Etsu available.

Also preferred are (hydroxypropyl) methyl celluloses, For example, the one under the trade name Methocel E4M the Dow Chemical Comp. available.

Also advantageous according to the invention is sodium carboxymethyl cellulose, the sodium salt of glycolic acid ether cellulose, for which R in structural formula I is a hydrogen and / or CH2-COONa can represent. The one under the trade name is particularly preferred Natrosol Plus 330 CS available from Aqualon, also as cellulose Gum designated sodium carboxymethyl cellulose.

It is also in accordance with the invention if such an O / W emulsion according to the invention water soluble cosmetic and / or contains dermatological active ingredients, auxiliaries and / or additives.

The method of manufacture is according to the invention an O / W emulsion according to the invention, which is characterized in that by spray drying and / or freeze drying dried O / W emulsion according to the invention in a mixing device with water-soluble and / or volatile active ingredients, Auxiliaries and / or additives are mixed.

According to the invention, “volatile” means that these compounds a boiling point of at most Have 30 ° C.

Also an O / W emulsion that after such a method is produced is according to the invention.

The emulsion according to the invention can thus be water-soluble and / or contain water-dispersible ingredients. These become the preparation according to the invention added advantageously after freeze or spray drying.

The emulsion according to the invention can contain water-soluble ingredients according to the invention contain, for example alcohols, diols or polyols lower Carbon number and their ethers, preferably ethanol, isopropanol, propylene glycol, Ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, -monoethyl or monobutyl ether, diethylene glycol monomethyl or -monoethyl ether and analog products.

The emulsions can be one or more polyols chosen from the group sorbitol, propylene glycol and butylene glycol.

The polyols particularly preferred according to the invention are sorbitol and mannitol.

It is advantageous in the sense of the present Invention when the cosmetic and / or dermatological invention Emulsion a total amount of polyols from 5.0 to 40.0% by weight, preferably from 7.5 to 35.0% by weight and very particularly preferably from 10.0 to 25.0% by weight, in each case based on the total weight the preparation. The weight data relate to the composition preparation before drying by freeze and / or spray drying.

The emulsion according to the invention is advantageously used as a sunscreen. It is also before Partly in the sense of the present invention to create cosmetic and dermatological preparations, the main purpose of which is not protection against sunlight, but which nevertheless contain UV protection substances. So z. B. in day creams or makeup products usually incorporated UV-A or UV-B filter substances. UV protection substances, like antioxidants and, if desired, preservatives, also provide effective protection of the preparations themselves against spoilage. Cosmetic and dermatological preparations which are in the form of a sunscreen are also favorable.

Accordingly, the preparations contain in the sense of the present invention preferably at least one UV-A and / or UV-B filter substance. The formulations can, although not necessary, possibly also one or more organic ones and / or contain inorganic pigments as UV filter substances.

Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (TiO ₂ ), zinc (ZnO), iron (e.g. Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon ( SiO ₂ ), manganese (e.g. MnO), aluminum (Al ₂ O ₃ ), cerium (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides, as well as the sulfate of barium (BaSO ₄ ).

The titanium dioxide pigments can both in the crystal modification rutile as well as anatase and can be in Advantageously treated for the purposes of the present invention ("Coated"), for example a hydrophilic, amphiphilic or hydrophobic character is formed will or should be preserved. This surface treatment can consist of that the Pigments according to known methods with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer be provided. The different surface coating can be in According to the present invention also contain water.

Described coated and uncoated Titanium dioxides can in the sense of the present invention also in the form of commercially available oily or aqueous predispersions come into use. These predispersions can advantageously be used as dispersants and / or solubilizing agents may be added.

The titanium dioxides according to the invention stand out by a primary particle size between 10 nm to 150 nm.

In the sense of the present invention particularly preferred titanium dioxides are the MT-100 Z and MT-100 TV from Tayca Corporation, Eusolex T-2000 and Eusolex TS from Merck and the titanium dioxide T 805 by Degussa.

For the purposes of the present invention, zinc oxides can also be used in the form of commercially available oily or aqueous predispersions. Zinc oxide particles and predispersions of zinc oxide particles suitable according to the invention are distinguished by a primary particle size of <300 nm and are available under the following trade names from the companies listed:

Particularly preferred zinc oxides in The Z-Cote HP1 from BASF and the Zinc oxide NDM from Haarmann & Reimer.

The total amount of one or more inorganic pigments in the finished cosmetic preparation is advantageously selected from the range 0.1% by weight to 25% by weight, preferably 0.5 wt% to 18 wt%.

An advantageous organic pigment for the purposes of the present invention is 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) [INCI : Bisoctyltriazole], which is available under the trade name Tinosorb ^® M from CIBA-Chemicals GmbH.

Advantageous UV-A filter substances for the purposes of the present invention are dibenzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS-Nr. 70356-09-1), marketed by Givaudan under the trade name Parsol ^® 1789 and is sold by Merck under the trade name Eusolex ^® 9020.

Further advantageous UV-A filter substances are the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and their salts, especially the corresponding sodium, potassium or Triethanolammonium salts, in particular the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate, which for example is available from Haarmann & Reimer under the trade name Neo Heliopan AP.

The 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene are also advantageous and its salts (especially the corresponding 10-sulfato compounds, in particular the corresponding sodium, potassium or triethanolammonium salt), also called benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) becomes.

worin

• – R¹ und R² unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₃-C₁₀-Cycloalkyl oder C₃-C₁₀-Cycloalkenyl bedeuten, wobei die Substituenten R¹ und R² gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-Ring bilden können und
• – R³ einen C₁-C₂₀-Alkyl Rest bedeutet.

Further advantageous UV-A filter substances are hydroxybenzophenones, which are characterized by the following structural formula:

wherein

• - R ¹ and R ² independently of one another are hydrogen, C ₁ -C ₂₀ alkyl, C ₃ -C ₁₀ cycloalkyl or C ₃ -C ₁₀ cycloalkenyl, where the substituents R ¹ and R ² together with the nitrogen atom to which they are bound, can form a 5 or 6 ring and
• - R ^{3 is} a C ₁ -C ₂₀ alkyl radical.

und unter dem Handelsnamen Uvinul A Plus bei der Fa. BASF erhältlich ist.A particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2'-hydoxybenzoyl) benzoic acid hexyl ester (also: aminobenzophenone), which is distinguished by the following structure:

and is available under the trade name Uvinul A Plus from BASF.

Advantageous UV filter substances In the sense of the present invention, so-called broadband filters are also i.e. Filter substances that contain both UV-A and UV-B radiation absorb.

wobei R¹, R² und R³ unabhängig voneinander gewählt werden aus der Gruppe der verzweigten und unverzweigten Alkylgruppen mit 1 bis 10 Kohlenstoffatomen bzw. ein einzelnes Wasserstoffatom darstellen. Insbesondere bevorzugt sind das 2,4-Bis-{[4-(2-Ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (INCI: Aniso Triazin), welches unter der Handelsbezeichnung Tinosorb® S bei der CIBA-Chemikalien GmbH erhältlich ist.Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyltriazine derivatives with the following structure:

where R ¹ , R ² and R ^{3 are} independently selected from the group of branched and unbranched alkyl groups having 1 to 10 carbon atoms or represent a single hydrogen atom. Particularly preferred are 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: Aniso triazine), which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH.

Particularly advantageous preparations in the sense of the present invention, which is characterized by a high or very high UV-A protection, preferably contain several UV-A and / or broadband filters, especially dibenzoylmethane derivatives [for example the 4- (tert-butyl) -4'-methoxydibenzoylmethane], benzotriazole derivatives [for example the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol)], Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts, the 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and / or its salts and / or the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine , each individually or in any combination with each other.

aufweisen, sind vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung, beispielsweise die in der Europäischen Offenlegungsschrift EP 570 838 A1 beschriebenen s-Triazinderivate, deren chemische Struktur durch die generische Formel

wiedergegeben wird, wobei
R einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkylrest, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄-Alkylgruppen, darstellt,
X ein Sauerstoffatom oder eine NH-Gruppe darstellt,
R₁ einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkylrest, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄-Alkylgruppen, oder ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe oder eine Gruppe der Formel

bedeutet, in welcher
A einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkyl- oder Arylrest darstellt, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄-Alkylgruppen,
R₃ ein Wasserstoffatom oder eine Methylgruppe darstellt,
n eine Zahl von 1 bis 10 darstellt,
R₂ einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkylrest, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄-Alkylgruppen, darstellt, wenn X die NH-Gruppe darstellt, und
einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkylrest, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄-Alkylgruppen, oder ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe oder eine

bedeutet, in welcher
A einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkyl- oder Arylrest darstellt, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄-Alkylgruppen,
R₃ ein Wasserstoffatom oder eine Methylgruppe darstellt,
n eine Zahl von 1 bis 10 darstellt,
wenn X ein Sauerstoffatom darstellt.Also other UV filter substances, which the structural motif

have, are advantageous UV filter substances in the sense of the present invention, for example those in the European patent application EP 570 838 A1 described s-triazine derivatives, their chemical Structure through the generic formula

is reproduced, whereby
R represents a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ alkyl groups,
X represents an oxygen atom or an NH group,
R _{1 is} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more C ₁ -C ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of formula

means in which
A represents a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
R _{2 represents} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more C ₁ -C ₄ alkyl groups, when X represents the NH group, and
a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more C ₁ -C ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a

means in which
A represents a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
when X represents an oxygen atom.

wiedergegeben wird, welches im Folgenden auch als Dioctylbutylamidotriazon (INCI: Dioctylbutamidotriazone) bezeichnet wird und unter der Handelsbezeichnung UVASORB HEB bei Sigma 3V erhältlich ist.A particularly preferred UV filter substance in the sense of the present invention is also an asymmetrically substituted s-triazine, the chemical structure of which is represented by the formula

is reproduced, which is also referred to below as dioctylbutylamidotriazon (INCI: dioctylbutamidotriazone) and is available under the trade name UVASORB HEB from Sigma 3V.

A symmetrically substituted s-triazine which is 4,4 ', 4''(1,3,5-triazine-2,4,6-triyltrümino) tris-benzoic acid tris (2 -ethylhexyl ester), synonymous: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone), which is from from BASF Aktiengesellschaft under the trade name UVINUL ^® T 150.

wiedergegeben wird, wobei R₁, R₂ und A₁ verschiedenste organische Reste repräsentieren.European laid-open specification 775 698 also describes bis-resorcinyltriazine derivatives which are preferably to be used and whose chemical structure is represented by the generic formula

is reproduced, wherein R ₁ , R ₂ and A _{1 represent a} wide variety of organic radicals.

Advantageous in the sense of the present The invention also relates to 2,4-bis - {[4- (3-sulfonato) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine Sodium salt, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5 triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- [4- (2-methoxyethylcarboxyl) phenylamino] -1,3,5-triazine . the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- [4- (2-ethylcarboxyl) phenylamino] -1 , 3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (1-methyl-pyrrol-2-yl) -1,3,5-triazine, the 2,4-bis - {[4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, the 2,4-bis - {[ 4- (2 '' - methylpropenyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine and the 2,4-bis - {[4- (1 ', 1', 1 ', 3', 5 ', 5', 5'-heptamethylsiloxy-2 "-methylpropyloxy) -2-hydroxy] phenyl} - 6- (4-methoxyphenyl) -1,3,5-triazine.

An advantageous broadband filter in the sense of the present invention is the 2,2'-methylenebis (6- (2N-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), which under the Trade name Tinosorb ^® M is available from CIBA-Chemicals GmbH.

Advantageous broadband filter in For the purposes of the present invention, 2- (2Hbenzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl is furthermore also ] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.

• – 3-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylbenzyliden)campher, 3-Benzylidencampher;
• – 4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2-ethylhexyl)ester, 4-(Dimethylamino)benzoesäureamylester;
• – 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazin;
• – Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethylhexyl)ester;
• – Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester, 4-Methoxyzimtsäureisopentylester;
• – Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon
• – sowie an Polymere gebundene UV-Filter.

The UV-B and / or broadband filters can be oil-soluble or water-soluble. Advantageous oil-soluble UV-B and / or broadband filter substances are e.g. B .:

• - 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
• - 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (di methylamino) benzoesäureamylester;
• - 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine;
• - Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;
• - Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
• - Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone
• - As well as UV filters bound to polymers.

• – Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Triethanolammonium-Salz, sowie die Sulfonsäure selbst;
• – Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäure und deren Salze.

Advantageous water-soluble UV-B and / or broadband filter substances are e.g. B .:

• - Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself;
• - Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and salts thereof.

Particularly advantageous at room temperature liquid UV filter substances in the sense of the present invention are homomenthyl salicylate (INCI: Homosalate), 2-ethylhexyl-2-hydroxybenzoate (2-ethylhexyl salicylate, Octyl salicylate, INCI: octyl salicylate), 4-isopropylbenzyl salicylate and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamate (Isopentyl-4-methoxycinnamate, INCI: Isoamyl p-methoxycinnamate), 3- (4- (2,2-bis Ethoxycarbonylvinyl) phenoxy) propenyl) methoxysiloxane / dimethylsiloxane copolymer (INCI: Dimethicodiethylbenzalmalonat) which, for example, under the trade name Parsol® SLX available from Hoffmann La Roche is.

A further light protection filter substance according to the invention to be used advantageously is ethylhexyl-2-cyano-3,3-diphenylacrylate, obtainable (octocrylene) from BASF under the name Uvinul ^® N 539th

auszeichnet und bei 3V Sigma unter der Handelsbezeichnung Uvasorb® K2A erhältlich ist.A particularly preferred benzoxazole derivative according to the invention is 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3 , 5-triazine with CAS No. 288254-16-0, which is characterized by the structural formula

distinguished and is available from 3V Sigma under the trade name Uvasorb® K2A.

It can also be of considerable benefit be polymer-bound or polymeric UV filter substances in preparations according to the present To use the invention, in particular those as described in WO-A-92/20690 to be discribed.

The list of UV filters mentioned, which can be used within the meaning of the present invention Of course not be limiting.

The preparations according to the invention advantageously contain the substances that UV radiation absorb in the UV-A and / or UV-B range, in a total amount from Z. B. 0.1% by weight to 80% by weight, preferably 0.5 to 70% by weight, in particular 1.0 to 60 wt .-%, each based on the total weight of the preparations to make cosmetic preparations available place the hair or skin in front of the entire area of the Protect ultraviolet radiation. You can also as sunscreen for Serve hair or skin.

The weight specifications refer thereby on the composition of the preparation before drying by means of freeze and / or spray drying. The weight data relate to the composition preparation before drying by freeze and / or spray drying.

Particularly preferred embodiments of the present invention contain as UV filters or several triazine derivatives, dibenzoylmethane derivatives, UV filters which are liquid at room temperature and / or inorganic pigments, in particular titanium dioxide.

Furthermore, it can be from Be advantageous to incorporate film formers into the emulsion according to the invention, for example to improve the water resistance of the preparations or to increase the UV protection performance (UV-A and / or UV-B boosting). Both water-soluble are suitable or dispersible as well as fat-soluble film formers, in each case individually or in combination with each other.

Advantageously water-soluble or dispersible film formers according to the invention, which can also be used as water-soluble polymers according to the invention, are e.g. B. Polyurethanes (e.g. the Avalure ^® types from Goodrich), Dimethicone Copolyol Polyacnlate (Silsoft Surface ^® from the Witco Organo Silicones Group), PVP / VA (VA = vinyl acetate) copolymer (Luviscol VA 64 Powder from BASF) etc ,

Advantageous water-soluble film formers are e.g. B., the film formers from the group of polymers based on polyvinylpyrrolidone (PVP)

Copolymers are particularly preferred of polyvinylpyrrolidone, for example the PVP hexadecene copolymer and the PVP eicosen copolymer, which is available under the trade names Antaron V216 and Antaron V220 at the GAF Chemicals Cooperation available are, as well as the Tricontayl PVP and the like.

According to the invention, the usual in the emulsion Antioxidants are used.

The antioxidants are advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tinphophane) and their derivatives, imidazoles (e.g. 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. α-carotene, β-carotene, lycopene) and their derivatives, aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N Acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and their derivatives ( Esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts . Bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, alanine diacetic acid, flavonoids, polyphenols, catechins, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg- Ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (e.g. vitamin E acetate), and coniferyl benzoate of benzoin, rutinic acid and its derivatives, ferulic acid and its derivatives, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajak resin acid, nordihydrogenroxyroxyne derivative, mannybenzoic acid, mannybenzoic acid, mannodisorbate, mannihydroxybenzoic acid, mannodisulfuric acid, mannihydroxybenzoic acid, mannohydrobenzoic acid, mannodisulfuric acid, and its counterpart Derivatives, zinc and its derivatives (e.g. ZnO, ZnSO ₄ ) selenium and its derivatives (e.g. selenium methionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, Nucleosides, peptides and lipids) of these active ingredients.

The amount of antioxidants (a or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.025-6.0% by weight, in particular 0.05-3.0% by weight, based on the total weight of the preparation. The weight data relate to the composition preparation before drying by freeze and / or spray drying.

If vitamin A or vitamin A derivatives, or carotenes or their derivatives represent the antioxidant (s), it is advantageous to have their respective concentrations out of the range from 0.001 to 30% by weight, based on the total weight of the formulation, to choose. The weight data relate to the composition preparation before drying by freeze and / or spray drying.

If vitamin E and / or its Derivatives that represent the antioxidants, it is advantageous to their respective concentrations in the range from 0.001 to 30% by weight, based on the total weight of the formulation. The Weight specifications relate to the composition of the Preparation before drying by freeze and / or spray drying.

Further advantageous active ingredients in the sense of the present invention are natural active ingredients and / or their derivatives, such as. B. alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creative, fumaric acid ester, ectoine and its derivatives, taurine, and / or β-alanine. These active ingredients can be contained in a concentration of 0.001 to 30% by weight, based on the total weight of the emulsion. The weight information be refer to the composition of the preparation before drying by means of freeze and / or spray drying.

Recipes according to the invention, which, for. B. known anti-wrinkle active ingredients such as flavone glycosides (in particular α-glycosyl rutin), Contain coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for prophylaxis and treatment cosmetic or dermatological skin changes, such as z. B. at skin aging (such as dryness, roughness and formation of dryness wrinkles, Itching, reduced regreasing (e.g. after washing), visible vasodilation (telangiectasia, Cuperosis), flaccidity and formation of wrinkles and fine lines, local hyper, hypo and incorrect pigmentation (e.g. age spots), increased vulnerability across from mechanical stress (e.g. cracking) and the like). Farther they are advantageous against the appearance of dry or rough skin.

However, other pharmaceutically or dermatologically active substances such as, for example, substances that soothe and care for the skin can also be incorporated into the preparations according to the invention. These include, for example, panthenol, allantoin, tannin, antihistamines (e.g. loratadine, cetirizine, dimetionden, clemastine, capsaicin, H ₁ -antagonists, tannin preparations), local anesthetics, opiate antagonists (e.g. naltrexone, naloxone), antiphortal anticoagulants, tucrolocinic agents, tucalucin, glucosaccharides, glucocinocletics, glucocorticosteroids, gluciminoporins, glucocorticosteroids, glucinocorticans, tucolocinicides, glucocinocletics, tucolacin, and glucocorticans A) as well as plant substances such as azulene and bisabolol, glycyrrhizin, hamamelin and plant extracts such as chamomile, aloe vera, hamazelis, licorice root. The vitamin D ₃ analogues tacalcitol, calcipotriol, tacalcitol, colecalciferol and calcitrol (vitamin D ₃ ) and / or fumaric acid esters can also be successfully incorporated into the preparations.

These active substances can be used in a concentration of 0.001 to 30% by weight, based on the Total weight of the emulsion to be contained in this. The weights relate to the composition of the preparation drying by freeze and / or spray drying.

Advantageous moisturizing or moisturizing agents (so-called moisturizers) for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccaride Gum-1, glycine soybean, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides. Particularly advantageous are, for example, hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registration number 178463-23-5 and z. B. is available under the name Fucogel ^® 1000 from the company SOLABIA SA.

The preparations according to the invention can be advantageous Solid support contained in the form of microfine solid particles. According to the invention, these can be advantageous superficial treated to be water-repellent ("coated"), whereby a amphiphilic character of these solid particles are formed or should be preserved. The surface treatment can consist of that the Solid particles according to known methods with a thin hydrophobic or hydrophilic layer.

The average particle diameter the microfine solid support used as stabilizer is preferred smaller than 100 μm, selected particularly advantageously less than 50 microns. It is essentially irrelevant in what form (platelets, Rod, globule etc.) or modification of the solid particles used.

• – Titandioxide (gecoatet und ungecoatet): z. B. Eusolex T-2000 von der Fa. Merck, Titandioxid MT-100 Z von der Fa. Tayca Corporation
• – Zinkoxide z. B. Z-Cote und Z-Cote HP1 von der BASF AG, MZ-300, MZ-500 und MZ-505M von der Fa. Tayca Corporation
• – Eisenoxide

The microfine solid supports are preferably selected from the group of amphiphilic metal oxide pigments. The following are particularly advantageous:

• - Titanium dioxides (coated and uncoated): e.g. B. Eusolex T-2000 from Merck, titanium dioxide MT-100 Z from Tayca Corporation
• - Zinc oxides e.g. B. Z-Cote and Z-Cote HP1 from BASF AG, MZ-300, MZ-500 and MZ-505M from Tayca Corporation
• - iron oxides

Furthermore, it is advantageous when the microfine solid carrier can be selected from the following group: Boron nitrides, starch derivatives (Tapioca Starch, Sodium Corn Starch Octynylsuccinat etc.), talc, Latex particles.

The microfine solid particles are advantageous according to the invention in a concentration of 0.5 to 60% by weight, preferably in one Concentration from 1 to 50% by weight and particularly preferably in a concentration of 3 to 30% by weight, based on each the total weight of the preparation used. The weights relate to the composition of the preparation drying by freeze and / or spray drying.

The cosmetic or dermatological preparations according to the invention can furthermore advantageously, although not necessarily, contain fillers which, for. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or intensify a velvety or silky feeling on the skin. Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as tapioca starch, distarch phosphate, aluminum or sodium starch, octenyl succinate and the like), pigments that have neither a primary UV filter nor coloring effect (such as boron nitride etc.) and / or aerosils ^® (CAS No. 7631-86-9).

The compositions contain according to the invention except the above-mentioned substances, if appropriate, those customary in cosmetics Additives, for example perfume, dyes, antimicrobial Lipid-replenishing substances Agents, complexing and sequestering agents, pearlescent agents, Plant extracts, vitamins, active ingredients, preservatives, bactericides, Repellents, self-tanners (e.g. DHA), depigmenting agents (e.g. 8-hexadecen-1,16-dicarboxylic acid (Dioic acid, CAS number 20701-68-2; provisional INCI name Octadecendioic acid)), pigments that have a coloring Have softening, moisturizing and / or moisturizing effects Substances, or other common Components of a cosmetic or dermatological formulation such as emulsifiers, polymers, foam stabilizers, peeling substances (Abrasives, e.g. polymer beads or powder made of polyethylene, polypropylene etc. inorganic oxides, Silicates etc.), antiperspirant salts (e.g. acidic aluminum and / or Aluminum / zirconium salts such as aluminum chlorohydrate and / or aluminum / zirconium chlorohydrate) and electrolytes.

According to the invention, the repellent active ingredients listed below are preferred:

Particularly beneficial repellent active ingredients For the purposes of the present invention, the above-mentioned active substances N, N-Diethyl-3-methylbenzamide, 3- (N-n-butyl-N-acetylamino) propionic acid ethyl ester and dimethyl phthalate. The repellent is very particularly preferred 3- (N-n-butyl-N-acetyl-amino) -propionic acid ethyl ester.

Advantageous embodiments according to the invention the emulsion of the invention contain one or more repellent active ingredients in one concentration of 1-50% by weight, based on the total weight of the formulation. The weight data relate to the composition preparation before drying by freeze and / or spray drying.

According to the invention, the following can advantageously be used as self-tanners:
Glycerol aldehyde, hydroxymethylglyoxal, γ-dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone), 2-hydroxy-1,4-naphthoquinone (Lawson) and particularly preferably 1, 3-dihydroxyacetone.

Advantageous embodiments according to the invention with at least one self-tanning substance these in a total concentration of 0.1 to 30% by weight on the total weight of the emulsion. Obtain the weight information refer to the composition of the preparation before drying by means of freeze and / or spray drying.

The emulsion according to the invention can advantageously contain one or more preservatives according to the invention. Advantageous preservatives in the sense of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available, for example, from Lonza under the trade name Glydant ^™ ), iodopropyl butyl carbamates (for example those under the trade names Glycacil-L, Glycacil -S available from Lonza and / or Dekaben LMB from Jan Dekker), parabens (ie alkyl p-hydroxybenzoate, such as methyl, ethyl, propyl and / or butyl paraben), phenoxyethanol, ethanol, benzoic acid and the like. According to the invention, the preservation system usually also advantageously includes preservation aids, such as, for example, octoxyglycerol, glycine soya, etc. The table below gives an overview of some preservatives which are advantageous according to the invention:

Are also advantageous in cosmetics common Preservatives or preservatives, such as dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile), phenoxyethanol, 3-1od-2-propynyl butyl carbamate, 2-bromo-2-nitro-propane-1,3-diol, imidazolidinyl urea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, Benzalkonium chloride, benzyl alcohol, salicylic acid and salicylates.

It is special according to the invention preferred if iodopropyl butyl carbamates are used as preservatives, Parabens (methyl, ethyl, propyl and / or butyl paraben) and / or Phenoxyethanol can be used.

According to the invention, one or several preservatives in a concentration of 2% by weight or less than 2% by weight, preferably 1.5% by weight or less 1.5% by weight and particularly preferably 1% by weight or less 1% by weight, based in each case on the total weight of the preparation contain. The weight data relate to the composition preparation before drying by freeze and / or spray drying.

The emulsion according to the invention advantageously contains one or more conditioning. Conditioning preferred according to the invention includes, for example, all compounds which are described in Section 4 below in the International Cosmetic Ingredient Dictionary and Handbook (Volume 4, publisher: RC Pepe, JA Wenninger, GN McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9th edition, 2002) the keywords Hair Conditioning Agents, Humectants, Skin-Conditioning Agents, Skin-Conditioning Agents-Emollient, Skin-Conditioning Agents-Humactant, Skin-Conditioning Agents-Miscellaneous, Skin-Conditioning Agents-Occlusive and Skin Protectans are all listed in the EP 0934956 (P.11-13) under water soluble conditioning agent and oil soluble conditioning agent. Some of these compounds are listed under the components of the aqueous phase and the oil phase. Further conditioners which are advantageous according to the invention are, for example, the compounds named polyquaternium according to the international nomenclature for cosmetic ingredients (INCI) (in particular polyquaternium-1 to polyquaternium-56).

The emulsion according to the invention can be advantageous according to the invention Contain glitter fabrics and / or other effect substances.

As hydrocolloids advantageous according to the invention, used as water-soluble polymers according to the invention can be agar agar, carrageenan, tragacanth, gum arabic, alginates, Pectins, polyoses, guar flour, locust bean gum, starch, dextrins, Polysaccharide-N-alkyl urethanes, inulin carbamates, gelatin, casein, Cellulose ethers, hydroxyethyl and propyl cellulose derivatives, polysaccharides, Polyacrylic and Polymethacni compounds, Ammoniumacnloyldimethyltaurate / Vinylpyrrolidon copolymers and ammonium polyacnl-dimethyltauramide, vinyl polymers, polycarboxylic acids, polyethers, Polyimines, polyamides, polysilicic acids, clay minerals, zeolites, silicas used.

Another advantageous hydrocolloid for the purposes of the present invention is xanthan (CAS no. 11138-66-2), also called xanthan gum, which is an anionic heteropolysaccharide, which is usually formed by fermentation from corn sugar and is isolated as the potassium salt.

An advantageous hydrocolloid in the According to the present invention, carrageenan is also a gel-forming and similar Extract from North Atlantic like agar, one of the ffor ideas Red algae (Chondrus crispus and Gigarfina stellata).

Polyacrylates are also advantageous hydrocolloids to be used in the sense of the present invention. According to the invention advantageous Polyacnlate are acrylate-alkyl acrylate copolymers, in particular those from the group of so-called carbomers or carbopols (Carbopol ^® is actually a registered trademark of NOVEON Inc.) are selected. In particular, the acrylate-alkyl acrylate copolymers which are advantageous according to the invention are distinguished by the following structure:

R 'represents a long-chain alkyl radical and x and y are numbers which represent the respective stoichiometric proportion of the respective Symbolize comonomers.

According to the invention preferably Acnlat copolymers and / or acrylate-alkyl acrylate copolymers sold under the trade names Carbopol ^® 1382, Carbopol ^® 981 and Carbopol ^® 5984, Aqua SF-1 from NOVEON Inc. or as Aculyn ^® 33 from International Specialty Products Corp. are available. The carbomers Carbopol EDT 2001, ETD 2020 and ETD 2050 are also preferred.

Copolymers are also advantageous from C10-30-alkylnlates and one or more monomers of acrylic acid, the methacrylic acid or their esters, which are cross-linked with an allyl ether Sucrose or an allyl ether of pentaerythritol.

Connections that are advantageous the INCI name "Acrylates / C 10-30 alkyl acrylate large polymer ". Particularly advantageous the under the trade names Pemulen TR1 and Pemulen TR2 from NOVEON Inc.

Connections that are advantageous the INCI-Acrylates / Vinyl Isodecanoate Crosspolymer ". In particular those under the trade names Stabylen 30 are advantageous available from 3V Sigma.

Also advantageous are compounds which have the INCI name "acrylates / C12-24 pareth-25 acrylate copolymer" (available under the trade names Synthalen ^® W2000 from 3V Inc.) and the INCI name "acrylates / steareth-20 methacrylate copolymer""(under the trade names Aculyn ^® 22 available from International Specialty Products Corp.), which the INCI name" acrylates / steareth-20 itaconate copolymer "(available under the trade names Structure 2001 ^® available from National Starch), the INCI the Designation "acrylates / aminoacrylates / C10-30 alkyl PEG-20 itaconate copolymer" (available under the trade names Structure Plus ^® from National Starch) and similar polymers.

According to the invention, it is particularly preferred neutralized or partially neutralized polyacrylates (e.g. Carbopole from the company Noveon).

The cosmetic and / or dermatological invention Emulsions can contain a number of pigments.

The dyes and pigments can be selected from the corresponding positive list in the Cosmetics Ordinance or the EC list of cosmetic colorants. In most cases, they are identical to the colorants approved for food. Advantageous color pigments are, for example, titanium dioxide, mica, iron oxides (for example Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the list below. The Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd edition, Society of Dyers and Colorists, Bradford, England, 1971.

It can also be advantageous to use a dye or select several substances from the following group: 2,4-dihydroxyazobenzene, 1- (2'-chloro-4'-nitro-1'phenylazo) -2-hydroxynaphthalene, Ceres red, 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, calcium salt the 2-hydroxy-1,2''azonaphthalene-1 '-' sulfonic acid, calcium and barium salts 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt 1- (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, aluminum salt 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid, 1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt 8-amino-2-phenylazo-1-naphthol-3,6-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -1- (4-sulfophenyl) -5-hydroxy-pyrazolone-3-carboxylic acid , 4 '- [(4' '- sulfo-1' '- phenylazo) -7'-sulfo-1'-naphthylazo] -1-hydroxy-8-acetylaminonaphthalene-3,5-disulfonic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluorescein, 3''4''5''6''Te trachloro-2,4,5,7-tetrabromofluorescein and its aluminum salt, aluminum salt of 2,4,5,7-tetraiodofluorescein, Aluminum salt of quinophthalone disulfonic acid, aluminum salt of indigo disulfonic acid, 4,4'-di'ethyl-6,6'-di'hlorthioindigo, complex salt (Na, Al, Ca) of carminic acid, red and black iron oxide (CIN: 77 491 (red) and 77 499 (black)), Iron oxide hydrate (CIN: 77 492), manganese ammonium diphosphate (CIN 77745), Ultramarine (CIN 77007) and titanium dioxide.

Emulsions according to the invention can titanium dioxide included, both in the rutile and crystal modification Anatase may be present and advantageously treated superficially within the meaning of the present invention ("Coated"), for example a hydrophilic, amphiphilic or hydrophobic character is formed will or should be preserved. This surface treatment can consist of that the Pigments according to known methods with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer be provided. The different surface coatings can be in the sense of the present invention also contain water.

Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (Al ₂ O ₃ ), aluminum hydroxide Al (OH) ₃ , or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaPO ₃ ) ₆ , sodium metaphosphate (NaPO ₃ ) _n , silicon dioxide (SiO ₂ ) (also: silica, CAS No .: 7631-86-9), zirconium oxide (ZrO ₂ ) or iron oxide (Fe ₂ O ₃ ). These inorganic surface coatings can occur alone, in combination and / or in combination with organic coating materials.

For this purpose, oxides, oxide hydrates or phosphates of, for example, the elements Al, Si, Zr in dense layers on the pigment surface precipitated.

The inorganic aftertreatment happens generally in an aqueous Suspension of the pigment by adding soluble aftertreatment chemicals, such as. Aluminum sulfate, and subsequent precipitation in the neutral area slightly soluble Hydroxides by adjusting the pH value with sodium hydroxide solution. After the inorganic post-treatment, the coated pigments separated from the suspension by filtration and washed thoroughly, to the solved Remove salts, then the isolated pigments are dried.

Particularly preferred in the sense of this Invention are titanium dioxide, on which aluminum hydroxide is applied to the surface such as the titanium dioxide types available from Sun Chemical C47-051 and C47-5175. Other preferred pigments are titanium dioxide, which are coated with aluminum and / or silicon oxides, e.g. from Krosnos Titan: Kronos 1071 and 1075 or from the company Kingfisher: A310.03 Tudor Aspen.

Organic surface coatings in the sense of the present invention consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, Lauric acid, Dimethylpolysiloxane (also: Dimethicone), methylpolysiloxane (Methicone), Simethicone (a mixture of dimethylpolysiloxane with an average chain length from 200 to 350 dimethylsiloxane units and silica gel) or alginic acid. This organic surface coatings can alone, in combination and / or in combination with inorganic Coating materials occur.

• – „Fischsilber" (Guanin/Hypoxanthin-Mischkristalle aus Fischschuppen) und
• – „Perlmutt" (vermahlene Muschelschalen),

monokristalline Perlglanzpigmente wie z. B. Bismuthoxychlorid (BiOCI), Schicht-Substrat Pigmente: z. B. Glimmer/MetalloxidFurthermore, it can be advantageous to use pearlescent pigments according to the invention. These include natural pearlescent pigments such as B.

• - "fish silver" (guanine / hypoxanthine mixed crystals from fish scales) and
• - "mother-of-pearl" (milled mussel shells),

monocrystalline pearlescent pigments such as B. bismuth oxychloride (BiOCI), layer-substrate pigments: e.g. B. mica / metal oxide

The basis for pearlescent pigments are, for example powdery Pigments or castor oil dispersions from Bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or Titanium dioxide on mica. Particularly advantageous is e.g. B. the under the CIN 77163 listed gloss pigment.

The following pearlescent pigment types based on mica / metal oxide are also advantageous:

Those of from Merck under the trade names Timiron, Colorona or Dichrona available Pearlescent pigments.

The list of the pearlescent pigments mentioned is of course not intended to be limiting. Pearlescent pigments which are advantageous in the sense of the present invention can be obtained in numerous ways known per se. For example, other substrates besides mica can be coated with other metal oxides, such as. B. silica and the like. Z are advantageous. B. with TiO ₂ and Fe ₂ O ₃ coated SiO ₂ particles ("Ronaspheren"), which are sold by Merck.

It can also be advantageous to completely do without a substrate such as mica. Pearlescent pigments which are produced using SiO ₂ are particularly preferred. Such pigments, which can also have gonichromatic effects, are e.g. B. available under the trade name Sicopearl Fantastico from BASF.

Pigments can also be advantageous from Engelhard / Mearl based on calcium sodium borosilicate, coated with titanium dioxide. These are available under the name Reflecks. Due to their particle size of 40 - 180 μm, they have a glitter effect in addition to the color on.

The dyes and pigments can both individually and in a mixture and mutually be coated, with different coating thicknesses different color effects are generally produced. The total amount the dyes and coloring pigments is advantageously from the Range of z. B. 0.1 wt .-% to 30 wt .-%, preferably from 0.5 up to 15% by weight, in particular from 1.0 to 10% by weight, in each case based on the total weight of the preparations. The weights relate to the composition of the preparation drying by freeze and / or spray drying.

Advantageous in the sense of the present Invention contains the O / W emulsion according to the invention one or several tablet excipients. According to the invention, these can be advantageous in a concentration of 0.1 to 60% by weight, preferably in one Concentration from 1 to 50% by weight and very particularly preferred in a concentration of 3 to 35% by weight, based in each case on the total weight of the preparation. The weights relate to the composition of the preparation as a preparation, the emulsion after freeze and / or spray drying together with any other water-soluble and / or volatile Compounds and tableting materials (incl. Hydrogen carbonates and acids solid at room temperature) is seen.

As tablet excipients, for example Filling and Auxiliary agents (e.g. starch and / or cellulose derivatives), superplasticizer (e.g. highly disperse silicon dioxide), flow regulators, lubricants, Mold release agents are used.

All can be advantageous according to the invention Substances are used that are in the H.P. Fiedler, Lexicon of auxiliary materials for pharmacy, Cosmetics and related areas, 5th edition, Editio Cantor Verlag, Aulendorf, 2002, under the keywords tablet binders, tablet fillers, Tablet lubricants, tablet auxiliaries, tablet disintegrants, Tablet covers listed are.

In one particularly according to the invention preferred embodiment contains the preparation according to the invention a combination of carbonates and / or hydrogen carbonates as well acids solid at room temperature (e.g. citric acid, ascorbic acid, Lactic acid, Tartaric acid, Etc). Strongly swelling polymers such as cross-linked According to the invention, polyvinylpyrrolidone can advantageously be used.

According to the invention, one or several bicarbonates (e.g. sodium bicarbonate, potassium bicarbonate) in an amount of 0.1 to 30% by weight, preferably in an amount from 0.5 to 20% by weight and particularly preferably in an amount from 0.5 to 15% by weight, in each case based on the total weight used the preparation, the preparation being the emulsion after freeze and / or spray drying together with further water-soluble and / or and / or volatile Compounds and tableting materials (incl. Hydrogen carbonates and acids solid at room temperature) is seen.

According to the invention, one or several acids solid at room temperature (particularly preferably citric acid) in an amount of 0.1 to 30% by weight, preferably in an amount from 0.5 to 20% by weight and particularly preferably in an amount from 0.5 to 15% by weight, in each case based on the total weight used the preparation, the preparation being the emulsion after freeze and / or spray drying together with any other water-soluble and / or volatile Compounds and tableting materials (incl. Hydrogen carbonates and acids solid at room temperature} is seen.

Such an embodiment is particularly advantageous in the sense of the present invention, if the emulsion of the invention is in the form of a tablet (e.g. an effervescent tablet) because the emulsion according to the invention in this embodiment can be re-emulsified particularly easily by adding water.

The method for Production of such a preparation, which is characterized is that the O / W emulsion according to the invention with one or more tablet excipients in a mixing device be mixed.

Preparations according to the invention are also the according to this inventive method getting produced.

Another method is according to the invention for the production of tablets and / or granules, which thereby is characterized in that a preparation according to the invention in a press is pressed or granulated into one or more tablets, as well as preparations made by this process.

Last but not least, the method is according to the invention for the production of a cosmetic, which is characterized is that a preparation according to the invention (one by spray drying and / or freeze-dried dried O / W emulsion, which if necessary with water soluble and / or volatile Active ingredients, auxiliary additives and / or tablet auxiliaries added and, if necessary, was tabletated or granulated) with water is added or emulsified in water. According to the invention Cosmetics made using this process.

Such a cosmetic according to the invention is then in the form of an ointment, cream, lotion or an emulsion foam (French mousse) or a sprayable Form before. It can be advantageous according to the invention used to treat and care for the skin, hair and nails. Is preferred according to the invention the use as a sunscreen.

The following examples are intended illustrate the present invention without restricting it. All Unless otherwise stated, quantities, proportions and percentages are the same specified, on the weight and the total amount or on the total weight of the preparations related.

The examples from Table 1 (emulsion Preparations after spray drying) are inventively with mixtures of substances the water-soluble / -dipergbare additions (Table 2) homogeneously mixed.

Optionally, the substance mixtures (table 1 + 2) mixed with tableting and granulating aids (Table 3) and granules according to the invention and / or tablets are produced by suitable processes.

Examples: Table 1: emulsion preparation after spray-1 or freeze-drying

Table 2: Water soluble / dispersible additives

Table 3: Additives for granulating / tableting the mixtures from 1 & 2

Claims (11)

A process for producing an O / W emulsion, characterized in that an O / W emulsion containing a) a lipid phase in a concentration of 20 to 95% by weight, b) one or more water-soluble polymers in a total concentration of 1 to 80 % By weight, each based on the total weight of the preparation, and c) one or more UV light protection filters and d) an aqueous phase, in addition to any other cosmetic and / or dermatological active ingredients, auxiliaries and additives, is dried by spray drying and / or freeze drying. O / W emulsion produced by a process according to Claim 1. Process for the preparation of an O / W emulsion, thereby characterized in that an O / W emulsion according to any one of claims 1 or 2 in a mixing device with water-soluble and / or volatile active ingredients, Auxiliaries and / or additives are mixed. O / W emulsion produced by a process according to Claim 3. Preparation containing an O / W emulsion after a of claims 2 or 4 and one or more granulating and / or tablet auxiliaries. Process for the preparation of a preparation according to Claim 5, characterized in that an O / W emulsion after one of the claims 2 or 4 with one or more tablet excipients in one Mixing device can be mixed. Preparation manufactured according to a procedure Claim 6. Process for the production of tablets and / or Granules, characterized in that a preparation according to claim 7 pressed into one or more tablets in a press or be granulated by means of suitable granulating devices. Preparation manufactured according to a procedure Claim B. Process for the production of a cosmetic thereby characterized in that a preparation according to one of claims 2, 4, 5, 7 and / or 9 are mixed with water. Cosmetic manufactured according to a process Claim 10.