DE102004047281A1 - Sunscreen concentrate with organic micropigments - Google Patents

Abstract

Process for the preparation of a cosmetic preparation, characterized in that an O / W emulsion containing DOLLAR A a) an aqueous phase, DOLLAR A b) an oil phase, DOLLAR A c) pigmentary UV light protection filters and DOLLAR A d) water-soluble polymers, DOLLAR A in addition to optionally other cosmetic and / or dermatological active ingredients, excipients and additives, dried by spray drying, freeze drying and / or drum drying.

Description

The The present invention relates to a process for the preparation of a cosmetic preparation based on a dried O / W emulsion as well as the process product.

Of the Wish, nice and looking attractive, is inherently rooted in man. Even if the ideal of beauty has undergone changes over time, so is the pursuit of a flawless appearance, always been the goal of the people. A substantial portion of one beautiful and attractive looks while the condition and the appearance of the skin and the skin appendages, i.e. the hair and the nails.

The Skin is the largest organ of the human. Among its many functions (for example, the heat control and as a sensory organ) is the barrier function, which is dehydration the skin (and ultimately the entire organism) prevents probably the most important. At the same time, the skin acts as a protection against the penetration and absorption of foreign substances and the UV radiation. This barrier function is caused by the epidermis, which as the outermost layer the actual protective cover opposite the Environment forms. At about one tenth of the total thickness, it is simultaneously the thinnest Layer of the skin.

In order to the skin can fulfill its biological functions to the full extent, it requires regular cleaning and care. The cleaning of the skin serves the removal of Dirt, sweat and leftovers Dead skin particles that provide 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 moisturizing of the skin. Often are added to them active ingredients that regenerate the skin and for example, their premature aging (e.g., the emergence of Pucker, To prevent and reduce wrinkles).

Skin Care Products usually consist of emulsions. Under emulsions understands one generally uses heterogeneous systems that do not consist of two or only limited to each other consist of miscible liquids, usually be referred to as 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 mere When viewed in the eye, emulsions appear homogeneous.

are the two liquids Water and oil and oil droplets are fine dispersed in water, it is an oil-in-water emulsion (O / W emulsion, eg milk). The basic character of an O / W emulsion is characterized by the water. For a water-in-oil emulsion (W / O emulsion, z. As butter) is the reverse principle, the Basic character here by the oil is determined.

Of the Trend away from the noble paleness towards the "healthy, sporty brown skin "is unbroken for years. To achieve this people are putting Their skin of solar radiation, as this is a pigmentation in the sense of melanin formation. The ultraviolet radiation However, sunlight also has a damaging effect on the skin. Besides the acute injury (Sunburn) occur long-term damage like an elevated one Risk of developing skin cancer from excessive exposure to light from the UVB range (wavelength: 280-320 nm). Excessive influence the UVB and UVA radiation (wavelength: 320-400 nm) leads about that out 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 results.

To the Therefore, a range of sunscreen filters have been developed to protect the skin, which can be used in cosmetic preparations. These UVA and UVB filters are in shape in most industrialized countries of positive lists such as Appendix 7 of the German Cosmetics Regulation summarized.

• • 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 have a high weight, which leads to higher energy consumption and higher costs during transport.
• • They have a larger volume, resulting in lower transport capacities during transport.
• • In particular, low-viscosity emulsions are much more expensive to store and transport, since the preparations can "leak".
• • The application concentrations of the ingredients (eg UV filter concentration and thus UV filter performance) are already given to the consumer. An individual adaptation to the conditions at the place of application are no longer possible.

It Therefore, the object of the present invention, the disadvantages of the prior art and a "dry" emulsion and a method of preparation to develop the same.

Although the person skilled in the art such "instant emulsions" known per se DE 102 54 334 and DE 102 54 335 "Dry" emulsions containing sunscreen filters, but these scripts could just as little point the way to the present invention as WO 00/26280, WO 02/32563, WO 02/47624 and WO 02/047620.

One Problem of dried emulsions consists in particular in the fact that during the drying of the emulsion comes to a coalescence of the oil droplets. Coalescing the droplets, no emulsion forms on addition of water.

It Therefore, the object of the present invention, the shortcomings of Prior art to eliminate and develop emulsions which dry easily and re-emulsify after re-addition of water to let.

• a) eine wässrige Phase,
• b) eine Ölphase,
• c) pigmentäre UV-Lichtschutzfilter und
• d) wasserlösliche Polymere,

neben gegebenenfalls weiteren kosmetischen und/oder dermatologischen Wirk-, Hilfs- und Zusatzstoffen, durch Sprühtrocknung, Gefriertrocknung und/oder Walzentrocknung getrocknet wird, sowie durch eine kosmetische Zubereitung, die nach diesem Verfahren hergestellt ist.The object is surprisingly achieved by a process for producing a cosmetic preparation, which comprises containing an O / W emulsion

• a) an aqueous phase,
• b) an oil phase,
• c) pigmentary UV photoprotective filters and
• d) water-soluble polymers,

in addition to optionally further cosmetic and / or dermatological active ingredients, auxiliaries and additives, by spray drying, freeze drying and / or drum drying, and by a cosmetic preparation, which is prepared by this method.

The Preparation prepared by this method is according to the invention.

The Tasks are also solved by using a combination of pigmented UV sunscreen filters and water-soluble Polymers for preparation by spray drying, freeze drying and / or Drum drying of dried re-emulsifiable O / W emulsions.

The inventive method for the preparation of a cosmetic preparation is advantageous according to the invention characterized in that the dried emulsion subsequently in a mixing device with water-soluble and / or volatile Active ingredients, excipients and / or additives is mixed.

The Preparation prepared according to this preparation step is according to the invention.

According to the invention advantageous can the preparation of one or more granulating and / or tablet adjuvants be added.

This is according to the invention Process for the preparation of a preparation which is characterized is that the preparation of the invention after the addition of one or more tablet excipients in one Mixing device are mixed.

The Preparation prepared according to this preparation step is according to the invention.

To the mixing process can According to the invention advantageous in a further process step from the preparation of tablets and / or granules are produced. This is done according to the invention advantageously characterized that the preparation in a press to one or more tablets pressed or granulated by means of suitable granulating become.

The Preparation prepared according to this preparation step is according to the invention.

A produced according to one of the method steps described above Preparation may be advantageous for use as a cosmetic according to the invention with water, which may have a temperature of 20 to 100 ° C, are added.

The Preparation prepared according to this preparation step is according to the invention.

Furthermore It is according to the invention that the user the dried emulsion without further addition of water directly e.g. as a "body powder" applies.

The pigmentary UV photoprotective filter according to the invention become advantageous according to the invention in a concentration of 0.5 to 35% by weight and preferably in a concentration of 2 to 15% by weight, based in each case on the weight of the O / W emulsion before drying or after the re-addition of water used.

According to the invention advantageous embodiments of the present invention are characterized in that as pigmentary UV sunscreen one or more compounds selected from the group of compounds 2,4,6-tris- (biphenyl) -1,3,5-triazine (especially 2,4,6-tribiphenyl-4-yl-1,3,5-triazine); 2,4,6-tris (terphenyl) -1,3,5-triazine be used.

The water-soluble according to the invention Polymers become advantageous according to the invention in a concentration of 1 to 80% by weight and preferably in a concentration of 2 to 50% by weight, based in each case on the weight of the O / W emulsion before drying or after the re-addition of water used.

According to the invention advantageous water-soluble Polymers can According to the invention advantageous from the group of water-soluble or dispersible film formers (for example polyurethanes, dimethicones Copolyol polyacrylates, polyvinyl pyrrolidone vinyl acetates PVP / VA, Polyvinyl pyrrolidones (PVP), polyvinyl alcohols (e.g., Mowiol 18-88) and from the group of hydrocolloids (e.g., agar-agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, Carob kernel flour, starch, Dextrins, polysaccharide N-alkyl urethanes, Inulin carbamates, gelatin, casein, cellulose ethers, hydroxyethyl and propylcellulose derivatives, polysaccharides, polyacrylic and polymethacrylic compounds, Ammonium acryloyldimethyltaurates / vinylpyrrolidone copolymers and ammonium polyacryldimethyltauramides, 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 which are preferred according to the invention are, for example, methylcelluloses, which are referred to as the methyl ethers of cellulose. 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 also generally referred to as methylcelluloses cellulose mixed ethers, in addition to a dominating content of methyl additionally 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl groups. Particularly preferred hydroxypropylmethylcelluloses (HPMC) have an average molar mass M _m <50,000 gmol ^-1 and are known, for example, as Pharmacoat 603, Pharmacoat 606 and Pharmacoat 645 or under the name Metolose 65 SH 50 or Metolose 60 SH 50 in the FA Shin Etsu available. Further preferred hydroxypropylmethylcelluloses are available under the trade name Methocel K100LV from Dow Chemicals or under the trade name Methocel E5 from Colorcon.

Of further preferred are (hydroxypropylmethylcelluloses, for example under the trade name Methocel E4M at Dow Chemical Comp. available.

Also advantageous according to the invention is sodium carboxymethylcellulose, the sodium salt of the glycolic acid ether of cellulose, for which R in structural formula I represents a hydrogen and / or CH 2 -COONa can. Particularly preferred is sodium carboxymethylcellulose, also known as cellulose gum, available under the tradename Natrosol Plus 330 CS from Aqualon.

Further according to the invention advantageous is the use of maltodextrin, preferably with a Dextrose equivalent from 10-30, more preferably with a dextrose equivalent from 15-20. Furthermore advantageous is the use of gum arabic, e.g. under the trade name Spray Gum available. Maltodextrin and gum arabic may be used singly or in admixture be used. According to the invention advantageous is the weight ratio of the raw material mixture of 1:10 to 10: 1 and preferred according to the invention from 2:10 to 10: 2.

According to the invention advantageous is the weight ratio of pigmentary UV light protection filters to water-soluble Polymers of 1:10 to 10: 1 and according to the invention preferably from 3:10 to 10: 3.

It is advantageous according to the invention if the preparation according to the present Invention, further UV filter substances.

Furthermore, the preparation according to the invention can advantageously contain UV sunscreen filter substances based on inorganic pigments. Preferred inorganic pigments are metal oxides and / or other water-insoluble or insoluble metal compounds, in particular oxides of titanium (TiO ₂ ), zinc (ZnO), iron (eg Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon ( SiO ₂ ), manganese (for example MnO), aluminum (Al ₂ O ₃ ), cerium (for example Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides and also the barium sulfate (BaSO ₄ ).

The Pigments can advantageous in the context of the present invention also in the form of a commercial available oily or aqueous predispersions come into use. These predispersions may advantageously dispersants and / or solubilization promoters may be added.

The Pigments can According to the invention advantageous superficial be treated ("coated"), for example a hydrophilic, amphiphilic or hydrophobic character formed should be 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 used in the According to the present invention also contain water.

Inorganic surface coatings for the purposes of the present invention may 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), barium sulfate (BaSO ₄ ) or iron oxide (Fe ₂ O ₃ ). These inorganic surface coatings may be present alone, in combination and / or in combination with organic coating materials.

organic surface coatings For the purposes of the present invention may 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. These organic surface coatings can alone, in combination and / or in combination with inorganic Coating materials occur.

The Titanium dioxide pigments can in both the rutile and anatase crystal modifications and can Advantageously treated superficially in the sense of the present invention ("Coated"), for example a hydrophilic, amphiphilic or hydrophobic character formed should be 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 in According to the present invention also contain water.

described Coated and uncoated titanium dioxides may be used in the context of the present invention Invention also in the form of commercially available oily or aqueous predispersions come into use. These predispersions may advantageously dispersing agents and / or solubilization promoters may be added.

The Titanium dioxides according to the invention are characterized by a primary particle size between 10 nm to 200 nm, with particle sizes of 10 nm to 100 nm being preferred according to the invention are.

in the The meaning of the present invention are particularly preferred titanium dioxides the MT-100 Z and MT-100 TV from Tayca Corporation, Eusolex T-2000 and Eusolex T-AVO from Merck and the titanium dioxide T 805 from Degussa and the iron / titanium mixed oxide titanium dioxide T817 from 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 which are suitable according to the invention are distinguished by a primary particle size of <300 nm and can be obtained from the following companies under the following trade names:

special Preferred zinc oxides in the context of the invention are the Z-Cote HP1 from BASF and the zinc oxide NDM from Haarmann & Reimer.

advantageous further UV filter substances in the context of the present invention are, for example, those mentioned below which are present in the water and / or the oil phase may be present.

Advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalates), 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylates), 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate (INCI: Octocrylene) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamic acid isopentyl ester (isopentyl-4-methoxycinnamate, INCI (to ethoxycarbonylvinyl 4- (2,2) phenoxy) propenyl) -methoxysiloxan / dimethylsiloxane copolymer which is obtainable isoamyl p-Methoxycinnamate), 3- example, under the trade name Parsol ^® SLX from Hoffmann La Roche.

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 ^® 9020th

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 in the context of the present invention are hydroxybenzophenones, which are distinguished 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 attached are bound, can form a 5- or 6-ring and
R ^{3 is} a C ₁ -C ₂₀ -alkyl radical.

und unter dem 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'-hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone), which has the following structure:

and Uvinul A Plus is available from BASF.

• • Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure und ihre Salze, besonders die entsprechenden Natrium-, Kalium- oder Triethanolammonium-Salze, insbesondere das Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure-bis-natriumsalz mit der INCI-Bezeichnung Bisimidazylate (CAS-Nr.: 180898-37-7), welches beispielsweise unter der Handelsbezeichnung Neo Heliopan AP bei Haarmann & Reimer erhältlich ist;
• • Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Triethanolammonium-Salz sowie die Sulfonsäure selbst mit der INCI Bezeichnung Phenylbenzimidazole Sulfonsäure (CAS.-Nr. 27503-81-7), welches beispielsweise unter der Handelsbezeichnung Eusolex 232 bei Merck oder unter Neo Heliopan Hydro bei Haarmann & Reimer erhältlich ist;
• • 1,4-di(2-oxo-10-Sulfo-3-bornylidenmethyl)-Benzol (auch: 3,3'-(1,4-Phenylendimethylene)-bis-(7,7-dimethyl-2-oxo-bicyclo-[2.2.1]hept-1-ylmethan Sulfonsäure) und dessen Salze (besonders die entprechenden 10-Sulfato-verbindungen, insbesondere das entsprechende Natrium-, Kalium- oder Triethanolammonium-Salz), das auch als Benzol-1,4-di(2-oxo-3-bornylidenmethyl-10-sulfonsäure) bezeichnet wird. Benzol-1,4-di(2-oxo-3-bornylidenmethyl-10-sulfonsäure) hat die INCI-Bezeichnung Terephtalidene Dicampher Sulfonsäure (CAS.-Nr.: 90457-82-2) und ist beispielsweise unter dem Handelsnamen Mexoryl SX von der Fa. Chimex erhältlich;
• • 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 further UV filter substances in the context of the present invention are sulfonated, water-soluble UV filters, such as. B .:

• Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, especially the phenylene-1,4 bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate (CAS No .: 180898-37-7), which is available, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;
• Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), which is available, for example, from Trade name Eusolex 232 available from Merck or Neo Heliopan Hydro from Haarmann &Reimer;
• 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene (also: 3,3 '- (1,4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxo) bicyclo [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, in particular the corresponding sodium, potassium or triethanolammonium salt), also known as benzene-1,4 benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) has the INCI name Terephtalidene Dicampher sulfonic acid (CAS.No. : 90457-82-2) and is available, for example, under the trade name Mexoryl SX from Chimex;
• Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and salts thereof.

advantageous UV filter substances in the context of the present invention are further so-called broadband filters, i. Filter substances containing both UV-A as well as absorb UV-B radiation.

An advantageous broadband filter for the purposes of the present invention is also the 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), which is available under the trade name Tinosorb ^® M from CIBA-Chemikalien GmbH.

Favorable Broadband filter according to the present invention is also the 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] 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;
• • Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethylhexyl)-ester;
• • Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone), welches unter der Handelsbezeichnung UVASORB HEB bei Sigma 3V erhältlich ist;
• • 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,
• • Homomenthylsalicylat (INCI: Homosalate) und
• • 2-Ethylhexyl-2-hydroxybenzoat (2-Ethylhexylsalicylat, Octylsalicylat, INCI: Octyl Salicylate).

The other UV filter substances can be oil-soluble or water-soluble. Advantageous oil-soluble filter substances are z. B .:

• 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
• 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 4- (dimethylamino) benzoic acid amyl ester;
• Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;
• Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone), which is available under the trade name UVASORB HEB from Sigma 3V;
• 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 and
• Polymer-bound UV filters,
• Homomenthyl salicylate (INCI: Homosalate) and
• 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylates).

• • Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure-bis-natriumsalz (INCI: Bisimidazylate, Handelsname: Neoheliopan AP),
• • Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone, Handelsname: Uvasorb HEB),
• • 2-(4'-Diethylamino-2'-hydoxybenzoyl)-benzoesäurehexylester (auch: Aminobenzophenon) (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoat, Handelsname: Uvinul A plus),
• • (3Z)-1,7,7-trimethyl-3-(4-methylbenzylidene)bicyclo[2.2.1]heptan-2-one (INCI: 4-Methylbenzylidene Campher, Handelsname: Eusolex 6300),
• • 2-Ethylhexyl-2-cyano-3,3-diphenylacrylat (INCI: Octocrylene, Handelsname: Uvinul N-539),
• • Benzol-1,4-di(2-oxo-3-bornylidenmethyl-10-sulfonsäure) (INCI: Terephtalidene Dicampher Sulfonsäure, Handelsname: Mexoryl SX),
• • 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-phenol (INCI: Drometrizole Trisiloxane, Handelsname: Mexoryl XL). 2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1,3,5-triazin mit der (CAS Nr. 288254-16-0, erhältlich bei 3V Sigma unter der Handelsbezeichnung Uvasorb^® K2A) in gelöster Form.

Particularly advantageous UV filter substances are:

• Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt (INCI: bisimidazylate, trade name: Neoheliopan AP),
• Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone, trade name: Uvasorb HEB),
• • 2- (4'-diethylamino-2'-hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone) (INCI: diethylamino hydroxybenzoyl hexyl benzoate, trade name: Uvinul A plus),
• • (3Z) -1,7,7-trimethyl-3- (4-methylbenzylidenes) bicyclo [2.2.1] heptan-2-one (INCI: 4-methylbenzylidenes camphor, trade name: Eusolex 6300),
• 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: Octocrylene, trade name: Uvinul N-539),
• Benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) (INCI: Terephtalidene dicampher sulfonic acid, trade name: Mexoryl SX),
• 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] propyl] - phenol (INCI: Drometrizole Trisiloxane, trade name: Mexoryl XL). 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine having the (CAS No . 288254-16-0, available from 3V Sigma under the trade name Uvasorb K2A ^®) in dissolved form.

• • 2-Ethylhexyl-4-methoxycinnamat (INCI: Octyl Methoxycinnamat, Handelsname: Parsol MCX),
• • 4-(tert.-Butyl)-4'-methoxydibenzoylmethan (INCI: Butylmethoxydibenzoylmethan, Handelsname: Parsol 1789),
• • Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Triethanolammonium-Salz sowie die Sulfonsäure selbst mit der INCI Bezeichnung Phenylbenzimidazole Sulfonsäure (Handelsname: Eusolex 232).
• • Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure und ihre Salze, besonders die entsprechenden Natrium-, Kalium- oder Triethanolammonium-Salze, insbesondere das Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäure-bis-natriumsalz mit der INCI-Bezeichnung Bisimidazylate (CAS-Nr.: 180898-37-7), welches beispielsweise unter der Handelsbezeichnung Neo Heliopan AP bei Haarmann & Reimer erhältlich ist;
• • 2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (INCI: Aniso Triazin, erhältlich unter dem Handelsnamen Tinosorb S) in gelöster Form,
• • 4,4',4''-(1,3,5-Triazin-2,4,6-triyltriimino)-tris-benzoesäure-tris(2-ethylhexylester) (auch: 2,4,6-Tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazin (INCI: Octyl Triazone), welches von der BASF Aktiengesellschaft unter der Warenbezeichnung UVINUL^® T 150 vertrieben wird) in gelöster Form,
• • Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone, Handelsname: Uvasorb HEB).

Very particularly advantageous UV filter substances in the context of the present invention are:

• 2-ethylhexyl-4-methoxycinnamate (INCI: octyl methoxycinnamate, trade name: Parsol MCX),
• 4- (tert-butyl) -4'-methoxydibenzoylmethane (INCI: butylmethoxydibenzoylmethane, trade name: Parsol 1789),
• Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or its triethanolammonium salt and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (trade name: Eusolex 232).
• Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, especially the phenylene-1,4 bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate (CAS No .: 180898-37-7), which is available, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;
• 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: aniso triazine, available at the trade name Tinosorb S) in dissolved form,
• • 4,4 ', 4''- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) (also: 2,4,6-tris [ anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl Triazone), which is sold by BASF Aktiengesellschaft under the trade name UVINUL T 150 ^®) in dissolved Shape,
• Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone, trade name: Uvasorb HEB).

These additional UV filter substances can According to the invention advantageous in a total concentration of 0.01 to 20% by weight and preferred according to the invention in a total concentration of 0.5 to 10% by weight, respectively based on the total weight of the hydrous preparation in this be included.

The oil phase of preparations according to the invention is chosen favorably from the group of polar lipids with a polarity ≤ 35 mN / m Especially Advantageous lipids in the context of the present invention are all native lipids, such as. Olive oil, Sunflower oil, Soybean oil, Peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grapeseed oil, thistle oil, evening primrose oil, macadamia nut oil, corn oil, avocado oil and the like as well as those listed below.

From The hydrocarbons are especially paraffin oil as well other hydrogenated polyolefins such as hydrogenated polyisobutenes, squalane and squalene to be used advantageously within the meaning of the present invention.

The Content of the lipids is advantageously less than 50 wt .-%, preferably between 1 and 40 wt .-%, particularly preferably between 5 and 20 wt .-%, each based on the total weight of the water-containing Preparation.

If the lipid phase oil-soluble UV filter substances contains it is advantageous the content of the lipid phase less than 80 wt .-% to choose, preferably between 1 and 40 wt .-%, particularly preferably between 5 and 30 wt .-%, each based on the total weight of the hydrous Preparation.

It may optionally be advantageous, although not mandatory is when the oil phase the preparations in the context of the present invention also non-polar Contains lipids.

The aqueous phase of the preparations according to the invention may advantageously contain customary cosmetic auxiliaries, for example alcohols, in particular those of low C number, preferably ethanol and / or isopropanol, diols or polyols of low C number and their ethers, preferably propylene glycol, glycerol, ethylene glycol, propanediol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, polymers , Foam stabilizers, electrolytes, self-tanning and in particular one or more thickening agents, which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, for. As hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.

The inventive preparation can according to the invention a or contain several emulsifiers, where known for the cosmetic emulsions O / W emulsifiers can be used.

According to the invention preferred however, are O / W emulsions that are solid-stabilized and no O / W emulsifiers included.

The cosmetic according to the invention Preparations can as usual be composed. Particularly advantageous in the sense of the present Invention are preparations for the care of the skin: they can the cosmetic sunscreen, furthermore for cleaning or care of the skin and / or the hair and as a make-up product in decorative cosmetics serve. A further advantageous embodiment of the present invention Invention consists in after-sun products.

Corresponding their structure can hydrous cosmetic compositions according to the present Invention, for example be used as skin protection cream, day cream or night cream etc. It may be possible and advantageously, the compositions of the invention as a basis for pharmaceutical To use formulations.

It is advantageous in the context of the present invention, when the water-containing preparations according to the invention be used as a sunscreen. Also, the watery ones preparations according to the invention usable according to the invention as preparations whose principal Purpose is not the protection from sunlight, but still a Contain content of UV protection substances. So z. B. in day creams or Makeup products usually Incorporated UV-A or UV-B filter substances. Also, UV protectors, as well as antioxidants and, if desired, preservatives, effective protection of the preparations themselves against spoilage. Cheap are also cosmetic preparations in the form of a sunscreen available.

to Application are the water-containing, cosmetic according to the invention Preparations in the for Cosmetics usual Applied to the skin and / or hair in sufficient quantity.

The cosmetic preparations according to the invention can contain cosmetic excipients, such as those commonly used in such preparations be used, for. Preservatives, preservatives, Complexing agents, bactericides, perfumes, preventing substances or increasing the foaming, dyes, Pigments that have a coloring Have effect, thickener, moisturizing and / or moisturizing Substances, fillers, the skin feeling improve, fats, oils, Waxes or other usual Ingredients of a cosmetic formulation such as alcohols, polyols, Polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as DMDM hydantoin, which is available, for example, under the trade name Glydant ^™ from Lonza), iodopropyl butylcarbamates (for example those sold under the trade names Glycacil-L, Glycacil -S. From the company. Lonza available and / or Dekaben LMB from Jan Dekker), parabens (ie p-Hydroxybenzoesäurealkylester, such as methyl, ethyl, propyl and / or Butylparaben), phenoxyethanol, ethanol, benzoic acid and the like. Usually, the preservation system according to the invention also advantageously also preservation aids, such as ethylhexylglycerol, glycine soy etc.

Advantageous complexing agents for the purposes of the present invention, for example, EDTA, [S, S] -Ethylendiamindisuccinat (EDDS), which is available, for example, under the trade name Octaquest from the company. Octel, pentasodium ethylenediamine tetramethylene phosphonate, which z. B. under the trade name Dequest 2046 from the company Monsanto is available and / or iminodisuccinic acid, which inter alia from the company. Bayer AG under the trade name Iminodisuccinat VP OC 370 (about 30% solution) and Baypure CX 100 is firmly available.

Especially advantageous preparations are also obtained if, as additional or agents used antioxidants. Included in the invention the preparations advantageously one or more antioxidants. As cheap, but yet optional antioxidants can all be used for cosmetic Applications suitable or common Antioxidants are used.

Especially For the purposes of the present invention, water-soluble antioxidants may be advantageous be used, such as vitamins, eg. As ascorbic acid and their derivatives.

preferred Antioxidants are also vitamin E and its derivatives as well as vitamin A and its derivatives.

The Amount of antioxidants (one or more compounds) in the Preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20 Wt .-%, in particular 0.1 to 10 wt .-%, based on the total weight the hydrous preparation.

Provided Vitamin E and / or derivatives thereof are the antioxidant (s), is advantageous, their respective concentrations from the field from 0.001 to 10% by weight, based on the total weight of the hydrous Formulation, to choose.

Provided Vitamin A or vitamin A derivatives, or carotenes or their derivatives the one or more antioxidants are advantageous, their respective Concentrations from the range of 0.001 to 10 wt .-%, based on the total weight of the hydrous formulation, to choose.

It is particularly advantageous when the cosmetic preparations according to the present Contain cosmetic active ingredients, preferred agents Antioxidants are what protect the skin from oxidative stress protect can.

Further advantageous active ingredients in the context of the present invention natural Active ingredients and / or their derivatives, such as. Alpha-lipoic acid, phytoene, Niacinamide, panthenol, D-biotin, coenzyme Q10, alpha-glucosylrutin, Carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, creatinine, taurine and / or β-alanine and 8-hexadecene-1,16-dicarboxylic acid (Dioic acid, CAS number 20701-68-2; provisional INCI name Octadecendioic acid) and / or licochalcone A.

Licochalcon may also be used advantageously as a component of plant extracts, in particular of aqueous radix Glycyrrhizae inflatae, are used.

It is advantageous according to the invention when the cosmetic preparations 0.001 to 10 wt .-%, in particular 0.05 to 5 wt .-%, especially 0.01 to 2 wt .-% of an extract from Radix Glycyrrhizae inflatae, in each case based on the Total weight of the preparation.

All it is particularly advantageous to start from an extract which under the name Polyol Soluble Licorice Extract PU (INCI name Glycyrrhiza Inflata) can be obtained from the company Maruzen. The extract from Radix Glycyrrhizae inflatae contains about 25% % Licochalcone A.

Inventive formulations, which z. B. known anti-wrinkling agents such as flavone glycosides (especially α-glycosylrutin), Coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for protection against aesthetics unattractive skin changes, as they are z. B. occur during skin aging (such as Dryness, roughness and formation of dry wrinkles, itching, reduced refatting (eg after washing), visible vascular dilations (telangiectasias, Cuperosis), slackness and development of wrinkles and wrinkles, local hyper-, hypo- and false pigmentations (eg age spots), increased susceptibility across from mechanical stress (eg cracking) and the like). Farther Advantageously, they are suitable against the appearance of dry or rough skin.

The Preparations according to the present invention Invention can furthermore advantageously also self-tanning substances such as dihydroxyacetone and / or melanin derivatives in concentrations of 1 wt .-% up to 8 wt .-%, based on the Total weight of the hydrous preparation.

Further advantageously, the compositions according to the present invention may also contain repellents for protection against mosquitoes, ticks and spiders and the like. Advantageous z. N, N-diethyl-3-methylbenzamide (trade name: meta-delphphene, "DEET"), dimethyl phthalate (trade name: Palatinol M, DMP), 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester, and especially 3- (Nn-butyl-N-acetyl-amino) -propionic acid ethyl ester (available under the trade name insect repellent ^® 3535 from Fa. Merck). the repellents may be used as well in combination, both separately.

When Moisturizers are substances or mixtures of substances, which give cosmetic properties the property after application or distributing on the skin surface the moisture release of the Horn layer (also called transepidermal water loss (TEWL)) to reduce and / or to positively influence the hydration of the horny layer.

Advantageous 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, methylpropanediol, biosaccharide gum-1, glycine soya, 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-gellable polysaccharides. Hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, for example, which are filed in the Chemical Abstracts under the registry number 178463-23-5 and z. B. under the name Fucogel ^® 1000 of the company SOLABIA SA is available. Moisturizers can also be used advantageously as anti-wrinkle active ingredients for the protection of cosmetic skin changes, as described, for example, in US Pat. B. occur during skin aging, can be used.

The cosmetic preparations according to the invention may also advantageously, although not necessarily, contain fillers which are e.g. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or enhance a velvety or silky feel on the skin. Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as, for example, tapioca starch, distarch phosphate, aluminum or sodium starch, octenylsuccinate and the like), pigments which have neither chiefly UV filter nor coloring action (such as, for example, US Pat. B. boron nitride etc.) and / or Aerosils ^® (CAS no. 7631-86-9).

The The following examples are intended to illustrate the present invention, without restricting it. All Quantities, percentages and percentages are, unless otherwise stated indicated on the weight and the total amount or on the total weight the preparations.

Emulsion preparations after spray / freeze / drum drying:

Excipient blends (can be combined with all powder examples):

Claims (12)

Process for the preparation of a cosmetic preparation, characterized in that an O / W emulsion comprising a) an aqueous phase, b) an oil phase, c) pigmentary UV light protection filters and d) water-soluble polymers, optionally further cosmetic and / or dermatological active -, auxiliaries and additives, is dried by spray drying, freeze drying and / or drum drying. Cosmetic preparation prepared by a method according to claim 1. Process for the preparation of a cosmetic preparation, 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, excipients and / or additives is mixed. Preparation prepared by a method according to Claim 3. Preparation containing an O / W emulsion after a the claims 2 or 4 and one or more granulating and / or tablet adjuvants. Process for the preparation of a preparation according to claim 5, characterized in that a O / W emulsion according to any one of claims 2 or 4 are mixed with one or more tablet excipients in a mixing device. Preparation prepared by a method according to Claim 6. Process for the preparation of tablets and / or Granules, characterized in that a preparation according to claim 7 pressed in a press to one or more tablets or Granulated by suitable granulation. Preparation prepared by a method according to Claim 8. Process for the preparation of a cosmetic formulation characterized in that a preparation according to one of claims 2, 4, 5, 7 and / or 9 are mixed with water. Cosmetic formulation made after one Method according to claim 10. Process or preparation according to one of the preceding Claims, characterized in that as pigmentary UV sunscreen a or more connections selected from the group of compounds 2,4,6-tris (biphenyl) -1,3,5-triazine; 2,4,6-tris (terphenyl) -1,3,5-triazine.