WO2006034996A1

WO2006034996A1 - Organic micropigments in cosmetic lathers

Info

Publication number: WO2006034996A1
Application number: PCT/EP2005/054776
Authority: WO
Inventors: Kerstin Skubsch; Claudia Mundt; Anja Eitrich
Original assignee: Beiersdorf Ag
Priority date: 2004-09-27
Filing date: 2005-09-23
Publication date: 2006-04-06
Also published as: DE102004047287A1

Abstract

The invention relates to foam-forming or foamable cosmetic preparations containing at least one organic micropigment.

Description

Beiersdorf Aktiengesellschaft Hamburg

description

Organic micropigments in cosmetic foams

The present invention relates to foam-like or foamable cosmetic preparations containing organic micropigments.

Foams or foam-like preparations belong to the disperse systems.

By far the most important and well known disperse system are emulsions. Emulsions are two- or multi-phase systems of two or more liquids which are not or not very soluble in one another. The liquids (pure or as solutions) are present in an emulsion in a more or less fine distribution, which is generally only limited stability.

Foams are structures of gas-filled, spherical or polyhedron-shaped cells, which are bounded by liquid, semi-liquid, highly viscous or solid cell webs. The cell barriers, connected by so-called nodal points, form a coherent framework. The foam lamellae (closed-cell foam) stretch between the cell bridges. If the foam lamellae are destroyed or flow back into the cell ridges at the end of foaming, an open-celled foam is obtained. Foams are also thermodynamically unstable because surface energy can be obtained by reducing the surface area. The stability and thus the existence of a foam is therefore dependent on how far it succeeds in preventing its self-destruction.

Cosmetic foams are typically dispersed systems of liquids and gases, where the liquid is the dispersant and the gas is the dispersed substance. Foams made from low-viscosity liquids are temporarily stabilized by surface-active substances (surfactants, foam stabilizers). Such surfactant foams have a strong adsorptivity due to their large internal surface area for example, is used in cleaning and washing operations. Accordingly, cosmetic foams find particular use in the areas of cleaning, for example as shaving cream, and hair care use.

To generate foam, gas is blown into suitable liquids, or foaming is achieved by vigorously beating, shaking, splashing or stirring the liquid in the gas atmosphere concerned, provided that the liquids contain suitable surfactants or other surfactants (so-called foaming agents) Apart from interfacial activity, they also have some film-forming ability.

Cosmetic foams have the advantage over other cosmetic preparations that they allow a fine distribution of active ingredients on the skin. However, cosmetic foams are usually only to be achieved by using special surfactants which, moreover, are often less tolerated by the skin.

A disadvantage of the prior art is that such foams are not very stable, which is why they usually coincide within about 24 hours. A requirement of cosmetic preparations, however, is that they have as many years of stability as possible. This problem is generally taken into account that the consumer generates the actual foam itself when using a suitable spray system itself, including, for example, spray cans can be used, in which a liquefied compressed gas serves as a propellant gas. When the pressure valve is opened, the propellant-liquid mixture escapes through a fine nozzle, the propellant evaporates and leaves a foam.

Foaming cosmetic preparations are also known per se. They are first applied in liquid form from an aerosol container on the skin and develop after a short delay only there under the influence of the contained Nachschäum- means the actual foam, such as a shaving cream. Post-foaming preparations are often in special embodiments such as post-foaming shaving gels or the like. The state of the art also knows cosmetic preparations which are foamed during the preparation and in this case have a sufficiently high stability to be packed, stored and marketed in the usual way (see, for example, DE-100 63 340-A1 , DE-100 63 341-A1 and DE-100 63 342-A1).

A disadvantage of the preparations of the prior art, however, is often the quality of the foam, ie the foam is soft, coarse bubble and after removal from the container only slightly stable. Even foamable cosmetic emulsions (so-called "aerosol foams") can not be formulated or technically produced according to the prior art without the use of special surfactants, in particular systems _A based on conventional emulsifiers with the addition of propellant only aqueous-moist foams that break quickly after application.

The object of the present invention was therefore to enrich the state of the art and to provide cosmetic self-foaming and / or foam-like preparations which do not have the disadvantages of the prior art.

Cosmetic foams which are used in the field of UV light protection have the disadvantage that they are not particularly waterproof and can be quickly removed from the skin when bathing. Cosmetic sunscreen products are mainly used on the beach or swimming pool by consumers. The alternating bath of sunbathing and water bathing has always been one of the favorite leisure activities of the people.

It was therefore a further object of the present invention to develop a particularly water-resistant, foamed or foamable cosmetic UV light protection preparation.

Many cosmetic sunscreen products have a certain stickiness, which regularly leads to unwanted sand deposits on the skin when used on the beach. This phenomenon occurs in particular in waterproof UV light protection preparations.

Object of the present invention was therefore to develop sand-repellent, foamable or foamed cosmetic sunscreen preparations. It is a fundamental problem of foamed or foamable cosmetic preparations that it is extremely difficult to incorporate particulate components stable in storage and temperature. In particular, larger amounts of particulate matter, such as those required for sunscreens based on pigmentary filters in order to ensure adequate UV protection, can hardly be produced according to the prior art.

The advantages of micropigments as UV filter substance in cosmetic preparations are mainly due to the fact that the pigments, in contrast to soluble / liquid organic sunscreen filters, are physically and chemically very stable. They are not prone to decomposition or photoreactions even with strong UV radiation. Due to the fact that the pigments are solids, there is no risk of excessive penetration of the filters into the skin. The occurrence of allergic reactions is excluded.

The object of the present invention was therefore to eliminate the disadvantages of the prior art and to develop stable cosmetic sunscreen formulations with a high sun protection factor based on foams. When applied to the skin, the formulations should have a stable absorption spectrum over a longer period of use with a balanced UV-A / UV-B absorption balance.

The tasks are solved by surprise

• Look m shaped, or foamable cosmetic preparations containing one or more organic micropigments, • the use of organic micropigments for foam reinforcement and

Foam stabilization of self-foaming, foamy, post-foaming or foamable cosmetic preparations,

The use of organic micropigments to increase the water resistance of self-foaming, foam-like, post-foaming or foamable cosmetic preparations.

Within the scope of the present disclosure, "inventive" means both the preparations according to the invention and also preparations which are used according to the invention. It is advantageous according to the invention if the organic micropigments have an average particle size of from 10 to 500 nm.

The particle size of the UV sunscreen filter pigments was determined by means of

Scanning electron microscopy (SEM) determined.

According to the invention, the organic micropigments according to the invention can advantageously be present in an aqueous dispersion. Examples of dispersing aids which are advantageous according to the invention are C8-C16-alkylpolyglucoside and / or amphiphilic polymers, as described in EP 1093796 B1.

For the purposes of the present invention, "self-foaming", "milled", "post-foaming" or "foamable" is to be understood as meaning that the gas bubbles are (randomly) distributed in one (or more) liquid phase (s), the Preparations macroscopically do not necessarily have to have the appearance of a foam. Cosmetic preparations in the context of the present invention (hereinafter also referred to as foams for the sake of simplicity) may be, for. B. represent macroscopically visible dispersed systems of dispersed gases in liquids. However, the foam character can also be visible only under a (light) microscope, for example. In addition, foams according to the present invention - especially if the gas bubbles are too small to be detected under a light microscope - also recognizable by the strong volume increase of the system.

For the first time, a rich, compact cream mousse ("mousse") is made available by the invention, which is distinguished by a long storage life and by an extraordinarily high stability and a compact appearance.Compositional compositions of the invention develop during their production, for example during stirring or according to the invention, fine-bleached, rich foams of outstanding cosmetic elegance are obtainable According to the invention, particularly well-tolerated skin-friendly preparations are obtainable, it being possible to distribute valuable ingredients particularly well on the skin. For the purposes of the present invention, "bubbles" mean the gas bubbles, "bubble size" is accordingly to be understood as the diameter of the gas bubbles.

This effect can very well be illustrated by a microscopic foam examination. The aim of this study is the microscopic determination of the number and size of bubbles in cosmetic products.

A microscopic foam investigation can for example be carried out as if a constant temperature of 21 ⁰ C follows: • From the cosmetic to be tested preparation is (for example, top, middle, below.) At three different locations each taken a sample using a spatula from the container (corresponding to three samples per preparation). (Aerosol foams are sprayed into a reservoir or pulp and samples are drawn from the reservoir.)

• 9 mg ± 0.5 mg on slides. • Cover the sample with a cover glass

• Before the actual recording, place a weight of 20 g on the slide with cover glass for 15 sec.

• Subsequently, three images are taken of each sample, with the area under investigation being 6.22 mm x 4.66 mm = 28.11 mm ² . The microscope is set to 125x magnification and the sample is illuminated in transmitted light (digital camera Polaroid

DMC and image analysis program KS400).

Advantageous preparations according to the present invention have an average blister size of 0.005 to 0.5 mm ² , advantageously 0.005 to 0.2 mm ² , particularly advantageously 0.005 to 0.1 mm ² and a blister number of 100 to 4000, advantageous from 500 to 3000, particularly advantageously from 1000 to 3000, in each case based on the examined image section (see above).

Furthermore, it is advantageous according to the invention if the organic micropigments are selected from the group of UV light protection filters.

It is inventively preferred if the particulate organic sunscreen is selected from the group of 2,4,6-tris (biphenyl) -1,3,5-triazine and 2,4,6-tris (terphenyl) -1, 3rd , 5- triazine. Particularly preferred according to the invention is 2,4,6-tribiphenyl-4-yl-1,3,5-triazine.

Advantageous embodiments of the present invention are characterized in that they contain organic micropigments in a concentration of 0.05 to 30% by weight, preferably in a concentration of 0.1 to 10% by weight and more preferably of 0.5 to 5.0 % By weight, based in each case on the total weight of the preparation.

It is advantageous according to the invention if the preparation or use according to the present invention contains 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 the barium sulfate (BaSO ₄ ).

For the purposes of the present invention, the pigments can also be used advantageously in the form of commercially available oily or aqueous predispersions. Dispersants and / or solubilizers may advantageously be added to these pre-dispersions.

According to the invention, the pigments can advantageously be surface-treated ("gecoatef"), it being intended, for example, to form or retain a hydrophilic, amphiphilic or hydrophobic character. This surface treatment can consist in providing the pigments with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by processes known per se. The various surface coatings may also contain water in the sense of the present invention.

Inorganic surface coatings for the purposes of the present invention may be composed 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 J ₆ , sodium metaphosphate (NaPO ₃ J _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 used 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 having an average molecular weight) Chain length from 200 to 350 dimethylsiloxane units and silica gel) or alginic acid. These organic surface coatings can occur alone, in combination and / or in combination with inorganic coating materials.

The titanium dioxide pigments can be present both in the rutile and anatase crystal modifications and can advantageously be surface-treated ("coated") for the purposes of the present invention, with a hydrophilic, amphiphilic or hydrophobic character, for example, being formed or retained This surface treatment may consist in providing the pigments with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by processes known per se.The various surface coatings may also contain water for the purposes of the present invention.

Coated and uncoated titanium dioxides described in the present invention can also be used in the form of commercially available oily or aqueous predispersions. Dispersants and / or solubilizers may advantageously be added to these predispersions.

The titanium dioxides according to the invention are distinguished by a primary particle size of between 10 nm and 200 nm, particle sizes of from 10 nm to 100 nm being preferred according to the invention.

For the purposes of the present invention, particularly preferred titanium dioxides are the MT-100 Z and MT-500 SAS 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:

Particularly 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 sense of the present invention are, for example, those mentioned below which may be present in the water phase and / or the oil phase. 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: isoamyl p-methoxycinnamate), 3- (4- (2,2-bisethoxycarbonylvinyl) phenoxy) propenyl) methoxysiloxane / dimethylsiloxane copolymer, which is available, for example, under the trade name Parsol® SLX from Hoffmann La Roche.

Advantageous UV-A filter substances for the purposes of the present invention are dibenzoyl methane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which has been sold by Givaudan under the trademark Parsol ^® 1789 and sold by Merck under the trade name Eusolex® 9020.

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 are independently hydrogen, CrC ₂ -alkyl, C ₃ -C ₀ cycloalkyl or C ₃ -C ₀ -

Cycloalkenyl, wherein the substituents R ¹ and R ² together with the

Nitrogen atom to which they are attached, can form a 5- or 6-membered ring and

R ^{3 is} a C 1 -C ₂₀ -alkyl radical.

A particularly advantageous hydroxybenzophenone in the context of the present invention is 2- (4'-diethylamino-2 ¹ -hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone), which has the following structure:

and Uvinul A Plus is available from BASF.

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 _J 5'-tetrasulfonic acid and its salts, particularly the corresponding sodium, potassium or triethanolammonium salts, in particular phenylene-1,4 bis (2-benzimidazyl) -3,3'-5 _J 5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate (CAS No .: 180898-37-7), which is sold, 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, under the trade name Eusolex 232 from Merck or under Neo Heliopan Hydro from Haarmann &Reimer;

1, 4-di (2-oxo-10-sulfo-3-bomylidenemethyl) 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), which is also known as benzene-1, Benzo-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 for the purposes of the present invention are also so-called broadband filters, ie filter substances which absorb both UV-A and UV-B radiation. An advantageous broadband filter for the purposes of the present invention is also the 2,2'-methyl-bis (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.

Another advantageous broadband filter in the context of the present invention is the 2- (2H-benzotriazole) -ylH-methyl-eP-methyl-S-ti.SSS-tetramethyl-i-trimethylsilyoxyldisiloxanyl] propyl] -phenol (CAS). No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.

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 di-2-ethylhexyl 4-methoxybenzalmalonate;

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: homosalates) and

• 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylate).

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 ¹ -hydroxybenzoyl) -benzoic acid hexyl ester (also: aminobenzophenone) (INCI: diethylamino hydroxybenzoyl hexyl benzoate, trade name: Uvinul A plus),

• (3Z) -1,7,7-trimethyl-3- (4-niethylbenzylidenes) bicyclo [2.2.1] heptan-2-one (INCI: 4-methylbenzylidenes camphor, trade name: Eusolex 6300), 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-i - [(trimethylsilyl) oxy] disiloxanyl] propyl ] -phenol (INCI: Drometrizole Trisiloxane, trade name: Mexoryl

XL).

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, tradename: Parsol 1789),

Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and also the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (trade name: Eusolex 232).

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 marketed by BASF Aktiengesellschaft under the trade name UVINUL® T 150) in dissolved form .

Dioctylbutylamidotriazone (INCI: diethylhexyl butamido triazone, trade name: Uvasorb HEB).

• Titanium Dioxide Eusolex T-AVO

According to the invention, these additional UV filter substances may advantageously be present in a total concentration of from 0.01 to 30% by weight and, preferably, in a total concentration of from 0.5 to 15% by weight, based in each case on the total weight of the preparation. It is advantageous according to the invention if the preparation according to the invention represents an O / W emulsion.

Particularly advantageous preparations according to the present invention contain an emulsifier system which consists of

A. at least one emulsifier A, selected from the group of wholly, partially or not neutralized, branched and / or unbranched, saturated and / or unsaturated fatty acids having a chain length of 10 to 40 carbon atoms, B. at least one emulsifier B. from the group of polyethoxylated Fettsäu¬ ester with a chain length of 10 to 40 carbon atoms and with a degree of ethoxylation of 5 to 100 and

C. at least one co-emulsifier C, selected from the group of saturated and / or unsaturated, branched and / or unbranched fatty alcohols having a chain length of 10 to 40 carbon atoms.

The emulsifier or emulsifiers A are preferably selected from the group of the fatty acids which are completely or partially mixed with customary alkalis (such as, for example, sodium and / or potassium hydroxide, sodium and / or potassium carbonate and also mono- and / or triethanolamine). are neutralized. For example, stearic acid and stearates, isostearic acid and isostearates, palmitic acid and palmitates as well as myristic acid and myristates are particularly advantageous.

The emulsifier (s) B are preferably selected from the following group: PEG-9 stearate, PEG-8 distearate, PEG-20 stearate, PEG-8 stearate, PEG-8 oleate, PEG-25

Glyceryl trioleate, PEG-40 sorbitan lanolate, PEG-15 glyceryl ricinoleate, PEG-20 glyceryl stearate,

PEG-20 glyceryl isostearate, PEG-20 glyceryl oleate, PEG-20 stearate, PEG-20 methyl glucose sesquistearate, PEG-30 glyceryl isostearate, PEG-20 glyceryl laurate, PEG-30 stearate, PEG-30

Glyceryl stearate, PEG-40 stearate, PEG-30 glyceryl laurate, PEG-50 stearate, PEG-100 stearate, PEG-150 stearate, PEG-150 laurate. For example, polyethoxylated stearic acid esters are particularly advantageous.

The co-emulsifier (s) C according to the invention are preferably selected from the following group: behenyl alcohol (C ₂₂ H ₄₅ OH), cetearyl alcohol [a mixture of Cetyl alcohol (Ci ₆ H ₃₃ OH) and stearyl alcohol (Ci ₈ H ₃₇ OH)], lanolin alcohols (wool wax alcohols, which represent the unsaponifiable alcohol fraction of the wool wax obtained after saponification of wool wax). Cetyl- and cetylstearyl alcohol are particularly preferred.

It is advantageous according to the invention to choose the weight ratios of emulsifier A to emulsifier B to coemulsifier C (A: B: C) such as a: b: c, where a, b and c independently of one another are rational numbers from 1 to 5, preferably from 1 to 3 can represent. Particularly preferred is a weight ratio of about 1: 1: 1.

It is advantageous for the purposes of the present invention, the total amount of the emulsifiers A and B and the Coemulgators C from the range of 2 to 20 wt .-%, preferably from 5 to 15 wt .-%, in particular from 7 to 13 parts by weight. %, in each case based on the total weight of the formulation.

It may be advantageous, although not necessary, if the formulations according to the present invention contain further emulsifiers. It is preferable to use those emulsifiers which are suitable for the preparation of W / O emulsions, these being able to be present both individually and in any desired combinations with one another.

For the purposes of the present invention, preference is given to choosing the emulsifier or other emulsifiers from the group of hydrophilic emulsifiers. Particularly preferred according to the invention are mono-, di-, tri-fatty acid esters of sorbitan.

The total amount of the further emulsifiers is advantageously less than 5 wt .-%, based on the total weight of the formulation selected.

The list of other emulsifiers mentioned, which can be used in the context of the present invention, is of course not intended to be limiting.

Particularly advantageous preparations according to the present invention are free from mono- or diglyceryl fatty acid esters. Particular preference is given to preparations according to the invention which contain no glyceryl stearate, glyceryl isostearate, glyceryl diisostearate, glyceryl ceryl oleate, glyceryl palmitate, glyceryl myristate, glyceryl lanolate and / or glyceryl laurate.

The oil phase of the preparations according to the invention is advantageously selected from the group of polar lipids having a polarity <35 mN / m. Particularly advantageous lipids in the context of the present invention are all native lipids, such as. As olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, thistle oil, evening primrose oil, macadamia nut oil, corn oil, avocado oil and the like, and those listed below.

It is very particularly advantageous for the purposes of the present invention to use one or more UV filter substances for foam reinforcement of self-foaming, foam-like, post-foaming or foamable cosmetic preparations, which Butylene glycol caprylates / caprate, C12-15 alkyl benzoates and / or di-CI 2/13 alkyl tartrates.

Of the hydrocarbons, in particular paraffin oil and further hydrogenated poly-olefins such as hydrogenated polyisobutenes, squalane and squalene are to be used advantageously in the context of the present invention.

The content of the lipids is advantageously chosen to be less than 50% by weight, preferably between 1 and 40% by weight, particularly preferably between 5 and 15% by weight, in each case based on the total weight of the foamable preparation.

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

It may optionally be advantageous, although it is not mandatory, if the oil phase of the preparations according to the present invention also contains non-polar lipids.

The aqueous phase of the preparations according to the invention may advantageously comprise customary cosmetic adjuvants, 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 agents, and in particular one or more thickeners, which are advantageously chosen can be selected from the group silicon dioxide, 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 cosmetic preparations according to the invention can be composed as usual. Particularly advantageous in the context of the present invention are preparations for the care of the skin: they can be used for cosmetic sunscreen, for cleaning or care of the skin and / or hair and as a make-up product in decorative cosmetics. A further advantageous embodiment of the present invention is Af ter-Sun products.

According to their structure, cosmetic compositions in the sense of the present invention can be used, for example, as a skin protection cream, day cream or night cream, etc. It may be possible and advantageous to use the compositions according to the invention as a basis for pharmaceutical formulations.

Just as emulsions of liquid and solid consistency are used as cosmetic cleansing lotions or cleansing creams, the preparations according to the invention can also be "cleaning foams" which are used, for example, to remove make-up and / or make-up or as a mild wash foam - if appropriate also for Such cleansing foams can advantageously also be used as so-called rinse-off preparations which are rinsed off the skin after use

The cosmetic preparations according to the invention may also advantageously be present in the form of a foam for the care of the hair or the scalp, in particular a foam for inserting the hair, a foam which is used in hair-drying the hair, a Frisierschaums.

It is also advantageous in the context of the present invention to prepare cosmetic preparations whose main purpose is not the protection from sunlight, but which nevertheless contain a content of UV protective substances. So z. B. in day creams or makeup products usually incorporated UV-A or UV-B filter substances. UV-protective substances, as well as antioxidants and, if desired, preservatives, also represent an effective protection of the preparations themselves against spoilage. Cosmetic preparations which are in the form of a sunscreen agent are also favorable. For use, the cosmetic preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.

The cosmetic compositions according to the invention can be removed, for example, from aerosol retained and thereby foamed. Aerosol container according to the invention are spray devices with a filling of the liquid or mushy substances, which are under the pressure of a propellant (compressed gas or aerosols). Deratige containers can be equipped with valves of very different design, which allow the removal of the content as a foam.

Further advantageously, the preparations according to the present invention can be taken from propellant-free, mechanically operated pump atomizers (pump dispensers). Particularly advantageous in the context of the present invention are pump systems which operate without compressed gas, but with a filter which causes special turbulences.

The cosmetic preparations according to the invention may furthermore preferably be taken, for example, from bicameral aerosol containers and applied to the skin. Packaging means which are advantageous according to the invention are containers in which a chamber with a filling of the liquid or mushy preparations is under the pressure of a stationary primary blowing agent located in a second chamber. Such containers may be equipped with valves of very different design, which allow the removal of the contents of the first chamber as an emulsion or gel in any position - even with the valve down -.

An advantageous embodiment Bičan ^® -Aerosolbehälter in which the product is enclosed in a flexible bag made of metal or plastic inside the can.

Foaming compositions according to the invention are non-foamed, ie immediately after they leave an aerosol container, two-phase or multi-phase systems - usually emulsions. They can already be easily triturated, for example in the hands or during application and rubbing on the skin, but also through Stirring or other Aufschäumvorgänge to foams are designed. In addition, it has surprisingly been found that in the use of (secondary) blowing agents, particularly advantageously of blowing agents which are soluble in the oil phase which may be present, that is to say, for example, conventional propane-butane mixtures, the preparations according to the invention are not simply sprayed as aerosol droplets, but develop into fine bubbles, rich foams, as soon as such laden with such (secondary) propellants systems undergo pressure relaxation.

When using hydrocarbons or mixtures thereof with 4 or 5 carbon atoms, in particular isobutane, n-pentane and isopentane, as (secondary) blowing agent, it is possible to delay the self-foaming after leaving the pressure pack.

By evaporating the secondary blowing agent in the applied cosmetic product, the skin is further deprived of heat and obtained a pleasant cooling effect. Such post-foaming preparations are therefore also regarded as advantageous embodiments of the present invention with independent inventive step.

For the purposes of the present invention, pressurized gas containers are in particular cylindrical vessels made of metal (aluminum, tinplate, content <1000 ml), protected or non-splintering glass or plastic (content <220 ml) or splintering glass or plastic (content <150 ml_) in question, in the selection pressure and breaking strength, corrosion resistance, ease of filling, sterilization if necessary, etc., but also esthetic aspects, handiness, printability, etc. play a role. The maximum permissible operating pressure of spray cans made of metal at 50 ⁰ C is 12 bar and the maximum filling volume at this temperature for approximately 90% of the total volume. For glass and plastic cans, lower operating pressure values depend on the size of the tank and the propellant (whether liquefied, compressed or dissolved gas).

Particularly advantageous in the context of the present invention are tinplate, aluminum and glass cans. For corrosion protection reasons, metal cans can be painted inside (silver or gold lacquered), for which purpose all commercially available interior protective lacquers are suitable. Preferred for the purposes of the present invention are polyester, epoxy-phenolic and polyamide-imide coatings. Also foil laminations made of polyethylene (PE), polypropylene (PP) and / or polyethylene terephthalate (PET) inside cans are advantageous, especially for tinplate cans.

The compressed gas containers are usually one or two, but usually three-piece cylindrical, conical or otherwise shaped. If plastics are used as spray container material, they should be stable to chemicals and sterilization temperatures, gas-tight, impact-resistant and stable against internal pressures above 12 bar. In principle suitable for spray container purposes are polyacetals and polyamides.

The internal structure of the spray cans and the valve design are depending on the purpose and the physical nature of the content -. B. whether as a two- or as a three-phase system - very varied and can be determined by the skilled artisan by simple experimentation without inventive step. For suitable embodiments, reference is made to the "Aerosol Technology Handbook of Aersosol Packaging" (Wolfgang Tauscher, Melcher Verlag GmbH Heidelberg / Munich, 1996).

According to the invention advantageous valves may be formed with or without riser. The individual parts of which valves according to the invention are usually constructed preferably consist of the following materials:

Plate: Tinplate: bright, gold or clear lacquered, foil-laminated (PE, PP or PET)

Aluminum: bright, silver or gold lacquered, different lacquer variants, Stoner Mudge version

Seal: natural or synthetic elastomers or thermoplastic (sleeve gaskets, foils laminated with PE or PP) Inner and outer seals, eg. B. from Perbunan, Buna, neoprene, butyl, CLB, LDPE, Viton, EPDM, chlorobutyl, bromobutyl and / or various compounds

Cone: PA, POM, brass and various special materials,

Standard holes (eg: 0.25 to 0.70 mm or 2 x 0.45 to 2 x 1.00 mm), different shank diameters Spring: metal, more preferably V2A, stainless steel; Plastic and also elastomer

Enclosures: Standard and Impact VPH holes, RPT holes or slotted for overhead applications

Materials: z. As polyacetal, PA, PE, POM and the like

Riser: plastic (polymer resin), e.g. PE, PP, PA or polycarbonate

Advantageous spray heads for the purposes of the present invention, for example, foam heads for upright use (can hold vertically) or foam heads for overhead application with one or more channels.

Suitable propellants are the customary "conventional" volatile, liquefied propellant gases, such as, for example, dimethyl ether (DME) and / or linear or branched-chain hydrocarbons having two to five carbon atoms (in particular ethane, propane, butane, isobutane and / or pentane), which can be used alone or mixed with each other.

Also compressed air and other gases under pressure such as air, oxygen, nitrogen, hydrogen, helium, krypton, xenon, radon, argon, nitrous oxide (N ₂ O) and carbon dioxide (CO ₂ ) are advantageous in the context of the present invention as propellants (both individually as in any mixtures with each other).

Of course, the person skilled in the art knows that there are other nontoxic propellant gases which would in principle be suitable for the realization of the present invention in the form of aerosol preparations, but which should nevertheless be dispensed with because of a harmful effect on the environment or other accompanying circumstances, in particular halogenated (fluorine, chlorine, bromine, iodine and / or astate substituted) hydrocarbons such as fluorocarbons and chlorofluorocarbons (CFCs).

For the purposes of the present invention, the gases mentioned can be used individually or in any desired mixtures with one another. Advantageous in the context of the present invention, the volume fraction of propellant gas from the range of 0.1 to 30 vol .-%, based on the total volume of filling material and propellant gas selected (corresponding to a volume fraction of 70 to 99.9 vol .-% of contents) ,

Particularly preferred propellant gas in the context of the present invention is carbon dioxide. Foams obtainable from preparations according to the invention which contain carbon dioxide as one or the active ingredient are particularly advantageous.

Particularly advantageous, fine-creamy and rich foams are obtainable when the preparations according to the invention are foamed with the aid of linear or branched-chain, halogenated or non-halogenated hydrocarbons. Very particularly advantageous foams are obtainable by foaming the novel preparations with carbon dioxide, oxygen, compressed air, helium, krypton, xenon, radon, argon and / or nitrogen (either individually or in any desired mixtures with one another).

The cosmetic preparations according to the invention may contain cosmetic adjuvants, such as are commonly used in such preparations, for. Preservatives, preservatives, complexing agents, bactericides, perfumes, substances for preventing or increasing foaming, dyes, pigments which have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fillers which improve the feel on the skin, fats, oils, Waxes or other common 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, for example, DMDM hydantoin, which is available 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-hydroxy-benzoic acid alkyl esters, such as methyl, ethyl, propyl and / or butylparaben), phenoxyethanol, ethanol, benzoic acid and the like , According to the invention, the preserving system also advantageously also comprises preserving aids, such as, for example, ethylhexylglycerol, glycine soya, etc. Advantageous complexing agents for the purposes of the present invention are, for example, EDTA, [S, S] -ethylenediamine disuccinate (EDDS), which is obtainable, for example, under the trade name Octaquest from the company Octel, pentasodium ethylenediamine tetramethylenephosphonate, which, for example, B. under the trade name Dequest 2046 from the company. Monsanto is available and / or iminodisuccinic, which among other things from the company. Bayer AG under the trade name Iminodisuccinat VP OC 370 (about 30% solution) and Baypure CX 100 is permanently available.

Particularly advantageous preparations are also obtained when antioxidants are used as additives or active substances. According to the invention, the preparations advantageously contain one or more antioxidants. All antioxidants which are suitable or customary for cosmetic applications can be used as inexpensive but nevertheless optional antioxidants.

Particularly advantageous in the context of the present invention, water-soluble Antioxi¬ dantien can be used, such as vitamins, eg. As ascorbic acid and its derivatives.

Further preferred antioxidants are 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% by weight, in particular from 0.1 to 10% by weight, based on the total weight of the preparation.

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

If vitamin A or vitamin A derivatives, or carotenes or derivatives thereof, are the antioxidant (s), it is advantageous if their respective concentrations are in the range from 0.001 to 10% by weight, based on the total weight of the formulation choose. It is particularly advantageous if the cosmetic preparations according to the present invention contain cosmetic active ingredients, preferred active substances being antioxidants which can protect the skin against oxidative stress.

Further advantageous active ingredients in the context of the present invention are natural active substances and / or their derivatives, such as. Alpha-lipoic acid, phytoene, niacinamide, panthenol, D-biotin, coenzyme Q10, alpha-glucosylrutin, camitine, camosine, natural and / or synthetic isoflavonoids, creatine, creatinine, taurine and / or beta-alanine, and 8-hexadecene. 1, 16-dicarboxylic acid (dioic acid, CAS number 20701-68-2, provisional INCI name octadecenedioic acid) and / or licochalcone A, which is characterized by the following structural formula:

Licochalcone can also be used advantageously as a constituent of herbal extracts, in particular of aqueous radix Glycyrrhizae inflatae.

It is advantageous according to the invention if the cosmetic preparations contain 0.001 to 10% by weight, in particular 0.05 to 5% by weight, very particularly 0.01 to 2% by weight of an extract of Radix Glycyrrhizae inflatae, in each case on the total weight of the preparation.

It is particularly advantageous to start from an extract which is obtainable from Maruzen under the name Polyol Soluble Licorice Extract PU (INCI name Glycyrrhiza Inflata). The extract of Radix Glycyrrhizae inflatae contains about 25% licochalcone A.

Erfindunαsαemäße formulations, which z. B. known anti-wrinkle active ingredients such as flavone glycosides (especially α-glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like, are particularly advantageous for protection against aesthetically unattractive skin lesions, as z. Skin aging (such as dryness, roughness, dryness wrinkles, itching, decreased refatting (eg, after washing), visible vascular dilation (telangiectasia, cuperosis), slackness and wrinkle and wrinkle formation, localized hypersensitivity). , Hypo and false pigmentation (eg, age spots), increased susceptibility to mechanical stress (eg, cracking), and the like). Furthermore, they are advantageously suitable against the appearance of dry or rough skin.

The preparations according to the present invention can also advantageously contain self-tanning substances, for example dihydroxyacetone and / or melanin derivatives in concentrations of from 1% by weight to 8% by weight, based on the total weight of the preparation.

Further advantageously, the preparations 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-delphene, "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 from Merck under the tradename Insekt Repellent® 3535.) The repellents can be used either individually or in combination.

Moisturizers are substances or mixtures of substances which give cosmetic preparations the property, after application or distribution on the skin surface, to reduce the moisture release of the hom layer (also called transepidermal water loss (TEWL)) and / or to positively influence the hydration of the initial 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 polymers Moisturizer from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides to use. 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 may advantageously also be used as anti-wrinkle agents for protecting 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. the sensory and cosmetic

Further improve the 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, octenyl succinate, and the like), pigments which have neither primary UV filtering nor coloring action (such as e.g.

Boron nitride etc.) and / or Aerosils ^® (CAS no. 7631-86-9).

The following examples are intended to illustrate the present invention without restricting it. Unless stated otherwise, all amounts, proportions and percentages are based on the weight and the total amount or on the total weight of the preparations.

Examples

To produce the (aerosol) foam, in each case 80-97% by volume of the emulsion (A-G) is foamed with 3-20% by volume of a suitable gas (eg propane / butane, compressed air, nitrogen).

Claims

claims:

Foam-form or foamable cosmetic preparations containing one or more organic micropigments.

2. Use of organic micropigments for foam reinforcement and foam stabilization of self-foaming, foam-like, post-foaming or foamable cosmetic preparations.

3. Use of organic micropigments to increase the water resistance of self-foaming, foam-like, post-foaming or foamable cosmetic preparations.

4. Preparations according to claim 1 or uses according to claim 2 or 3, characterized in that the organic micropigments have an average particle size of up to nm. 10-500 nm

5. Preparations or uses according to one of the preceding claims, characterized in that the organic micropigments are selected from the group of UV light protection filters.

6. Preparations or uses according to one of the preceding claims, characterized in that the particulate organic sunscreen is selected from the group 2,4,6-tris (biphenyl) -1, 3,5-triazine; 2,4,6-tris- (terphenyl) -1, 3,5-triazine.

7. Preparations or uses according to one of the preceding claims, characterized in that it contains organic micropigments in a concentration of 0.05 to 30% by weight, based on the total weight of the preparation.

8. Preparations or uses according to one of the preceding claims, characterized in that the preparations have a mean bubble size of 0.005 to 0.5 mm ² .

9. Preparations or uses according to one of the preceding claims, characterized in that the preparation is an O / W emulsion.